JP2009098588A - PHOTOSENSITIVE COMPOSITION, LAMINATE OBTAINED BY USING THE SAME, METAL-CONTAINING FILM MATERIAL, PROCESS FOR PRODUCING THE SAME - Google Patents

Abstract

【選択図】なしA photosensitive composition having high sensitivity and excellent stability over time, a laminate comprising a polymer layer capable of holding a functional material at a high density using the photosensitive composition, metal particles at a high density, and Provided are a light-shielding material provided with an image-like metal film having excellent adhesion to a support and a method for producing the same.
A photosensitive composition comprising (A) a photopolymerization initiator and (B) a crosslinkable polymer represented by the following general formula (1). In general formula (1), R ^{1 to} R ⁴ represent a hydrogen atom or an alkyl group. A represents a substituent containing an acid group such as a carboxyl group, B represents a substituent containing a partial structure selected from ammonium salts of the carboxyl group and the like, and C represents a substituent containing a crosslinkable group. D is an alkyl group or the like. w, x, y, and z represent the molar ratio of the displayed structural units.

[Selection figure] None

Description

  The present invention relates to a photosensitive composition useful for forming a thin metal film, a polymer layer laminate obtained by using the same, a light shielding material as an application thereof, and a simple method for producing the light shielding material.

In recent years, a metal film material in which a thin metal film is formed in a desired region on a substrate has been used in various fields such as various metal wirings, electrodes, and magnetic materials.
Further, the above metal film material is also used as a photomask. A photomask is an original for transferring a pattern formed on a flat plate to another flat plate using a photolithographic technique. As a conventional photomask, a chrome blank or a glass plate using a photographic light-sensitive material obtained by coating a silver halide emulsion on a glass support has been used.

Chromium blanks are manufactured by polishing a glass, forming a metal thin film by a sputtering method, and further applying a photosensitive resist with a spinner (see, for example, Patent Document 1).
Because of these polishing and sputtering costs, chrome blanks are expensive. In addition, there is a troublesome process of etching chromium, which is unfavorable for the environment because harmful chromium is used.
On the other hand, the problem with glass dry plates is that they are inferior in film strength.

By bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to the base material, bringing an unsaturated compound capable of radical polymerization into contact therewith, and then exposing in a pattern form A metal film material in which a metal film exists in a pattern is formed by forming a graft polymer generation region and reducing the metal ions imparted to the graft polymer generation region or metal ions in the metal salt to precipitate the metal. A manufacturing method is known (see, for example, Patent Document 3).
At this time, in order to form a polymer with high sensitivity, a photosensitive composition obtained by adding a compound having a photopolymerization initiator and a crosslinkable group and, if necessary, a sensitizing dye is used to form the polymer layer. be able to.
As the photopolymerization initiator used in such a photosensitive composition, lophine dimer, oxime ester compound or the like is used. (For example, see Patent Document 4)
Moreover, in order to improve the sensitivity of such a photosensitive composition, a technique using a maleic acid derivative as an ammonium salt is also known (see, for example, Patent Document 5).
However, such photosensitive compounds are often unstable to acids, and in particular, binders such as those described in Patent Document 3 that contain a large amount of carboxylic acid groups are used to improve the ability to adsorb metal ions. There was a problem that it was easy to decompose over time.
Therefore, a light-sensitive film having a lower energy and higher density of metal particles and excellent adhesion to the substrate can be formed, and a photosensitive composition having excellent stability over time is also desired. ing.
Japanese Patent Laid-Open No. 1-154060 JP-A-5-53253 JP 2005-275173 A JP 2006-259557 A JP 2005-141084 A

The present invention has been made in consideration of the problems in the prior art described above, and it is an object of the present invention to achieve the following objects.
That is, the object of the present invention is that it is capable of adsorbing metal ions at high density and has excellent temporal stability that can suppress decomposition of photopolymerization initiators and sensitizing dyes by acid, and is useful for the formation of light-shielding materials. The present invention provides a photosensitive composition and a laminate useful for forming a metal film using the photosensitive composition.
Another object of the present invention is to produce the intermediate layer produced by bringing a photosensitive composition having excellent stability over time into contact with an intermediate layer provided on a support, and applying energy like the image to the composition. A laminate having an image-like polymer layer composed of a polymer directly bonded to the surface, a metal-containing film material in which metal particles are contained in the image-like polymer layer, and such a metal-containing film material An object of the present invention is to provide a production method that can be efficiently formed, and a light-shielding material that is a suitable application of the metal-containing film material.

The above-described problems have been solved by the following metal-containing film material and a manufacturing method thereof.
The configuration of the present invention is as follows.
<1> A photosensitive composition comprising (A) a photopolymerization initiator and (B) a crosslinkable polymer including each structural unit represented by the following general formula (1). object.

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms. An alkyl group is shown.
A represents a substituent having 0 to 10 carbon atoms including a group selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a conjugate base thereof, and B represents an ammonium salt of a carboxyl group and an ammonium salt of a sulfonic acid group. A substituent having a carbon number of 0 to 10 including a partial structure selected from a salt and an ammonium salt of a phosphate group, C represents a substituent including a crosslinkable group, and D is a straight chain of 1 to 20 carbons. A chain or branched alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms is shown.
“w”, “x”, “y”, and “z” are mole fractions of the monomer units constituting each of the displayed structural units, each representing a real number of 0 to 1, each having the relationship shown below. (W + x + y) / (w + x + y + z) represents a real number of 1 or less, (w + x) / (w + x + y) represents a real number of 0.5 to 0.99, and (w) / (w + x) represents a real number of 0.05 to 1. Represents.

<2> The photosensitive composition according to <1>, further comprising a sensitizing dye.
<3> The photosensitive composition according to <1> or <2>, further comprising a polymerizable compound.
<4> A support, an intermediate layer formed using a coupling agent having a polymerizable group or a photoinitiator moiety on the support, and the intermediate layer, <1> to <3> After contacting the photosensitive composition according to any one of the above, the polymer formed by applying energy to the photosensitive composition in an image-like manner and directly bonded to the surface of the intermediate layer And an image-like polymer layer.
<5> A support, an intermediate layer formed using a coupling agent having a polymerizable group or a photoinitiator site on the support, and the intermediate layer, A polymer formed by bringing the photosensitive composition according to claim 3 into contact with the photosensitive composition and then bonding the photosensitive composition directly to the surface of the intermediate layer, which is formed by applying energy to the photosensitive composition in an image-like manner. A metal-containing film material comprising: an image-like polymer layer; and metal particles contained in the image-like polymer layer.
<6> The metal-containing film material according to <5>, wherein the polymer layer has a thickness in a range of 200 nm to 2000 nm.
<7> A light-shielding material using the metal-containing film material according to <5> or <6>.

<8> A step of forming an intermediate layer using a coupling agent having a polymerizable group or a coupling agent having a photoinitiator site on a support, and the intermediate layer according to claim 1 to claim 3. After contacting the photosensitive composition according to any one of the above, an image-like polymer layer composed of a polymer formed by directly applying energy to the photosensitive composition and directly bonding to the surface of the intermediate layer is formed. A method for producing a metal-containing film material, comprising: a step of forming; and a step of applying metal ions to the polymer layer and then reducing the metal ions to precipitate metal particles.

The preferable aspect in the photosensitive composition of this invention is demonstrated below.
That is, in the present invention, the initiator contained in the photosensitive composition containing the polymer represented by the general formula (1) which is a compound having a crosslinkable group is a photocleavable radical polymerization initiator. preferable. This polymerization initiator may be introduced by a coupling agent having a photoinitiator site.
Moreover, it is a preferable aspect that the polymerizable group in the coupling agent having a polymerizable group and the crosslinkable group in the compound having a crosslinkable group are the same functional group.

Furthermore, in this invention, it is a preferable aspect that the coupling agent which has a polymeric group has an acryloyl group or a methacryloyl group.
On the other hand, it is preferable that the compound having a crosslinkable group has an acryloyl group or a methacryloyl group, or a vinyl group or an epoxy group.
In the present invention, it is preferable that the metal particles have absorption in a wavelength region of 365 nm or more.

  In this specification, “image-like” refers to a two-dimensional pattern constituted by the existence region and non-existence region of the polymer layer. For example, when the light shielding material of the present invention is applied to a photomask, the existing region of the polymer layer is a light shielding portion, and the non-existing region is a non-light shielding portion. Here, it is necessary that the light shielding part mainly does not transmit light of 300 to 400 nm. The non-light-shielding part desirably has a transmittance of 300 to 400 nm of 90% or more. Moreover, although the thickness of the thin line | wire of a light-shielding part and a non-light-shielding part needs to be changed with the use of a photomask, it is desirable that it is 150 nm-1 micrometer.

Although the operation of the present invention is not clear, it is estimated as follows.
When the polymer used in the photosensitive composition of the present invention forms a polymer layer due to the presence of a structural unit containing a crosslinkable group C in the general formula, for example, a cup having a polymerizable group bonded to a support. A photosensitive composition containing this polymer is brought into contact with an intermediate layer composed of a coupling agent having a ring agent or a photoinitiator moiety, and energy is imparted to the composition to thereby have a crosslinkable group C in the composition. As the reaction between the partial structures proceeds, the reaction between the compound having a crosslinkable group and the coupling agent having a polymerizable group in the composition also proceeds. In addition, the coupling agent which has a polymeric group reacts from the time of providing on a support body, and couple | bonds with a support body. From these things, the formed polymer layer is excellent in adhesiveness with a support body.
Furthermore, the photosensitive composition of the present invention comprises a structural unit containing an acidic group ammonium salt B in addition to a structural unit containing an acidic group A as shown in the general formula (1). Decomposition of photopolymerization initiators and sensitizing dyes in the photosensitive composition because the acidic protons in the product are replaced with ammonium salts to reduce the acidity of the acidic groups without impairing the ability to adsorb metal ions. It is thought that it can be suppressed.

When a layer including a photopolymerization initiation site introduced by a coupling agent having a photoinitiator site is provided as an intermediate layer, sufficient exposure is performed to generate radicals or cations from the photopolymerization initiator site If this does not occur, adhesion to the support does not occur. Therefore, if the activity of the photopolymerization initiator site is low, long exposure is required and adhesion to the support is delayed. On the other hand, in the present invention, if a radical or a cation is generated in a photosensitive composition containing a photopolymerization initiator and a polymer represented by the general formula (1) having a crosslinkable group C as a partial structure, the crosslinking is performed. Since the functional group and the polymerizable group of the intermediate layer are quickly bonded by copolymerization, a polymer layer having a large film thickness can be formed.
It should be noted that an image-like polymer layer having excellent adhesion to the support is formed by applying energy imagewise.
In addition, as described above, when a polymer layer having a large film thickness is formed, a large amount of functional components can be retained in the polymer layer. Therefore, by retaining metal ions in such a polymer layer, It becomes a polymer layer containing higher-density metal particles, and a light-shielding material having high light-shielding properties can be obtained.

According to the present invention, it is possible to adsorb metal ions at a high density and has excellent temporal stability capable of suppressing decomposition of a photopolymerization initiator, a sensitizing dye, and the like by an acid, and is useful for the formation of a light shielding material. Composition and a laminate useful for forming a metal film using the photosensitive composition can be provided.
According to the present invention, the intermediate layer provided on the support is brought into contact with the photosensitive composition containing a photopolymerization initiator or acidic dye of the photosensitive composition containing an acidic group, which suppresses decomposition of the sensitizing dye. A laminate having an image-like polymer layer formed by applying an image-wise energy to the composition and composed of a polymer directly bonded to the surface of the intermediate layer, and a metal in the image-like polymer layer It is possible to provide a metal-containing film material containing particles, a light-shielding material which is a preferred application thereof, and a production method capable of easily forming the metal-containing film material.

Hereinafter, the present invention will be described in detail.
The photosensitive composition of the present invention comprises (A) a photopolymerization initiator and (B) a crosslinkable polymer constituted by each structural unit represented by the following general formula (1).

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms. An alkyl group is shown.
A represents a substituent having 0 to 10 carbon atoms including a group selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a conjugate base thereof, and B represents an ammonium salt of a carboxyl group and an ammonium salt of a sulfonic acid group. A substituent having a carbon number of 0 to 10 including a partial structure selected from a salt and an ammonium salt of a phosphate group, C represents a substituent including a crosslinkable group, and D is a straight chain of 1 to 20 carbons. C1-C20 straight chain having a chain or branched alkyl group, a C3-C20 cycloalkyl group, a C6-C15 aryl group or a C2-C20 heterocyclic group, or a cyano group Or a branched alkyl group is shown.
w, x, y, and z are mole fractions of the monomer units constituting the displayed structural unit, and represent a real number of 0 to 1, each having the relationship shown below. (W + x + y) / (w + x + y + z) represents a real number of 1 or less, (w + x) / (w + x + y) represents a real number of 0.5 to 0.99, and (w) / (w + x) represents a real number of 0.05 to 1. Represents.
First, (B) the crosslinkable polymer represented by the general formula (1), which is an important component of the present invention, will be described.

<(B) Crosslinkable polymer represented by general formula (1)>
(B) The crosslinkable polymer represented by the general formula (1) (hereinafter, appropriately referred to as a specific crosslinkable polymer) that can be used in the present invention has a structure represented by the general formula (1).

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ may each independently have a hydrogen atom or a linear or branched substituent having 1 to 10 carbon atoms. An alkyl group or a cycloalkyl group having 3 to 10 carbon atoms is shown.
Specific examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, and n-pentyl. Group, isopentyl group, cyclohexyloxymethyl group, methoxymethyl group and the like.
Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclohexylmethyl group.
When these represent an alkyl group, they may further have a substituent. Examples of the substituent that can be introduced include an alkoxy group, an alkylamino group, a hydroxyl group, an aryloxy group, an arylamino group, an aryl group, and a carbonyl group. Group, alkoxycarbonyl group, imino group, alkylene group and the like.
R ¹ , R ² , R ³ , and R ⁴ are preferably a hydrogen atom, a methyl group, or the like.

A (substituent A) represents a substituent having 0 to 10 carbon atoms including a group selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a conjugate base thereof. Group, 2-carboxyethyloxy group.
The structural unit containing the substituent A expresses hydrophilic and soluble functions in the specific crosslinkable polymer according to the present invention, and the content of the structural unit is w which represents a polymerization mole fraction of 35 to 35. A range of 70 is preferable, and a range of 50 to 60 is more preferable.

In general formula (1), B (substituent B) is a C 0-10 substituent containing a partial structure selected from an ammonium salt of a carboxyl group, an ammonium salt of a sulfonic acid group, and an ammonium salt of a phosphoric acid group. Specifically, preferred are a tributylammonium salt of a carboxyl group, a triethylammonium salt of a carboxyl group, a diethylethylbenzylammonium salt of a carboxyl group, and a tributylammonium salt of a 2-carboxyethyloxy group.
The structural unit containing the substituent B suppresses decomposition of the photopolymerization initiator and sensitizing dye in the photosensitive composition by the acidic proton in the specific crosslinkable polymer according to the present invention, and contributes to improvement in sensitivity and stability over time. is doing.
The substituent B may be introduced by copolymerizing a structural unit containing the substituent or by a polymer reaction, or by synthesizing a polymer having the substituent A, adding a predetermined amount of an ammonium salt compound thereto, It can produce | generate by making the carboxyl group which the group A has, a sulfonic acid group, and a phosphoric acid group into an ammonium salt. The content of the substituent B after converting the substituent A to the substituent B can be controlled by the amount of the acid group introduced into the polymer and the amount of the ammonium salt compound added.
Presence of substituent B which is an ammonium salt of such an acid group can be confirmed by NMR.
As content of this structural unit, it is preferable that x showing a polymerization molar fraction is the range of 5-99, and it is more preferable that it is the range of 25-60.

The structural unit containing the substituents A and B expresses a hydrophilic and soluble function in the specific crosslinkable polymer according to the present invention, and the content of the structural unit is w + representing a polymerization mole fraction. x is preferably in the range of 70 to 99, and more preferably in the range of 80 to 95.
In the present invention, the ratio of the substituent A containing an acidic group to the substituent B selected from an ammonium salt of an acid affects the performance, and the relationship between w and x is [(w) / (W + x)] is preferably in the range of a real number from 0.05 to 1, and more preferably, [(w) / (w + x)] is a real number from 0.1 to 0.5.

C (substituent C) represents a substituent containing a crosslinkable group. The crosslinkable group in C and the crosslinkable structural unit having the same are described in detail below.
The structural unit containing the substituent C is useful for forming a polymer directly bonded to the intermediate layer having a polymerizable group when forming the laminate described later in the specific crosslinkable polymer according to the present invention.
As content of this structural unit, it is preferable that y showing a polymerization molar fraction is the range of 1-30, and it is more preferable that it is the range of 5-15. Speaking of the relationship between y and w and x, w, x, and y are preferably in the range where [(w + x) / (w + x + y)] represents a real number of 0.5 to 0.99. More preferably, it is in the range of 6 to 0.95.

D (substituent D) is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms. Indicates a group.
Here, specific examples of the linear or branched alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isobutyl group, An isopentyl group, a neopentyl group, etc. are mentioned.
Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furyl group, furfuryl group, 2-thienyl group, 2-pyrrolyl group, piperidino group, piperidyl group Etc.
The alkyl group, aryl group, and heterocyclic group may further have a substituent. Examples of the substituent that can be introduced include an aryl group, an alkyl group, an alkoxy group, an aryloxy group, an alkylamino group, and an amino group. Hydroxy group, carboxy group, alkoxycarbonyl group, imino group, mercapto group, acyl group, halogen atom and the like.
Among these, D is preferably a benzyl group, a cyclohexyl group, or a butyl group.
The structural unit containing D in the specific crosslinkable polymer according to the present invention has a function of imparting various physical properties according to the purpose to the specific crosslinkable polymer of the present invention, and the content z is from 0 to 99. A real number is represented, and 0-10 are preferable. Describing these relationships, (w + x + y) / (w + x + y + z) represents a real number of 1 or less, and preferably represents a real number of 0.01 to 0.1. When (w + x + y) / (w + x + y + z) represents 1, z is 0, and the specific crosslinkable polymer is a terpolymer.

<Quaternary ammonium salt structure>
In the general formula (1), the substituent on the nitrogen of the quaternary ammonium salt contained in the substituent B is not limited as long as it is a functional group that does not inhibit the polymerization, and a plurality of types of substituents may be used. Good. Preferred examples of the substituent on the nitrogen of the quaternary ammonium salt include an alkyl group and an aryl group which may have a substituent. Examples of the quaternary ammonium salt having such a substituent include tetrabutylammonium salt, tetraethylammonium salt, tetramethylammonium salt, dimethylbenzylammonium salt and the like.

In the specific crosslinkable polymer used in the present invention, the crosslinkable group which the substituent C has may be either a radical polymerizable group or a cationic polymerizable group. The specific crosslinkable polymer is preferably a compound having a high affinity for metal ions when used in a light-shielding material described later. In addition to the crosslinkable group, the substituent A as a metal ion adsorption group And substituent B is required.
Examples of the crosslinkable group include radically polymerizable groups and cationically polymerizable groups as described above, and it is possible to select those having sufficient copolymerizability with the polymerizable group in the intermediate layer described later. desirable. In particular, the polymerizable group in the coupling agent having a polymerizable group and the crosslinkable group in the compound having a crosslinkable group are preferably the same functional group.

As the radical polymerizable group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, and a methacryloylamino group are preferable.
Examples of the cationic polymerizable group include a cyclic ether group (epoxy group, oxetane group, etc.), a vinyl group, a lactone group, an aziridine group, and the like. Among these, a vinyl group or an epoxy group is preferable.
In the present invention, a compound having a radical polymerizable group can be preferably used from the viewpoint of storage stability and sensitivity.

Specific examples of the vinyl compound that is one of the compounds having a cationic polymerizable group include styrene compounds, alkyl vinyl ether compounds, alkenyl vinyl ether compounds, aryl vinyl ether compounds, polyfunctional vinyl compounds, propenyl compounds, isopropenyl compounds, and cationic polymerizable compounds. Examples thereof include nitrogen-containing compounds.
Specific examples of the epoxy compound that is one of the compounds having a cationic polymerizable group include various glycidyl ether type epoxy compounds, alicyclic epoxy compounds, epoxidized vinyl compounds, and the like.

  Further, as the metal ion adsorbing group introduced into the specific crosslinkable polymer in the present invention, carboxyl groups, sulfonic acid groups, and phosphoric acid groups contained in the substituents A and B are effective. In addition to the group, a substituent can be introduced for the purpose of increasing the metal ion adsorption ability of the specific crosslinkable polymer. Examples of such substituents include cyano group, isocyano group, amino group, imino group, hydrazine, imidazole group, imide group, urea group, pyridine group, ammonium group, pyrrolidone group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group. Group, amide group, triazine ring structure, carbamoyl group, hydrazinocarbonyl group, group containing isocyanuric structure, urethane group, nitro group, nitroso group, azo group, diazo group, amidino group, azide group, cyanate group (RO -CN) -containing functional group, hydroxyl group (including phenol), ether group, carbonyl group, peroxycarboxy group, ester group, group containing N-oxide structure, group containing S-oxide structure, N-hydroxy structure Oxygen-containing functional groups such as benzene-containing groups, mercapto groups, sulfide groups, thiols Rare group, thioxy group, sulfoxide group, sulfone group, sulfite group, group containing sulfoximine structure, group containing sulfoxynium salt structure, thiocarboxy group, dithiocarboxy group, sulfoxy group, sulfino group, sulfeno group, oxycarbonyl Group, a sulfur-containing functional group such as a group containing a sulfonate structure, a phosphine group, a phosphino group, a phosphono group, a phosphorus-containing functional group such as a hydroxyphosphoryl group, a group containing a halogen atom such as chlorine, bromine or fluorine, And unsaturated carbon groups such as alkenes, alkynes, and benzene rings. These can be introduced as a substituent into any structural unit described in the general formula (1) constituting the specific crosslinkable polymer.

  The molecular weight of the specific crosslinkable polymer in the present invention is not particularly limited as long as it can be dissolved in a general solvent at the time of coating, and a solid unnecessary substance can be removed by filtration.

  Specific examples of the monomer containing the substituent A or B used for the synthesis of the specific crosslinkable polymer according to the present invention include (meth) acrylic acid or an ammonium salt thereof, itaconic acid or an ammonium salt thereof, and styrene. Sulfonic acid or its ammonium salt, 2-sulfoethyl (meth) acrylate or its ammonium salt, 2-acrylamido-2-methylpropanesulfonic acid or its ammonium salt, phosphooxypolyoxyethylene glycol mono (meth) acrylate or its ammonium salt, etc. Can be mentioned.

The polymer as the specific crosslinkable compound that can be used in the present invention includes a metal ion adsorption group, an ethylene addition polymerizable unsaturated group (polymerizable group) such as a vinyl group, an allyl group, and a (meth) acryl group, an acid group, The polymer is preferably a polymer in which an ammonium salt of an acid group is introduced. This polymer has an ethylene addition polymerizable unsaturated group at least at the terminal or side chain, more preferably has an ethylene addition polymerizable unsaturated group at the side chain, and has no ethylene addition polymerizable unsaturated group at the terminal and side chain. Those having a saturated group are more preferred.
The useful weight average molecular weight of the specific crosslinkable polymer of the present invention is in a range of 500 to 500,000, and a particularly preferable range is 1000 to 50,000.

As a method for synthesizing a polymer compound having a metal ion adsorbing group and a polymerizable group, i) a method of copolymerizing a monomer having a metal ion adsorbing group and a monomer having two or more polymerizable groups, ii) a metal ion A method in which a monomer having an adsorbing group and a monomer having a polymerizable group precursor are copolymerized and then a double bond is introduced by treatment with a base or the like; iii) a polymer having a metal ion adsorbing group and a polymerizable group Examples thereof include a method in which a monomer is reacted to introduce a polymerizable group.
A preferred synthesis method is, from the viewpoint of synthesis suitability, ii) a method of copolymerizing a monomer having a metal ion adsorption group and a monomer having a polymerizable group precursor, and then introducing a polymerizable group by treatment with a base, iii) A method of introducing a polymerizable group by reacting a polymer having a metal ion adsorbing group with a monomer having a polymerizable group. In addition, other substituents useful for the present invention, such as a substituent A containing an acid group or a conjugated salt thereof, or a substituent B containing a partial structure selected from an ammonium salt of an acid group, should be introduced by the same means. Can do.

  In the synthesis method i), examples of the monomer having two or more polymerizable groups copolymerizable with the monomer having a metal ion adsorption group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.

  Moreover, as a monomer which has a polymeric group precursor used for the synthetic | combination method of said ii), 2- (3-chloro- 1-oxopropoxy) ethyl methacrylate [*], and Unexamined-Japanese-Patent No. 2003-335814 are described. Compounds (i-1 to i-60) can be used, and among these, the following compound (i-1) is particularly preferable.

  Furthermore, polymerization is performed by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in the polymer having a metal ion adsorption group used in the synthesis method of iii) above. Examples of the monomer having a polymerizable group used for introducing a group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

  For the method of introducing a polymerizable group by treatment with a base after copolymerizing a monomer having a metal ion adsorption group and a monomer having a polymerizable group precursor in the synthesis method of ii), for example, The method described in JP2003-335814A can be used.

Examples of the polymerization reaction include radical polymerization, cationic polymerization, and anionic polymerization. From the viewpoint of reaction control, radical polymerization or cationic polymerization is preferably used.
The cyano group-containing crosslinkable polymer according to the present invention includes 1) a case where the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain, and 2) a polymerization form forming the polymer main chain. And the synthesis method of the polymerizable group introduced into the side chain is different in the synthesis method.

1) When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain 1-1) An embodiment in which the polymer main chain is formed by cationic polymerization and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization, and 1-2) the polymer main chain is formed by radical polymerization. There is a mode in which the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

1-1) A mode in which polymer main chain formation is performed by cationic polymerization, and a polymerization form of a polymerizable group introduced into a side chain is radical polymerization. In the present invention, polymer main chain formation is performed by cationic polymerization, and a side chain is formed. Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into the radical polymerization is radical polymerization include the following compounds.

-Monomers used to form polymerizable group-containing units As monomers used to form polymerizable group-containing units used in this embodiment, vinyl (meth) acrylate, allyl (meth) acrylate, 4- ( (Meth) acryloylbutane vinyl ether, 2- (meth) acryloylethane vinyl ether, 3- (meth) acryloylpropane vinyl ether, (meth) acryloyloxydiethylene glycol vinyl ether, (meth) acryloyloxytriethylene glycol vinyl ether, (meth) acryloyl 1st ter Pioneer, 1- (meth) acryloyloxy-2-methyl-2-propene, 1- (meth) acryloyloxy-3-methyl-3-butene, 3-methylene-2- (meth) acryloyloxy-norbornane, 4,4′-ethylidene diphenol di (meth) acrylate, methacrolein di (meth) acryloyl acetal, p-((meth) acryloylmethyl) styrene, allyl (meth) acrylate, 2- (bromomethyl) vinyl acrylate, 2- (Hydroxymethyl) allyl acrylate and the like.

Polymerization methods include general cation polymerization methods described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 2-4 (p74) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu, Chapter 7 (p195). Can be used. In the cationic polymerization, proton acids, metal halides, organometallic compounds, organic salts, metal oxides and solid acids, and halogens can be used as initiators. As possible initiators, the use of metal halides and organometallic compounds is preferred.
Specifically, boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, tin bromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, iron chloride, Examples include dichloroethylaluminum, chlorodiethylaluminum, dichloromethylaluminum, chlorodimethylaluminum, trimethylaluminum, trimethylzinc, and methylgrineer.

1-2) A mode in which polymer main chain formation is performed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization In the present invention, polymer main chain formation is performed by radical polymerization, and the side chain Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into is cationic polymerization include the following compounds.

-Monomer used for forming polymerizable group-containing unit The same monomers as those used for forming the polymerizable group-containing unit mentioned in the embodiment 1-1) can be used.

Polymerization methods include general radical polymerization methods described in Experimental Chemistry Course “Polymer Chemistry” Chapter 2-2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu Chapter 5 (p125). Can be used. As the initiator for radical polymerization, a high-temperature initiator that requires heating at 100 ° C. or higher, a normal initiator that starts by heating at 40 to 100 ° C., a redox initiator that starts at a very low temperature, and the like are known. In general, an initiator is preferred from the viewpoint of stability of the initiator and ease of handling of the polymerization reaction.
Usual initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, azovir-2,4-dimethylvaleronitrile.

2) When the polymerization form forming the polymer main chain is the same as the polymerization form of the polymerizable group introduced into the side chain Polymerization form forming the polymer main chain and the polymerization form of the polymerizable group introduced into the side chain Are the same, 2-1) both are cationic polymerization, and 2-2) both are radical polymerization.

2-1) Both are aspects of cationic polymerization In both aspects of cationic polymerization, the monomer used for forming the cyano group-containing unit mentioned in the aspect of 1-1) as a monomer having a metal adsorbing group; The same can be used.
From the viewpoint of preventing gelation during polymerization, a polymer having a metal adsorbing group is synthesized in advance, and then a compound having the polymer and a polymerizable group (hereinafter, referred to as “reactive compound” as appropriate). It is preferable to use a method in which a polymerizable group is introduced.

2-2) Aspect in which both are radical polymerizations In a mode in which both are radical polymerizations, the synthesis method is as follows: i) a method of copolymerizing a monomer having a metal adsorbing group and a monomer having a polymerizable group, ii) A method in which a monomer having a metal adsorbing group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like; iii) a polymer having a metal adsorbing group and a polymerizable group And a method of introducing a double bond (introducing a polymerizable group). From the viewpoint of synthesis suitability, ii) a method of copolymerizing a monomer having a metal-adsorbing group and a monomer having a double bond precursor, and then introducing a double bond by treatment with a base or the like, iii This is a method of introducing a polymerizable group by reacting a polymer having a metal adsorbing group with a monomer having a polymerizable group.

  Examples of the monomer having a polymerizable group used in the synthesis method i) include allyl (meth) acrylate and the following compounds.

  Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic group having a polymerizable group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. This is a leaving group, and the elimination reaction referred to here is one in which C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Further, in the synthesis method of ii), in order to convert the double bond precursor into a double bond, as shown below, a method for removing the leaving groups represented by B and C by elimination reaction, That is, a reaction in which C is extracted by the action of a base and B is eliminated is used.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

In the synthesis method of iii), the monomer having a polymerizable group to be reacted with the polymer having a metal-adsorptive group varies depending on the kind of the reactive group in the polymer having a metal-adsorptive group. Monomers having groups can be used.
That is, (reactive group of polymer, functional group of monomer) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide), (hydroxyl group) , Carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, benzyl halide) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group) and the like.
Specifically, the following monomers can be used.

In addition, the metal-adsorptive group-containing crosslinkable polymer in the present invention is a part selected from a metal-adsorptive group-containing unit, a polymerizable group-containing unit, a unit containing the aforementioned acid group or its conjugated salt, or an ammonium salt of an acid group In addition to the unit having the structure, other units may be included. As the monomer used to form the other unit, any monomer can be used as long as it does not impair the effects of the present invention.
However, when the polymerizable group is introduced by reacting with the polymer as described above, a small amount of reactive portion remains when it is difficult to introduce 100%, so this becomes the third unit. There is a possibility.
Specifically, when the polymer main chain is formed by radical polymerization, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Unsubstituted (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, Halogen-substituted (meth) acrylic esters such as 2-chloroethyl (meth) acrylate, ammonium group-substituted (meth) acrylic esters such as 2- (meth) acryloyloxyethyltrimethylammonium chloride, butyl (meth) acrylamide, Iso (Meth) acrylamides such as propyl (meth) acrylamide, octyl (meth) acrylamide, dimethyl (meth) acrylamide, styrenes such as styrene, vinylbenzoic acid, p-vinylbenzylammonium chloride, N-vinylcarbazole, vinyl acetate, Vinyl compounds such as N-vinylacetamide and N-vinylcaprolactam, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2 -Hydroxyethyl (meth) acrylate etc. can be used.
Moreover, the macromonomer obtained using the monomer of the said description can also be used.

  When the polymer main chain is formed by cationic polymerization, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol vinyl ether, di (ethylene glycol) vinyl ether, 1,4-butanediol vinyl ether, 2-chloroethyl vinyl ether, 2 -Vinyl ethers such as ethylhexyl vinyl ether, vinyl acetate, 2-vinyloxytetrahydropyran, vinyl benzoate, vinyl butyrate, styrenes such as styrene, p-chlorostyrene, p-methoxystyrene, allyl alcohol, 4-hydroxy-1- Terminal ethylenes such as butene can be used.

  The molecular weight (Mw) of the metal-adsorptive group-containing crosslinkable polymer in the present invention is preferably 3000 to 200,000, more preferably 4000 to 100,000.

Although the specific example of the specific crosslinkable polymer in this invention is shown below, it is not limited to these.
In addition, as for the weight average molecular weight of these specific examples, all are the range of 3000-100000.

[Method of introducing ammonium salt]
In the synthesis of the polymer of the general formula (1) in the present invention, the method for introducing the ammonium salt is not particularly limited, but after synthesizing the specific crosslinkable polymer not containing the ammonium salt, A method of replacing the proton with an ammonium salt is preferably used.
As a method of replacing the proton of the metal adsorbing group with an ammonium salt,
1) Method of adding a quaternary ammonium salt to the solution of the specific crosslinkable polymer not containing an ammonium salt 2) Adding a metal hydroxide or the like to the solution of the specific crosslinkable polymer not containing an ammonium salt, A method of adding a quaternary ammonium salt after replacing the proton of the metal-adsorbing group with a metal ion
Etc.

Especially, the method of the method of adding a quaternary ammonium salt with respect to the solution of the said specific crosslinkable polymer which does not contain an ammonium salt is preferable. When using the method of adding a quaternary ammonium salt to the solution of the specific crosslinkable polymer not containing an ammonium salt, the quaternary ammonium salt used is said to improve the addition rate of the reaction by neutralization. From the viewpoint, it is preferable to use quaternary ammonium hydroxide.
In the method of adding a metal hydroxide or the like to the solution of the specific crosslinkable polymer not containing an ammonium salt, replacing the proton of the metal adsorbing group with a metal ion, and then adding a quaternary ammonium salt, The metal compound is not particularly limited, and a basic metal hydroxide such as sodium hydroxide, potassium hydroxide or magnesium hydroxide is preferably used.
Moreover, you may use an ion exchange resin as needed for the purpose of improving the substitution rate of ammonium salt.
The polymer obtained by ammonium substitution of the specific crosslinkable polymer is not particularly limited as long as it satisfies the conditions of the specific crosslinkable polymer. For example, the following compounds are preferably used.

It is preferable that 30-99 mass% is contained in the photosensitive composition of this invention, and, as for the crosslinkable compound in this invention, it is more preferable that 50-90 mass% is contained.
Moreover, these (B) specific crosslinkable polymers may be used individually by 1 type, and may use 2 or more types together.

<(A) Polymerization initiator>
The photosensitive composition of the present invention contains a polymerization initiator.
Preferred polymerization initiators that can be used in the present invention include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, and (e) hexaarylbiimidazoles. Compounds, (f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, and the like. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones (a) Aromatic ketones preferred as the polymerization initiator used in the present invention include "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY" P. Fouassier, J. et al. F. Examples thereof include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following compounds are mentioned.

Among them, particularly preferred examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, such as the following compounds: Is mentioned.

  Examples of the α-substituted benzoin compounds described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example, the following compounds.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-181345 include the following compounds.

  Examples of the α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, such as the following compounds.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  The acylphosphine sulfide described in JP-B-2-9597, for example, the following compounds may be mentioned.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium Salt Compound As the polymerization initiator (b) preferable as the polymerization initiator used in the present invention, compounds represented by the following general formulas (1) to (3) may be mentioned.

In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In the general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of onium salts that can be suitably used in the present invention include paragraph numbers [0030] to [0033] of JP-A No. 2001-133969 and paragraph numbers [0096] to [0101 of JP-A No. 2001-92127. And those described in paragraph numbers [0015] to [0046] of JP-A-2001-343742.

  The onium salt used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. Thus, by setting the absorption wavelength in the ultraviolet region, such a photosensitive composition can be handled under white light.

(C) Organic peroxide Preferred as the polymerization initiator used in the present invention (c) Organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5. -Trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutylhydroperoxide, cumene hydroperoxide, diisopropylbenzenehydride Loperoxide, parameter hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl Cumyl peroxide, dicumyl peroxide, bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-xanoyl peroxide, peroxy Succinic oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate Nate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxyneodecanoate, tarsha Tributyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t -Butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3, 3'4, 4 -Tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxy) Carbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate), and the like.

  Among them, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4 4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylper) Peroxyesters such as (oxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred.

(D) Thio compound As a preferable (d) thio compound as a polymerization initiator used by this invention, the compound which has a structure shown by following General formula (4) is mentioned.

In the general formula (4), R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, and R ²⁷ represents a hydrogen atom or an alkyl group. R ²⁶ and R ²⁷ represent a group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may be bonded to each other and contain a hetero atom selected from oxygen, sulfur and nitrogen atoms.
As an alkyl group in the said General formula (4), a C1-C4 thing is preferable. The aryl group is preferably one having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group, and the substituted aryl group includes a halogen atom such as a chlorine atom, a methyl group as described above. And those substituted with an alkoxy group such as methoxy group and ethoxy group. R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compounds (e) Hexaarylbiimidazole compounds preferred as the polymerization initiator used in the present invention include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2 , 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra Phenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetrapheny Biimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5 , 5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.

(F) Ketooxime ester compound (f) The ketoxime ester compound preferable as a polymerization initiator used in the present invention includes 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.

(G) Borate Compound As an example of the (g) borate compound preferable as the polymerization initiator used in the present invention, a compound represented by the following general formula (5) can be given.

In the general formula (5), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. An alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are bonded to form a cyclic structure. May be. However, at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group. (Z ⁵ ) ⁺ represents an alkali metal cation or a quaternary ammonium cation.
Examples of the alkyl group for R ^{28 to} R ³¹ include straight-chain, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. The substituted alkyl group includes an alkyl group as described above, a halogen atom (for example, —Cl, —Br, etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, —COOR ³² (here R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —OCOR ³³ or —OR ³⁴ (where R ³³ and R ³⁴ are alkyl groups having 1 to 14 carbon atoms, or aryl. And a group having a substituent represented by the following formula.

Here, R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.
The aryl group of R ^{28 to} R ³¹ includes 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group for R ^{28 to} R ³¹ include linear, branched and cyclic groups having 2 to 18 carbon atoms. Examples of the substituent of the substituted alkenyl group include those listed as the substituents of the substituted alkyl group. Examples of the alkynyl group of R ^{28 to} R ³¹ include straight chain or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included. In addition, examples of the heterocyclic group of R ^{28 to} R ³¹ include a 5-membered ring or more, preferably a 5- to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. Compounds and those shown below are mentioned.

(H) Azinium Compound Preferred examples of the azinium salt compound used as the polymerization initiator used in the present invention include JP-A Nos. 63-138345, 63-142345, and 63-142346. And compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Metallocene compound (i) Metallocene compound preferred as a polymerization initiator used in the present invention is disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, Examples thereof include titanocene compounds described in JP-A-2-249 and JP-A-2-4705, and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl] ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bi [2,6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-chloro Benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium and the like.

(J) Active ester compound Preferred as the polymerization initiator used in the present invention (j) is an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59. And active sulfonates described in JP-A-174831.

(K) Compound having carbon halogen bond Preferred compounds (k) having a carbon halogen bond as the polymerization initiator used in the present invention include compounds represented by the following general formulas (6) to (12). be able to.

In the general formula (6), X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ . Here, R ³⁸ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³⁷ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

In the general formula (7), R ³⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group, X ³ is a halogen atom, and n is an integer of 1 to 3.

In the general formula (8), R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) — or —C (═S). - or -SO ₂ - is.

(R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, R ⁴⁴ is the same as R ³⁸ in the general formula (6), and X ³ is A halogen atom, and m is 1 or 2.)

In the general formula (9), R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1 2 or 3.

A carbonylmethylene heterocyclic compound having a general formula (10) and a trihalogenomethyl group, wherein L ⁷ is a hydrogen atom or a substitution of the formula: CO— (R ⁴⁷ ) q (C (X ⁴ ) ₃ ) r Q ² is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or an N—R group, and M ⁴ is a substituted or unsubstituted alkylene. Or an alkenylene group, or a 1,2-arylene group, R ⁴⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group, and R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group. And X ⁴ is a chlorine, bromine or iodine atom, q = 0 and r = 1, or q = 1 and r = 1 or 2. ).

General formula (11) is a 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative, wherein X ⁵ is a halogen atom, t is an integer of 1 to 3, and s is 1 to 1 4 of an integer, R ⁴⁹ is a hydrogen atom or a CH _3-t X ⁵ _t group, R ⁵⁰ represents an s-valent optionally substituted unsaturated organic group.

General formula (12) is a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative, wherein X ⁶ is a halogen atom, v is an integer of 1 to 3, and u is 1 to 1 4 of an integer, R ⁵¹ is a hydrogen atom or a CH _3-v X ⁶ _v group, R ⁵² represents an unsaturated organic group which may be substituted for u-valent.

  Specific examples of such a compound having a carbon-halogen bond include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), such as 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6 Bis (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho). -1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-to Chloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like.

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), such as 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4 , 6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. Can do. Furthermore, for example, the following compounds described in JP-A-62-258241 can be exemplified.

  Furthermore, for example, the following compounds described in JP-A-5-281728 can be exemplified.

  Alternatively, M. P. Hutt, E .; F. Elslager and L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Chemistry”, Volume 7 (No. 3) by Herbel, page 511 et seq. (1970) Examples of the group include the following compounds.

In addition, compounds such as those described in German Patent 2,641,100, such as 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3 4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone, compounds described in German Patent No. 3333450, compounds described in German Patent No. 3021590, or described in German Patent No. 3021599 A compound group, etc. can be mentioned.
Specific aromatic sulfonium salts described in JP-A No. 2001-92127, JP-A No. 2002-148790 and JP-A No. 20022482 previously proposed by the applicant of the present application can also be mentioned as preferable polymerization initiators. .
More preferable examples of the polymerization initiator used in the polymerizable composition of the present invention include (a) aromatic ketones, (b) aromatic onium salts, and (c) organic peroxides among the aforementioned polymerization initiators. , (E) hexaarylbiimidazole, (i) metallocene compound, (k) a compound having a carbon halogen bond, more preferably (e) hexaarylbiimidazole and (i) metallocene compound. From the viewpoint of the reactivity between the crosslinkable polymer and the starting radical species generated from the radical initiator, titanocenes or lophine dimers are preferred.
In the present invention, (A) the polymerization initiator may be used alone or in combination of two or more.
The (A) polymerization initiator in the photosensitive composition of the present invention is preferably added in an amount of 1 to 30% by mass, more preferably 3 to 20% by mass in the total solid content.

In the photosensitive composition of the present invention, in addition to (A) the polymerization initiator and (B) the specific crosslinkable polymer, other components can be used in combination depending on the purpose.
<Sensitizing dye>
The photosensitive composition of the present invention preferably contains a sensitizing dye from the viewpoint of improving sensitivity.
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034. Preferable specific examples include the following compounds.

  Cationic dyes described in JP-A-62-143044. Preferable specific examples include the following compounds.

  Quinoxalinium salts described in JP-B-59-24147. Preferable specific examples include the following compounds.

  New methylene blue compounds described in JP-A 64-33104. Preferable specific examples include the following compounds.

  Anthraquinones described in JP-A No. 64-56767. Preferable specific examples include the following compounds.

  Benzoxanthene dyes described in JP-A-2-17714, acridines described in JP-A-2-226148 and JP-A-2-226149. Preferable specific examples include the following compounds.

  The pyrylium salts described in Japanese Patent Publication No. 40-28499. Preferable specific examples include the following compounds.

  Cyanines described in JP-B-46-42363. Preferable specific examples include the following compounds.

  A benzofuran dye described in JP-A-2-63053. Preferable specific examples include the following compounds.

  Conjugated ketone dyes described in JP-A-2-85858 and JP-A-2-216154. Preferable specific examples include the following compounds.

  A dye described in JP-A No. 57-10605 and an azocinnamylidene derivative described in JP-B-2-30321. Preferable specific examples include the following compounds.

  Cyanine dyes described in JP-A-1-287105. Preferable specific examples include the following compounds.

  Xanthene dyes described in JP-A-62-31844, JP-A-62-31848, and JP-A-62-143043. Preferable specific examples include the following compounds.

  Aminostyryl ketone described in JP-B-59-28325. Preferable specific examples include the following compounds.

A dye represented by the following general formulas (13) to (15) described in JP-A-2-179634.

In general formulas (13) to (15), A ³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl or aryl-substituted nitrogen atom or a dialkyl-substituted carbon atom, and Y ² represents hydrogen Represents an atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group, R ⁵³ and R ⁵⁴ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or as a _{^{substituent, -OR 55, - (CH 2}} CH 2 O) w -R 55, halogen atom (F, Cl, Br, I ), and substitution of 1 to 18 carbon atoms and having a group represented by the following formula An alkyl group (wherein R ⁵⁵ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, B ¹ represents a dialkylamino group, a hydroxyl group, an acyloxy group, a halogen atom or a nitro group. W is an integer of 0 to 4) The It is.

A merocyanine dye represented by the following general formula (16) described in JP-A-2-244050.

In the general formula (16), R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ⁴ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom. X ⁷ represents a nonmetallic atom group necessary for forming a nitrogen-containing hetero five-membered ring. Y ³ represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z ⁷ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, and an acyl group, or an alkoxycarbonyl group, and Y ³ They may be bonded to each other to form a ring. Preferable specific examples include the following compounds.

  A merocyanine dye represented by the following general formula (17) described in JP-B-59-28326.

In the general formula (17), R ⁵⁸ and R ⁵⁹ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and they may be the same or different from each other. X ⁸ represents a substituent having a Hammett's sigma (σ) value in the range of −0.9 to +0.5.

  A merocyanine dye represented by the following general formula (18) described in JP-A-59-89303.

In general formula (18), R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ⁹ represents a substituent having a Hammett sigma (σ) value in the range of −0.9 to +0.5. Y ⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group. Preferable specific examples include the compounds shown below.

A merocyanine dye represented by the following general formula (19) described in Japanese Patent Application No. 6-269047.

In the general formula (19), R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁷⁰ , R ⁷¹ , R ⁷² and R ⁷³ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, Aryl group, substituted aryl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonate group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted Represents a phosphono group, a phosphonate group, a substituted phosphonate group, a cyano group, a nitro group, or R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁴ and R ⁶⁵ , R ⁷⁰ and R ⁷¹ , R ⁷¹ and R ⁷² may be bonded R ⁷² and R ⁷³ with each other to form an aliphatic or aromatic ring, R ⁶⁶ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, R ⁶⁷ Is a substitution, or Substituted alkenyl group, or a substituted or unsubstituted alkynyl group, R ^68, R ⁶⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted Represents a carbonyl group. Preferable specific examples include the compounds shown below.

  A benzopyran dye represented by the following general formula (20) described in Japanese Patent Application No. 7-164583.

In the general formula (20), independently R ⁷⁴ to R ⁷⁷ are each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. R ^{74 to} R ⁷⁷ may form a ring composed of a nonmetallic atom together with carbon atoms to which they can be bonded. R ⁷⁸ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group, or an alkenyl group. R ⁷⁹ is a group represented by R ⁷⁸ or —Z ⁷ —R ⁷⁸ , and Z ⁷ represents a carbonyl group, a sulfonyl group, a sulfinyl group or an arylene carbonyl group. R ⁷⁸ and R ⁷⁹ may both form a ring composed of a nonmetallic atom. A ⁵ represents an O atom, an S atom, NH or an N atom having a substituent. B ² represents an O atom or a group of ═C (G ⁷ ) (G ⁸ ). G ⁷ and G ⁸ may be the same or different, and may be a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, Or represents a fluorosulfonyl group. However, G ⁷ and G ⁸ are not hydrogen atoms at the same time. G ⁷ and G ⁸ may form a ring composed of a nonmetallic atom together with a carbon atom.

  In addition, specific indolenine cyanine dyes described in the specifications of Japanese Patent Application Nos. 2001-6326 and 2001-237840 previously proposed by the present inventors are also preferable examples.

  In addition, the following infrared absorbers (dyes or pigments) are also preferably used as sensitizing dyes. Preferred examples of the dye include cyanine described in, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787. And dyes, cyanine dyes described in British Patent 434,875, and the specific indolenine cyanine dyes.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and further substituted aryl benzoates described in US Pat. No. 3,881,924 are also used. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A 58-181051, 58-220143, 59 -41363, 59-84248, 59-84249, 59-146063, 59-146061, pyranyl compounds described in JP-A-59-216146, cyanine dyes described in US The pentamethine thiopyrylium salt described in Japanese Patent No. 4,283,475, and the like described in Japanese Patent Publication Nos. 5-13514 and 5-19702 That pyrylium compounds are also preferably used.

  In addition, the near-infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and the phthalocyanine dyes described in EP 916513A2 are also preferable dyes. Can do.

  Furthermore, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. An anionic infrared absorbing agent refers to an anionic infrared absorbing agent having an anionic structure without a cationic structure in the mother nucleus of a dye that substantially absorbs infrared rays. Examples include (c1) anionic metal complexes, (c2) anionic carbon black, (c3) anionic phthalocyanine, and (c4) a compound represented by the following general formula (21). The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

  Here, the (c1) anionic metal complex refers to an anion that forms an anion in the central metal and the entire ligand of the complex part that substantially absorbs light.

  Examples of (c2) anionic carbon black include carbon black to which anionic groups such as sulfonic acid, carboxylic acid, and phosphonic acid groups are bonded as substituents. In order to introduce these groups into carbon black, as described in Carbon Black Handbook 3rd Edition (Edited by Carbon Black Association, April 5, 1995, published by Carbon Black Association), page 12, What is necessary is just to take means, such as oxidizing carbon black.

  (C3) Anionic phthalocyanine refers to a phthalocyanine skeleton bonded with the anionic group previously mentioned in the description of (c2) as a substituent to form an anion as a whole.

Next, the compound (c4) represented by the general formula (21) will be described in detail. In the general formula (21), G ⁹ represents an anionic substituent, and G ¹⁰ represents a neutral substituent. (X ¹⁰ ) ⁺ represents a 1 to m-valent cation containing a proton, and m represents an integer of 1 to 6. M ⁵ represents a conjugated chain, and this conjugated chain M ⁵ may have a substituent or a ring structure. The conjugated chain M ⁵ can be represented by the following formula.

In the formula, R ⁸⁰ , R ⁸¹ and R ⁸² are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy A group and an amino group, which may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

  Of the anionic infrared absorbers represented by the general formula (21), those of the following IRA-1 to IRA-5 are preferably used.

  Moreover, the cationic infrared absorber shown to the following IRC-1-IRC-44 can also be used preferably.

In the structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (BF ₄ ⁻ , PF ₆ ⁻ , SbCl _6). ⁻ , ClO ₄ ⁻ ), an alkyl sulfonate anion, and an aryl sulfonate anion.

  The alkyl of the alkyl sulfonic acid means a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group. Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t- A butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group can be exemplified. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  The aryl of the aryl sulfonic acid includes one consisting of one benzene ring, two or three benzene rings forming a condensed ring, and one having a benzene ring and a 5-membered unsaturated ring forming a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Moreover, the nonionic infrared absorber shown to the following IRN-1-IRN-9 can also be used preferably.

  Among the exemplified compounds, IRA-1 is a particularly preferable anionic infrared absorber, and IRC-7, IRC-30, IRC-40, and IRC-42 are nonionic infrared absorbers as cationic infrared absorbers. Examples of the agent include IRN-9.

<Pigment>
Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, particularly 0.1 μm, from the viewpoint of dispersion stability and film uniformity. It is preferable to be in the range of ˜1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  Among the sensitizing dyes described above, more preferable examples that can be used in the present invention include merocyanine dyes described in JP-B-61-9621, merocyanine dyes described in JP-A-2-17943, and JP-A-2-244050. Merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, merocyanine dyes described in JP-A-8-129257, and JP-A-8-334897 Benzopyran dyes, short-wave type ketone and styryl dyes described in EP1048982A1, and infrared absorbers described in JP-A-11-209001.

Only one type of sensitizing dye in the present invention may be used, or two or more types may be used in combination.
In the present invention, from the viewpoint of improving the decomposability of the coexisting (A) polymerization initiator, a combination containing a styryl dye is preferable.
As content of a sensitizing dye, 0.5-20 mass% is preferable in the total solid of a photosensitive composition, and 1-10 mass% is more preferable.

<Other ingredients>
To the photosensitive composition of the present invention, other components suitable for its use and production method can be added as appropriate. Hereinafter, preferred additives will be exemplified.
(Co-sensitizer)
To the photosensitive composition of the present invention, a known compound having an action such as further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a co-sensitizer.
Examples of co-sensitizers that can be used in the present invention include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Further, thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and disulfide compounds described in JP-A-56-75643 Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like may be used in the same manner.

Examples of co-sensitizers include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), and hydrogen donations described in JP-B-55-34414. , Sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si—H, Ge—H compounds, etc. Can do.
When using a co-sensitizer, it is preferable to use 0.01-50 mass parts with respect to 1 mass part of (A) polymerization initiator.

(Polymerization inhibitor)
It is desirable to add a polymerization inhibitor to the photosensitive composition of the present invention in order to prevent undesired thermal polymerization of polymerizable groups during production and storage.
Usable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The amount of addition in the case of using a polymerization inhibitor is preferably about 0.01% by mass to 5% by mass in the total solid content of the photosensitive composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added in order to prevent polymerization inhibition by oxygen. The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass of the total composition.

(Coloring agent)
In the formation of the laminate described later, a dye or pigment may be added for the purpose of coloring the polymer layer in order to make it easy to visually determine the formation position of the polymer layer. However, when a metal material is further added to the polymer layer to form a metal-containing film material or a light shielding material, which will be described later, the use of a colorant is not particularly necessary.
As the colorant, it is preferable to select a colorant that does not cause a decrease in sensitivity in the photopolymerizable photosensitive composition. From such a viewpoint, the use of a pigment is preferable. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably 0.5% by mass to 5% by mass of the photosensitive composition.

  Since the photosensitive composition of the present invention contains a specific crosslinkable polymer excellent in reactivity and stability over time, in addition to the formation of a light-shielding material, which will be described later, applications in which photopolymers are generally used, such as printing materials, holograms, etc. It can be used as a forming material.

<Laminated body>
Next, a laminate using the photosensitive composition of the present invention and a metal-containing film material using the laminate will be described in detail together with the production method thereof. Such a metal-containing film material is useful as a light shielding material.

The laminate of the present invention comprises a support, an intermediate layer formed using a coupling agent having a polymerizable group on the support, and a compound having a crosslinkable group with respect to the intermediate layer. And an image-like polymer layer made of a polymer directly bonded to the surface of the intermediate layer, which is produced by applying image-wise energy to the composition after the contact. The metal-containing film material and the light-shielding material of the present invention can be obtained by incorporating metal particles in the image-like polymer layer.
Since the metal-containing film material of the present invention contains a specific crosslinkable polymer excellent in reactivity and stability over time, in addition to the formation of a light shielding material described later, an optical material such as an electrical wiring material, an infrared detector, or an optical isolator It can be applied to various uses such as a magnetic head.
The laminate of the present invention includes (a) a step of forming an intermediate layer on a support using a coupling agent having a polymerizable group (hereinafter referred to as “(a) intermediate layer forming step”); (B1) After contacting the composition containing a compound having a crosslinkable group on the intermediate layer, energy is imparted imagewise to the composition to form a polymer that is directly bonded to the surface of the intermediate layer. And a process of forming an image-like polymer layer.
In addition, in the case where a metal material is held in the polymer layer to form a metal-containing film material, a method of bringing a metal ion into contact with the polymer in addition to a method of applying and reducing metal ions to the laminate is also preferable. Since it can apply, the manufacturing method of a metal containing film | membrane material is mentioned later.

  The first production method of the metal-containing film material of the present invention (hereinafter referred to as “the production method (1) of the metal-containing film material of the present invention)” comprises (a) a polymerizable group on the support. A step of forming an intermediate layer using a coupling agent having a coupling agent or a polymerization agent having a polymerization initiation site (hereinafter referred to as “(a) intermediate layer forming step”), and (b1) crosslinkability on the intermediate layer. A step of forming an image-like polymer layer by bringing a composition containing a group-containing compound into contact and then applying image-wise energy to the composition to form a polymer directly bonded to the surface of the intermediate layer. (Hereinafter referred to as “(b1) polymer layer forming step”) and (c1) a step of applying metal ions to the polymer layer and then reducing the metal ions to precipitate metal particles (hereinafter referred to as “( c1) Metal particle precipitation step ”). Characterized in that it.

  In addition, the second method for producing a metal-containing film material of the present invention (hereinafter referred to as “the method for producing a metal-containing film material of the present invention (2)”) comprises (a) a polymerizable on a support. A step of forming an intermediate layer using a coupling agent having a group ((a) intermediate layer formation step); and (b2) a compound having a crosslinkable group on the intermediate layer and a composition containing a metal ion are contacted Then, energy is imparted imagewise to the composition to form a polymer directly bonded to the surface of the intermediate layer to form an imagewise polymer layer (hereinafter referred to as “(b2) polymer layer formation”. And (c2) a step of reducing metal ions contained in the polymer layer to precipitate metal particles (hereinafter referred to as “(c2) metal particle precipitation step”). It is characterized by having.

  Furthermore, the third method for producing a light-shielding material of the present invention (hereinafter referred to as “the method for producing a light-shielding material of the present invention (3)”) is (b3) a cup having a polymerizable group on a support. After contacting a composition containing a ring agent or a coupling agent having a polymerization initiation site and a compound having a crosslinkable group, image-wise energy is imparted on the composition and directly bonded to the support surface. A step of forming an image-like polymer layer (hereinafter referred to as “(b3) polymer layer forming step”), and applying a metal ion to the polymer layer, and then reducing the metal ion And a step of depositing metal particles (hereinafter referred to as “(c3) metal particle deposition step” as appropriate).

  In addition, the fourth method for producing a light-shielding material of the present invention (hereinafter described as “the method for producing a light-shielding material of the present invention (4)”) has (b4) a polymerizable group on the support. After contacting a composition comprising a coupling agent or a coupling agent having a polymerization initiation site, a compound having a crosslinkable group, and a metal ion, energy is imparted onto the composition imagewisely, and the support A step of forming an image-like polymer layer by forming a polymer directly bonded to the surface (hereinafter referred to as “(b4) polymer layer forming step”), and metal ions contained in the polymer layer And a step of reducing and precipitating metal particles (hereinafter referred to as “(c4) metal particle precipitating step” as appropriate).

  Hereinafter, the metal-containing film material (1) and (2) of the present invention will be described in detail through the description of each step of the metal-containing film material production methods (1) to (4) of the present invention.

[(A) Intermediate layer forming step]
The production methods (1) and (2) of the metal-containing film material of the present invention include (a) an intermediate layer forming step as shown below.
In this step, the intermediate layer is formed on the support using a coupling agent having a polymerizable group or a coupling agent having a polymerization initiation site.
First, the coupling agent having a polymerizable group and the coupling agent having a polymerization initiation site used in this step will be described.
The coupling agent having a polymerizable group is a compound having a polymerizable group and a substituent capable of forming a chemical bond with the support. The coupling agent having a polymerization initiation site is a compound having a partial structure having a polymerization initiation ability and a substituent capable of forming a chemical bond with the support.
The substituent capable of forming a chemical bond with the support is not particularly limited as long as it can be chemically bonded to the support by a covalent bond, an ionic bond, and a hydrogen bond. From the viewpoint, a substituent capable of forming a covalent bond is preferable.
Among these, an alkoxide group or a halide group of an element selected from Si, Ti, Zr, and Al represented by a silane coupling group with a support is preferable.
Hereinafter, as a coupling agent having a polymerizable group, a compound having a polymerizable group and a silane coupling group will be described as an example.

The coupling agent having a polymerization initiation site is not particularly limited as long as it is a compound having an initiator site and a base binding site that are usually used for photopolymerization initiators. For example, a coupling agent or oxime ester site having a triazine site is used. And the like.
(Coupling agent having a triazine moiety)
Examples of the coupling agent having a triazine moiety that can be applied to the present invention include a compound having a polymerization initiation site (Y) capable of initiating radical polymerization by photocleavage and a substrate binding site (Q) (hereinafter referred to as “appropriately” Photocleavable compound (QY) ") and the like.
Here, the polymerization initiation site where radical polymerization can be initiated by photocleavage (hereinafter simply referred to as “polymerization initiation site (Y)”) is a structure containing a single bond that can be cleaved by light.
As the single bond that is cleaved by this light, carbonyl α-cleavage, β-cleavage reaction, light-free rearrangement reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, benzyl Examples thereof include a single bond that can be cleaved using an imide cleavage reaction, a cleavage reaction of an active halogen compound, and the like. These reactions break a single bond that can be cleaved by light. Examples of the single bond that can be cleaved include a C—C bond, a C—N bond, a C—O bond, a C—Cl bond, a N—O bond, and a S—N bond. This compound is described in detail in paragraph Nos. [0014] to [0025] of Japanese Patent Application No. 2006131834.

In addition, since the polymerization initiation site (Y) containing a single bond that can be cleaved by light is the starting point of graft polymerization in the graft polymer production step, when the single bond that can be cleaved by light is cleaved, the cleavage reaction causes Has the function of generating radicals. As described above, examples of the structure of the polymerization initiation site (Y) having a single bond that can be cleaved by light and capable of generating radicals include structures containing the following groups.
That is, aromatic ketone group, phenacyl ester group, sulfonimide group, sulfonyl ester group, N-hydroxysulfonyl ester group, benzylimide group, trichloromethyl group, benzyl chloride group, and the like.

When such a polymerization initiation site (Y) is cleaved by exposure and a radical is generated, when a polymerizable compound is present in the vicinity of the radical, this radical functions as a starting point for the graft polymerization reaction. Can be generated.
Therefore, when a graft polymer is produced using a substrate having a photocleavable compound (QY) introduced on the surface, exposure at a wavelength that can cleave the polymerization initiation site (Y) as an energy imparting means. Must be used.

  Further, the base material binding site (Q) is composed of a reactive group capable of reacting with and binding to a functional group present on the surface of an insulating substrate typified by glass. As the reactive group, specifically, Examples of the base material-binding group include the following.

  The polymerization initiation site (Y) and the substrate binding site (substrate binding group) (Q) may be directly bonded or may be bonded via a linking group. Examples of the linking group include a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Specifically, for example, a saturated carbon group, an aromatic group, an ester group, an amide group. Ureido group, ether group, amino group, sulfonamide group, and the like. The linking group may further have a substituent, and examples of the substituent that can be introduced include an alkyl group, an alkoxy group, and a halogen atom.

  Specific examples [Exemplary compounds T1 to T5] of the compound (QY) having the substrate binding site (Q) and the polymerization initiation site (Y) are shown below together with the cleavage portion, but the present invention includes these compounds. It is not limited.

(Coupling agent having an oxime ester moiety)
Examples of the coupling agent having an oxime ester moiety include compounds represented by the following general formula (OS).

In the general formula (OS), R ¹ represents a single bond or a linking group, R ² represents a monovalent substituent, and Y ¹ represents a substrate binding site. This compound is described in detail in Japanese Patent Application No. 2007-211083 as a compound represented by the general formula (1).

Specific examples of the coupling agent having an oxime ester moiety that can be suitably used in the present invention include the following exemplary compounds (OS-1) to (OS-16), but the present invention is limited to these. is not.
Exemplified compounds (OS-1) to (OS-12) are polymers or oligomers, and are represented by displaying the structural units constituting them and their polymerization molar ratios. The weight average molecular weight (Mw) of the polymer is 10,000 to 50,000, and the weight average molecular weight (Mw) of the oligomer is 2000 to 9000.
Exemplified compounds (OS-13) to (OS-16) are low molecular weight compounds represented by the general formula (1).

  Further, the compound having a polymerizable group and a silane coupling group is not particularly limited as long as it is a commonly used silane coupling agent and has a polymerizable group in its molecule. It is preferable that it is a compound represented by General formula (1).

In the general formula (1), R ¹ , R ² , and R ³ each independently represent a hydroxy group, an alkoxy group, an acyloxy group, an acylamino group, or a halogen atom.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a benzyloxy group, a cyclohexyloxy group, an adamantyloxy group, a 2,4-dimethyl-3-pentyloxy group, and a phenoxy group. Can be mentioned.
Examples of the acyloxy group include formyl group, acetoxy group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, lauryl group, benzoyl group, methoxaloyl group, malonyl group, cyclohexanecarbonyl group and the like. Can be mentioned.
Examples of the acylamino group include an acetylamino group, a carbamoyl group, and a benzoylamino group.
Examples of the halogen atom include chlorine, bromine and iodine.

X in the general formula (1) represents a polymerizable group, and examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. From the viewpoint of storage stability and sensitivity, the radical polymerizable group may be used. Groups are preferred.
As the radical polymerizable group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, and a methacryloylamino group are preferable.
Examples of the cationic polymerizable group include a cyclic ether group (epoxy group, oxetane group, etc.), a vinyl group, a lactone group, an aziridine group, and the like. Among these, a vinyl group or an epoxy group is preferable.

  Y in the general formula (1) is a linking group that connects a polymerizable group and a silane coupling group, and is not particularly limited as long as it is a functional group that does not inhibit polymerization or silane coupling. For example, an alkylene group or an arylene group Alkenylene group, alkynylene group, etc. can be used.

Specific examples of the compound represented by the general formula (1) include trimethoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, trichlorosilylpropyl methacrylate, trichlorosilylpropyl acrylate, trimethoxysilylhexyl methacrylate, tribromosilylhexyl methacrylate. Etc.
Of these, trimethoxysilylpropyl methacrylate or trimethoxysilylpropyl acrylate is preferable from the viewpoint of in-plane uniformity during the reaction with the support.

In this step, a liquid composition is prepared using a coupling agent having a polymerizable group and an appropriate solvent, and the composition is contacted and placed on a support by coating or the like to remove the solvent. To form an intermediate layer. In this film forming process, a coupling reaction occurs, and an intermediate layer in which a coupling agent having a polymerizable group is bonded to the support surface by the coupling group is formed.
As a result, in the present invention, an intermediate layer having a polymerizable group is obtained.

The solvent used for preparing the liquid composition is not particularly limited as long as it has a boiling point of 150 ° C. or lower, but water, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate.
At this time, the concentration of the coupling agent having a polymerizable group in the liquid composition is preferably 0.01% by mass to 30% by mass, and particularly preferably 0.1% by mass to 15% by mass.

The coating amount of the liquid composition when coupling the coupling agent having a polymerizable group to the support is from the viewpoint of preventing reaction of the polymerizable group and preventing film peeling while maintaining film properties. The mass after drying is preferably 0.1 to 20 g / m ^{2, and} more preferably 0.5 to 15 g / m ² .
Moreover, as liquid temperature of the liquid composition in the case of making it contact, 0 to 100 degreeC is preferable. The contact time is preferably 1 second to 50 hours, and more preferably 10 seconds to 10 hours.

The intermediate layer in the present invention is formed by removing the solvent of the liquid composition. At this time, it is preferable to perform heating to form a film.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried. However, from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

[Support]
Especially as a support body in this invention, what is necessary is just to use the thing according to a use regardless of the shape and material. More specifically, the support is preferably a dimensionally stable plate-like material, for example, a glass substrate, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), Metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate , Polyvinyl acetal, polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), paper or plastic on which the above metal is laminated or deposited Irumu and the like.
The support used in the present invention is preferably an epoxy resin or a polyimide resin.

In addition, when applying the light shielding material of this invention to a photomask, it is preferable to use a glass substrate as a support body.
Moreover, it is preferable that it is 0.1-20 mm as thickness of a glass substrate.

[(B1) and (b2) polymer layer forming step]
In the present invention, in the case of (b1) polymer layer forming step, the photosensitive composition of the present invention containing a specific crosslinkable polymer is used. In the case of (b2) polymer layer forming step, the photosensitive composition is used. And a composition containing metal ions is required to form a polymer layer.
Specifically, in this step, after contacting one of the above compositions on the intermediate layer, image-wise energy is applied to the composition, and the polymerizable group in the intermediate layer and the specific crosslink An image-like polymer layer is formed by reacting with a photopolymer to form a polymer that is directly bonded to the surface of the intermediate layer.
Hereinafter, the composition containing a compound having a crosslinkable group used in the step (b1) and the composition containing a compound having a crosslinkable group and a metal ion used in the step (b2) are generally referred to as “reactivity”. This will be described in detail as “composition”.

[Metal ions]
(B2) In the polymer layer forming step, it is necessary to form a polymer layer using a reactive composition containing a metal ion in addition to the compound having a crosslinkable group described above.
The metal ions used here are silver ions, copper (I) ions, copper (II) ions, palladium ions (II), palladium ions (IV), aluminum ions, nickel ions, iron ions (II), iron ions. (III), ruthenium ion, rhodium ion, tin ion and the like can be mentioned. Among them, silver ion and palladium ion are preferable from the viewpoint of easy reduction.
In addition, when the above-mentioned crosslinkable compound has a metal ion adsorption group, a metal ion may be introduce | transduced in this compound by salt exchange.

It is preferable that 1-30 mass% is contained in the reactive composition used at this process, and, as for the metal ion in this invention, it is more preferable that 2-10 mass% is contained.
Moreover, these metal ions may be used individually by 1 type, and may use 2 or more types together.

In addition to the above components, the reactive composition used in this step can contain a polymerization initiator, a sensitizer, a chain transfer agent, a polymerization inhibitor, and the like as necessary. In addition, when the reactive composition used in this step is polymerized by applying energy, the polymerization initiator is not used, and light corresponding to the absorption wavelength of the crosslinkable compound contained in the reactive composition is irradiated. Polymerization can be initiated. For example, when a crosslinkable compound having an acryloyloxy group as a crosslinkable group is used, light at 254 nm is preferably used.
Hereinafter, various components added to the reactive composition used when forming the polymer layer will be described.

[Polymerization initiator]
In the present invention, the polymerization initiator used for the formation of the intermediate layer is a known thermal polymerization initiator that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, electron beam irradiation, etc. A photopolymerization initiator and the like can be appropriately selected and used depending on the purpose. Among these, use of photopolymerization is preferable from the viewpoint of production suitability, and therefore, it is preferable to use a photopolymerization initiator. That is, the reactive composition in the present invention is preferably a photopolymerizable composition by using a photopolymerization initiator.

As the photopolymerization initiator in the present invention, a hydrogen abstraction type radical polymerization initiator, a photocleavage type radical polymerization initiator, or the like may be used.
Examples of the hydrogen abstraction type radical polymerization initiator include known acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, thioxanthone and the like. A radical generator can be used. In addition, since sulfonium salts and iodonium salts that are usually used as photoacid generators also act as radical generators upon irradiation with light, these may be used in the present invention.

  The photocleavable radical polymerization initiator has a structure containing a single bond that is cleaved by light. Single bonds that can be cleaved by light include carbonyl α-cleavage, β-cleavage reaction, light-free transfer reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, benzyl Examples thereof include a single bond that can be cleaved using an imide cleavage reaction, a cleavage reaction of an active halogen compound, and the like. These reactions break a single bond that can be cleaved by light. Examples of the single bond that can be cleaved include a C—C bond, a C—O bond, a S—N bond, a C—N bond, a N—O bond, and a C—Cl bond.

Examples of the polymerization initiator having a single bond that can be cleaved by light and capable of generating a radical include those containing the following groups.
That is, for example, aromatic ketone group, phenacyl ester group, sulfonimide group, sulfonyl ester group, N-hydroxysulfonyl ester group, benzylimide group, trichloromethyl group, benzyl chloride group, oxime ester group and the like can be mentioned.

In the present invention, a thermal cationic polymerization initiator can also be used. Examples of the thermal cationic polymerization initiator include sulfonium salts, ammonium salts, onium salts such as phosphonium salts, silanol / aluminum complexes, and the like, for example, CP-66 and CP-77 manufactured by Asahi Denka Kogyo Co., Ltd. Any material can be used as long as it has a thermal cationic polymerization initiating action. Sulfonium salt thermal polymerization initiators such as CP-66 and CP-77 manufactured by Asahi Denka Kogyo Co., Ltd. are used.
Further, the reaction temperature in the crosslinking formation reaction by the thermal cationic polymerization may be appropriately set so that crosslinking is generated, and is not particularly limited.

The polymerization initiator used at this process is not specifically limited, What is necessary is just to select according to the energy provided, and you may combine with the sensitizer mentioned later.
In addition, it is preferable to use what can express the polymerization initiating ability corresponding to the polymeric group contained in the crosslinkable compound used for a reactive composition as the polymerization initiator used for this process.

It is preferable that 0.01-20 mass% is contained in the reactive composition used at this process, and, as for the photoinitiator in this invention, it is more preferable that 0.1-10 mass% is contained.
Moreover, these polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Sensitizer]
There is no restriction | limiting in particular as a sensitizer which can be used for this invention, According to the energy (especially exposure wavelength) provided, it can select suitably from well-known sensitizers.
Specifically, for example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, Thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (E.g., anthraquinone), squalium (e.g., squalium), acridone (e.g., acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroa) Lidon etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 '-Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7- Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 , 7-dipropoxycoumarin and others, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209 Etc.) and the like.

  As a combination of a photopolymerization initiator and a sensitizer, for example, an electron transfer type initiator system described in JP-A No. 2001-305734 [(1) electron donating type initiator and sensitizing dye, (2) electron accepting Type initiators and sensitizing dyes, (3) electron donating initiators, sensitizing dyes and electron accepting initiators (ternary initiation system)], and the like.

The addition amount of the sensitizer in the reactive composition used in this step is preferably in the range of 10 to 500% by mass and more preferably in the range of 50 to 200% by mass with respect to the polymerization initiator. preferable.
Moreover, these sensitizers may be used individually by 1 type, and may use 2 or more types together.

[Thermal polymerization inhibitor]
A thermal polymerization inhibitor can also be added to the reactive composition used in this step. A thermal polymerization inhibitor is added to prevent thermal polymerization or time-dependent polymerization of the reactive composition, which makes it possible to chemically react during preparation of the reactive composition or storage until use. Stability can be improved.
Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, benzoquinone, o-toluquinone, p-toluquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride , Phenothiazine, floranyl, chloranil, naphthylamine, pyridine, p-toluidine, β-naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, aluminum of N-nitrosophenylhydroxylamion Examples thereof include salts or ammonium salts, methylene blue organic copper, methyl salicylate, and aryl phosphite.
The preferable addition amount of the thermal polymerization inhibitor is 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, based on the solid content of the reactive composition, from the viewpoint of thermal stability and sensitivity. It is.

[solvent]
The reactive composition containing each of the above components is preferably a liquid composition for facilitating contact with the support or the intermediate layer, and an appropriate solvent is used for preparing the liquid composition. It is preferable to use it.
The solvent used here is not particularly limited as long as it can dissolve or disperse the crosslinkable compound as the main component, but is preferably an aqueous solvent such as water or a water-soluble solvent, and a mixture thereof. Also good.
Examples of solvents that can be used include water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, alcohol solvents such as acetic acid, acetone, methyl ethyl ketone, ketone solvents such as cyclohexanone, formamide, and dimethyl. Examples thereof include amide solvents such as acetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propylonitrile, and ester solvents such as methyl acetate and ethyl acetate.
Among these, in the case of a composition using a cyano group-containing crosslinkable polymer, amide, ketone, and nitrile solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propio Nitrile and N-methylpyrrolidone are preferred.
Moreover, when apply | coating the composition containing a cyano group containing crosslinkable polymer, the solvent whose boiling point is 50-150 degreeC is preferable from handling ease. In addition, these solvents may be used alone or in combination.

  Further, the surfactant that can be added to the liquid composition as necessary may be any one that dissolves in a solvent. Examples of such a surfactant include n-dodecylbenzenesulfonic acid. Anionic surfactants such as sodium, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxy Examples include ethylene sorbitan monolaurate (commercially available products such as “Tween 20”) and nonionic surfactants such as polyoxyethylene lauryl ether.

(Contact mode of photosensitive composition to intermediate layer)
In this step, as a method of bringing the photosensitive composition containing at least the above-mentioned specific crosslinkable polymer into contact with the intermediate layer, any method can be used. Specifically, a liquid photosensitive composition is used. Examples thereof include a method of immersing a support having an intermediate layer formed therein and a method of applying a liquid photosensitive composition on the intermediate layer.

Further, from the viewpoint of handling properties and production efficiency, a mode in which a liquid photosensitive composition is applied on the intermediate layer and dried to form a polymer-containing layer is preferable.
When forming a polymer-containing layer, the coating amount of the photosensitive composition is preferably from 0.1 to 10 g / ^{m 2} in terms of solid content, in particular 0.5 to 5 g / ^{m 2} is preferred.

(Granting energy)
In this step, energy is imparted in order to obtain a polymer obtained by reacting the polymerizable group in the intermediate layer with the specific crosslinkable polymer and directly bonding to the surface of the intermediate layer.
Examples of the energy applying means used here include irradiation with actinic rays, heating, and irradiation with electron beams. Among them, it is preferable to use pattern exposure as an energy applying means in order to apply image-like energy easily and accurately.

-Pattern exposure-
The pattern exposure is not particularly limited as long as the polymerizable group in the intermediate layer and the specific crosslinkable polymer can be reacted. Specifically, it is preferable to use a laser having a wavelength of 360 nm to 700 nm.
The necessary exposure amount is appropriately determined depending on the properties and content of the coupling agent having a polymerizable group, the specific crosslinkable polymer, the photopolymerization initiator, and the sensitizing dye, but is 25 to 400 mJ / cm ^2. Is preferred.

  As the pattern exposure, for example, scanning exposure using a cathode ray (CRT) can be used. For the cathode ray tube used for this exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one or two or more of a red light emitter, a green light emitter, and a blue light emitter are used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit yellow, orange, and purple light are also used.

  In this step, pattern exposure can be performed using various laser beams. For example, lasers such as gas lasers, light-emitting diodes, semiconductor lasers, semiconductor lasers, or second harmonic emission light sources (SHGs) that combine nonlinear lasers with solid-state lasers that use semiconductor lasers as excitation light sources, etc. A scanning exposure method using light can be preferably used. Furthermore, a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be used.

The resolution of the image-like polymer layer formed according to the present invention depends on the exposure conditions. That is, in the pattern exposure for forming the polymer layer, a high-definition pattern corresponding to the exposure is formed by performing high-definition pattern exposure. Examples of the exposure method for forming a high-definition pattern include light beam scanning exposure using an optical system, exposure using a mask, and the like, and an exposure method corresponding to the resolution of a desired pattern may be taken.
Specific examples of the high-definition pattern exposure include stepper exposure such as i-line stepper, g-line stepper, KrF stepper, and ArF stepper.

By the polymer layer forming step (b1) or (b2) described above, a polymer layer made of a polymer directly bonded to the surface of the intermediate layer can be formed in an image-like manner on the intermediate layer.
In addition, when the polymer layer forming step (b2) is used, a polymer layer containing metal ions is formed.

[(B3) and (b4) polymer layer forming step]
In the present invention, unlike the polymer layer forming steps (b1) and (b2), an image-like polymer layer may be formed directly on the support.
Hereinafter, (b3) and (b4) the polymer layer forming step will be described.

  In the present invention, in the case of (b3) polymer layer forming step, a composition containing a coupling agent having a polymerizable group and a specific crosslinkable polymer is used, and after contacting this on a support, the composition An image-like polymer layer is formed by imparting image-like energy to a product, reacting the support with a coupling agent having a polymerizable group, and reacting a coupling agent having a polymerizable group with a specific cross-linkable polymer. Form. At this time, if necessary, an image-like polymer layer formed by directly bonding to the surface of the support can be formed by performing a treatment such as heating.

  In the case of (b4) polymer layer forming step, a composition containing a coupling agent having a polymerizable group, a specific crosslinkable polymer, and a metal ion is used, and after contacting it on a support, Image-like energy is imparted to the composition, the support and the coupling agent having a polymerizable group are reacted, and the coupling agent having a polymerizable group and a specific crosslinkable polymer are reacted to form an image-like material. A polymer layer is formed. At this time, if necessary, an image-like polymer layer formed by directly bonding to the surface of the support can be formed by performing a treatment such as heating.

(B3) The coupling agent having a polymerizable group used in the polymer layer forming step is the coupling agent having a polymerizable group used in the step (a), and the specific crosslinkable polymer is the same as described above. This is the same as the specific crosslinkable polymer used in the steps (b1) and (b2).
Further, (b4) the coupling agent having a polymerizable group used in the polymer layer forming step includes the coupling agent having a polymerizable group used in the aforementioned step (a), and a specific crosslinkable polymer, In addition, the metal ions are the same as the specific crosslinkable polymer and metal ions used in the steps (b1) and (b2) described above, and preferred examples thereof are also the same.

In addition, in the case of a composition containing both a coupling agent having a polymerizable group and a specific crosslinkable polymer as in this step, the concentration of the coupling agent having a polymerizable group is set in the reactive composition. 0.1 to 50% by mass is preferable, and 5 to 20% by mass is particularly preferable.
Moreover, in the case of the composition containing both the coupling agent which has a polymeric group, and a specific crosslinkable polymer, it is preferable that 20-90 mass% of specific crosslinkable polymers are contained in the reactive composition, 50 More preferably, it is contained in 80% by mass.

  The photosensitive composition used in this step includes various optional components (polymerization initiator, sensitizer, chain transfer agent, and the like used in the above-described steps (b1) and (b2). Polymerization inhibitors etc.) can also be added. Moreover, the preferable addition amount of these arbitrary components is the same as that of the above-mentioned.

As a mode of bringing the photosensitive composition used in this step into contact with the support, any method can be used. Specifically, a method of immersing the support in a liquid photosensitive composition, or a liquid A method of coating the photosensitive composition on a support, and a method of coating a liquid photosensitive composition on the support and drying to form a polymerizable layer are used. In addition, the preferable application quantity of this polymeric layer is the same as that of the polymeric layer formed in the above-mentioned (b1) and (b2) process.
In addition, when forming a polymeric layer using a photosensitive composition, the coupling group derived from the coupling agent which has a polymeric group may couple | bond with a support body.

  In this step, energy is applied after bringing the above-mentioned photosensitive composition into contact with the support. The energy application method is the same as that used in the above-described steps (b1) and (b2), and the preferred embodiment is also the same.

By the polymer layer forming step (b3) or (b4) described above, a polymer layer composed of a polymer directly bonded to the surface of the support can be formed like an image on the support.
In addition, when the (b4) polymer layer forming step is used, a polymer layer containing metal ions is formed.

In the polymer layer forming step (b1) to (b4), after energizing the photosensitive composition as described above, the bond between the support and the coupling group having a polymerizable group is promoted. Moreover, you may heat-process as needed. This heat treatment may be performed on the polymer layer before development as described later or after development. However, when an image-like polymer layer is formed, it is preferably performed after development from the viewpoint of image refinement.
The heating temperature is preferably 40 ° C to 150 ° C, and more preferably 60 ° C to 80 ° C.

In the present invention, the support (layered product of the present invention) on which the polymer layer is formed as described above is subjected to treatment such as solvent immersion and solvent washing, and is applied to an unreacted composition, support or intermediate layer. Unbonded homopolymer or the like is removed (this process is also called a development process).
Specifically, water, acetone, sodium hydroxide aqueous solution, sodium bicarbonate aqueous solution, hydrochloric acid, methyl ethyl ketone, acetone, and ethanol are used for this treatment. In addition, it is preferable that drying is performed after processes, such as solvent immersion and solvent washing | cleaning.
In this treatment, an industrial wiper such as Bencott may be used in combination, and from the viewpoint of homopolymer removability, means such as ultrasonic waves may be taken.
After such treatment, the unreacted photosensitive composition and the homopolymer not bonded to the support or the intermediate layer are removed, and only the polymer firmly bonded to the support or the intermediate layer is present.

The film thickness of the formed polymer layer is preferably 200 to 2000 nm, preferably 500 to 1500 nm, and more preferably 600 to 1000 nm. When the thickness of the polymer layer is within this range, a large amount of metal particles can be contained in the polymer layer, which is preferable.
In particular, in order to set the content of the metal particles in the metal-containing film material of the present invention to a level at which a practically sufficient function is expressed, more specifically, for example, this is applied to a light-shielding material, particularly a photomask. In this case, the thickness of the polymer layer is preferably in the above range in order to contain metal particles that can exhibit sufficient light shielding properties. If the thickness of the polymer layer is less than 200 nm, the amount of metal particles contained is insufficient, so that a sufficient amount of metal adsorption and light shielding may not be obtained. In addition, when the thickness of the polymer layer exceeds 2000 nm, light wraparound during patterning, polarization, etc. occur, and when this material is used to produce a photomask and exposure is performed, the image resolution may be lowered. is there.

In the present invention, the thickness of the polymer layer is controlled by bringing the composition containing at least the crosslinkable compound into contact with the intermediate layer and controlling the amount of energy applied thereto (in the case of pattern exposure, the exposure amount). Can be adjusted.
The thickness of the polymer layer can be measured by AFM (NPX100M001, manufactured by Seiko Instruments Inc.).

[(C1) to (c4) metal particle precipitation step]
In the present invention, in step (c1) or (c3), metal ions are applied to the polymer layer formed in step (b1) or (b3) described above, and then the metal ions are reduced to deposit metal particles. .
In the step (c2) or (c4), since metal ions are already contained in the polymer layer in the step (b2) or (b4), the metal ions are reduced to deposit metal particles.
When the thin metal film is used as a photomask, the metal particles deposited from the viewpoint of light shielding ability preferably have absorption in the region of the exposure wavelength to be used, and particularly preferably have absorption at 365 nm or more.

As a method for imparting metal ions in the steps (c1) and (c2), a solution containing metal ions may be applied on the polymer layer formed in the steps (b1) and (b3). The support on which the polymer layer is formed may be immersed in the solution.
Examples of the metal ions used here include the same metal ions as those used in the reactive composition used in the step (b2) described above, and preferred examples are also the same.
Moreover, it is preferable that the density | concentration of the metal ion in the solution containing a metal ion is 0.1-10 mass%.
The solvent used in this solution is not particularly limited as long as it can dissolve a metal compound serving as a metal ion source, but water, methanol, ethanol, propanol, tetrahydrofuran, pyridine, aqueous ammonia and the like are preferably used.

The time for bringing the solution containing the metal ions into contact with the polymer layer may be appropriately determined according to the composition of the polymer layer, the metal ion concentration, the application, etc., but is usually between 10 seconds and 10 minutes. Preferably there is.
By this contact, metal ions may be introduced into the polymer layer by salt exchange.

After metal ions are introduced into the polymer layer as described above, metal particles are precipitated by reducing the metal ions in the polymer layer.
A reducing agent is used for the reduction of metal ions. The reducing agent is not particularly limited as long as it has a reducing power sufficient to reduce metal ions in the polymer layer, and a general reducing agent is used. For example, organic reducing agents such as formaldehyde, acetaldehyde, and hydrazine, metals such as NaBH ₄ , LiAlH ₄ , and borane, and metalloid reducing agents can be used.

As a method for reducing metal ions, a method of immersing a support on which a polymer layer is formed in a solution containing the above reducing agent is simple and preferably used. As the solvent used in the reducing agent solution, it is necessary to consider the reactivity and danger of the reducing agent used, but it is possible to use a commonly used solvent such as water, methanol, acetone, toluene, and tetrahydrofuran. it can.
The immersion time is appropriately determined depending on the metal ion concentration in the polymer layer and the content of the reducing agent in the solution, but is usually preferably 1 second to 600 seconds.

  In the present invention, the steps (c1) to (c4) may be performed before or after the above-described development processing, but may be performed after the development.

  As described above, an image-like polymer layer containing metal particles can be obtained.

  The light shielding material obtained by the present invention (the light shielding material of the present invention) has metal particles only in the region where the polymer layer is formed. Therefore, it can be used as a photomask using a polymer layer containing metal particles as a light shielding part, an electric wiring board, a light reflecting material, a decoration material, a metal particle transfer material, and a color filter.

  The photomask to which the light-shielding material of the present invention is applied has high light-shielding properties and excellent durability and is not particularly limited. For example, the photomask is suitably used as a photomask in LSI, LCD, PWB, PDP, package and the like. .

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples.

(Synthesis Example 1: Synthesis of Polymer P1 Having Polymerizable Group and Metal Ion Adsorbing Group)
18 g of polyacrylic acid (average molecular weight 25,000) is dissolved in 300 g of DMAc (dimethylacetamide), to which 0.74 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate are added, The reaction was carried out at 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. In addition to hexane, the polymer was precipitated and washed well to obtain a polymer P1 having a polymerizable group and a metal ion adsorbing group.

[Example 1]
[Intermediate layer forming step]
A glass substrate having a thickness of 2 mm was washed with acetone and distilled water, and then subjected to UV ozone treatment for 5 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.). Next, acryloyloxypropyltrimethoxysilane was dissolved in methyl ethyl ketone to prepare a 10.0% by mass solution, and this solution was spin-coated on the above glass substrate. The spin coat was first rotated at 300 rpm for 5 seconds and then at 1000 rpm for 20 seconds. After spin coating, heating was performed at 80 ° C. for 1 hour, and the surface was washed with methyl ethyl ketone. The glass substrate having the intermediate layer thus obtained is referred to as substrate A1.

[Ammonium salt substitution step]
After dissolving 0.25 g of the polymer P1 having a polymerizable group and a metal ion adsorbing group obtained in Synthesis Example 1 in 3 g of MFG, 0.43 g of 37% tetrabutylammonium hydroxide methanol solution was added and stirred for 5 minutes. A solution of Q1 (the following structure: weight average molecular weight (Mw): 26,000) was prepared.

  When 10 g of hexane was added to 0.1 g of this solution and the precipitated polymer was analyzed by NMR (BRUKER BIOSPIN, AV300M), the substitution rate of the ammonium salt was 89%.

[Polymer layer forming step]
Compound A: 20 mg and Compound B: 6.9 mg were added to 3.5 g of the MFG solution of polymer Q1 obtained as described above to prepare a liquid photosensitive composition.

The photosensitive composition containing the specific crosslinkable polymer Q1 and the polymerization initiator was spin-coated on the intermediate layer surface of the substrate A1. The spin coater was first rotated at 300 rpm for 5 seconds and then at 1000 rpm for 20 seconds. In this way, a polymerizable layer made of the photosensitive composition was formed.
Then, the board | substrate was dried at 80 degreeC for 5 minute (s), and board | substrate A1 in which the polymeric layer was formed was obtained.
(exposure)
The substrate A1 on which the polymerizable layer was formed was exposed at 500 mJ / cm ² according to a predetermined pattern using a laser exposure machine having a transmission wavelength of 405 nm. After the exposure, the surface of the polymerizable layer was washed with acetone while lightly rubbing with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.), and then wiped with nitrogen.
As described above, a glass substrate (laminate of the present invention) on which an image-like polymer layer composed of a polymer directly bonded to the surface of the intermediate layer was formed was obtained. The glass substrate having this image-like polymer layer is defined as a laminate B1.

The pattern of the obtained laminate B1 was observed with AFM (Nanopics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern having a line width of 10 μm and a gap width of 10 μm alternately formed on the surface of the glass substrate.
The film thickness of the image-like polymer layer was 1500 nm.

[Metal particle precipitation process]
The obtained laminate B1 was immersed in a 0.1% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 5 minutes and then immersed in formalin for 10 minutes. Thereafter, the substrate was washed by washing with 50 mL of water to obtain a substrate C1 having a polymer layer containing metal particles.
This obtained the light-shielding material of Example 1.

<Evaluation>
The obtained light shielding material was evaluated by measuring the absorbance of the polymer layer forming region and the non-forming region, and the pencil strength of the polymer layer (metal film).
The absorbance at 365 nm of the polymer layer (metal film) of the obtained metal film material was measured by the following measuring method to be 3.3.

-Measurement method of absorbance-
Absorbance was measured using a visible and near infrared spectrophotometer (UV-3600, Shimadzu). As a metal film material (photomask), the minimum practically necessary absorbance standard is 3.0 or more.

[Example 2]
A glass substrate (laminate B2) having an image-like polymer layer was obtained in the same manner as in Example 1 except that the substrate A1 obtained in Example 1 was stored at room temperature in the dark for 3 weeks. The film thickness of the image-like polymer layer was 1500 nm.
The absorbance at 365 nm of the polymer layer (metal film) of the obtained metal film material was measured by the following measuring method to be 3.2.

[Comparative Example 1]
Substrate B3, which is a glass substrate having an image-like polymer layer, was obtained in the same manner as in Example 1 except that polymer P1 was used instead of polymer Q1 used in Example 1. The film thickness of the image-like polymer layer was 1500 nm.
The absorbance at 365 nm of the polymer layer (metal film) of the obtained metal film material was measured by the following measuring method to be 3.3.
[Comparative Example 2]
Substrate B4, which is a glass substrate having an image-like polymer layer, was obtained in the same manner as in Example 1 except that A1 obtained in Comparative Example 1 was stored at room temperature in the dark for 3 weeks. The film thickness of the image-like polymer layer was 880 nm.
The absorbance at 365 nm of the polymer layer (metal film) of the obtained metal film material was measured by the following measurement method to be 2.0.

From the above results, the light-shielding material of the present invention having a polymer layer formed using the specific cross-linkable polymer of the present invention is excellent in light-shielding properties, and it is possible to preserve the laminate by comparing Example 1 and Example 2. Later, it was found that the light shielding property was excellent, and the laminate of the present invention was excellent in stability over time.
On the other hand, the light shielding material of Comparative Example 1 formed using a polymer outside the scope of the present invention which does not contain an acid group ammonium salt in the crosslinkable polymer exhibits a certain degree of light shielding property, but in contrast to Comparative Example 2. It can be seen that the stability of the crosslinkable polymer is inferior, and the light-shielding property of the light-shielding material obtained over time is significantly reduced over time. When the light-shielding property is lowered after storage for about 3 weeks, the performance necessary for practical use is not ensured.

Claims (8)

A photosensitive composition comprising (A) a photopolymerization initiator and (B) a crosslinkable polymer including each structural unit represented by the following general formula (1).

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms. An alkyl group is shown.
A represents a substituent having 0 to 10 carbon atoms including a group selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a conjugate base thereof, and B represents an ammonium salt of a carboxyl group and an ammonium salt of a sulfonic acid group. And a substituent having 0 to 10 carbon atoms including a partial structure selected from a salt, an ammonium salt of a phosphate group, and C represents a substituent including a crosslinkable group, and D is a straight chain having 1 to 20 carbon atoms. C1-C20 straight chain having a chain or branched alkyl group, a C3-C20 cycloalkyl group, a C6-C15 aryl group or a C2-C20 heterocyclic group, or a cyano group Or a branched alkyl group is shown.
“w”, “x”, “y”, and “z” are mole fractions of the monomer units constituting each of the displayed structural units, each representing a real number of 0 to 1, each having the relationship shown below. (W + x + y) / (w + x + y + z) represents a real number of 1 or less, (w + x) / (w + x + y) represents a real number of 0.5 to 0.99, and (w) / (w + x) represents a real number of 0.05 to 1. Represents.   The photosensitive composition according to claim 1, further comprising a sensitizing dye.   Furthermore, a polymerizable compound is contained, The photosensitive composition of Claim 1 or Claim 2 characterized by the above-mentioned. A support;
An intermediate layer formed on the support using a coupling agent having a polymerizable group or a coupling agent having a photoinitiator site;
The intermediate layer produced by bringing the photosensitive composition according to any one of claims 1 to 3 into contact with the intermediate layer and then applying energy like the image to the photosensitive composition. An image-like polymer layer composed of a polymer directly bonded to the layer surface;
A laminate characterized by comprising: A support;
An intermediate layer formed on the support using a coupling agent having a polymerizable group or a coupling agent having a photoinitiator site;
The intermediate layer produced by bringing the photosensitive composition according to any one of claims 1 to 3 into contact with the intermediate layer and then applying energy like the image to the photosensitive composition. An image-like polymer layer composed of a polymer directly bonded to the layer surface;
Metal particles contained in the image-like polymer layer;
A metal-containing film material characterized by comprising:   6. The metal-containing film material according to claim 5, wherein the film thickness of the polymer layer is in a range of 200 nm to 2000 nm.   A light-shielding material comprising the metal-containing film material according to claim 5. Forming an intermediate layer using a coupling agent having a polymerizable group on the support or a coupling agent having a photoinitiator site;
After contacting the photosensitive composition according to any one of claims 1 to 3 to the intermediate layer, energy is imparted to the photosensitive composition in an image-like manner to the surface of the intermediate layer. Forming an image-like polymer layer comprising a polymer formed by direct bonding;
A method of producing a metal film-containing film material, comprising: applying metal ions to the polymer layer, and then reducing the metal ions to precipitate metal particles.