JP2009191179A - Photopolymerization initiator, polymerizable composition, and method for producing polymer. - Google Patents

Abstract

（式中、ｎは１〜４を表し、ｍは２〜４を表す。Ｒ²、Ｒ¹⁰、Ｒ¹⁶、Ａｒ¹、Ａｒ²、およびＡｒ³は連結基を表し、Ｒ¹、Ｒ³〜Ｒ⁹、Ｒ¹¹〜Ｒ¹⁵は置換基を表す。）
【選択図】なしA novel photopolymerization initiator that can be cured with a small addition amount and with a small amount of light irradiation energy, and can suppress coloring and odor after curing of the polymerizable composition, and a polymerizable composition using the photopolymerization initiator Is to provide things.
A photopolymerization initiator represented by the following general formula (1). General formula (1)

(In the formula, n represents 1 to 4, m represents 2 to 4. R ² , R ¹⁰ , R ¹⁶ , Ar ¹ , Ar ² , and Ar ³ represent linking groups, and R ¹ , R ³ to R ⁹ and R ^{11 to} R ¹⁵ represent a substituent.)
[Selection figure] None

Description

  The present invention relates to a novel photopolymerization initiator, a polymerizable composition, and a method for producing a polymer using the polymerizable composition. More specifically, free radicals are efficiently generated by irradiation with energy rays, particularly light, and the polymerizable composition is reliably polymerized in a short time by a polymerization reaction or a crosslinking reaction using the generated radicals and has good physical properties. Regarding materials and methods capable of obtaining a polymer, and further, molding resin, casting resin, stereolithography resin, sealant, dental polymerization resin, printing ink, inkjet ink, paint, photosensitive for printing plate Resin, Color proof for printing, Resist for color filter, Resist for black matrix, Photo spacer for liquid crystal, Screen material for rear projection, Optical fiber, Rib material for plasma display, Dry film resist, Resist for printed circuit board, Solder resist, For semiconductor Photoresist for microelectronics Resist, etching resist, microlens array, insulation material, hologram material, optical switch, waveguide material, overcoat agent, powder coating, adhesive, adhesive, release agent, optical recording medium , Adhesives, release coating agents, compositions for image recording materials using microcapsules, novel photopolymerization initiators and polymerizations for obtaining polymers having good physical properties in the fields of various devices, etc. The present invention relates to a polymerizable composition and a method for producing a polymer using the polymerizable composition.

  Photopolymerization initiators that cause polymerization of acrylates and the like by irradiation with UV light are used in a wide range of fields. For commercially available photopolymerization initiators, Photopolymer Social Network, “Sensitive Material List Book”, 55-72. Page, 1996 (Bunshin Publishing).

  In recent years, researches on photopolymerization initiators having higher sensitivity than those of commercially available photopolymerization initiators have been actively conducted, and an example thereof is an α-aminoketone derivative (Patent Document 1). When the derivative has a substituent containing a sulfur atom or an oxygen atom at the 4-position of the phenyl group, the derivative is, for example, a photocuring initiator of a photocuring system containing a pigment such as a UV curable printing ink. It is known that this is suitable (Patent Documents 2 and 3). It is also known that an α-aminoketone derivative having an amino group at the 4-position of the phenyl group is used in combination with a photosensitizer of an aromatic carbonyl compound (Patent Document 4). An α-aminoketone derivative in which the phenyl group of the α-aminoketone derivative is an N-substituted carbazole group is also known (Patent Document 5). It is known that the polymerizable composition containing the α-aminoketone derivative is a highly sensitive polymerizable composition that can be cured with a small amount of light irradiation. However, from the viewpoint of cost reduction and productivity improvement in recent years, while there is a need for a highly sensitive polymerizable composition that can be cured in a shorter time and with a smaller amount of light irradiation, the above α-aminoketone can be used. Even systems using both derivatives and aromatic carbonyl compound photosensitizers were not sensitive enough to accommodate the various newly proposed processes. Therefore, a polymerizable composition containing an α-aminoketone containing at least one allyl group or arylalkyl group at the α-position as a highly sensitive photopolymerization initiator has been proposed (Patent Document 6). Moreover, the alpha-amino ketone derivative which contains two functional groups in the same molecule as a highly sensitive photoinitiator was also proposed (patent document 7). Furthermore, a polymerizable composition containing an α-aminoketone derivative (Patent Document 8) containing a heteroatom-containing aromatic ring condensed group having an arylcarbonyl group introduced therein has also been proposed.

  On the other hand, when a conventional photoinitiator is used, various problems occur in addition to the curable surface of the polymerizable composition. Among them, the problems of coloring such as yellowing due to the photopolymerization initiator derived after curing of the polymerizable composition, and the problems of volatilization and odor of the photopolymerization initiator caused by the polymerizable composition cured after light irradiation are the major problems in recent years. Has been. The problem of coloring due to the photopolymerization initiator derived after curing of the polymerizable composition is not preferable because it deteriorates the color tone of the polymerizable composition, and may further limit the use that can be used. In addition, the problem of volatilization and odor of the photopolymerization initiator that occurs from the polymerizable composition cured after light irradiation not only affects the coated product, but also the environment of the coated site, and further the performance of the coated product. Improvements are needed because it can lead to degradation. Then, the photoinitiator which aimed at the volatilization and odor improvement of the photoinitiator after polymeric composition hardening was also proposed (patent document 7, 9, 10). However, even in a polymerizable composition using these photopolymerization initiators, suppression of volatilization and odor of the photopolymerization initiator that occurs from the polymerizable composition after further curing is desired.

JP-A-54-99185 JP 58-157805 A JP 59-167546 A JP-A-60-84248 JP 61-21104 A Japanese Unexamined Patent Publication No. 63-264560 JP-T-2002-530372 JP 2006-206799 A JP-T-2006-525399 Special table 2007-525573

  The polymerizable composition containing these conventionally known polymerization initiators can be used in various applications. However, from the viewpoint of cost reduction and productivity improvement, a material that can be cured with a small addition amount and a small light irradiation energy, that is, a highly sensitive material is required. On the other hand, these polymerizable compositions need to suppress coloring as much as possible because coloring such as yellowing after curing of the polymerizable composition becomes a problem. In addition, the volatilization and odor generation of the photopolymerization initiator and photopolymerization initiator decomposition products that occur from the polymerizable composition after curing may damage the environment of the coated product and the coating site, and may deteriorate the performance of the coated product. Therefore, improvement is required. In the polymerizable composition, it is difficult to satisfy all the requirements regarding curability, coloring that occurs after curing of the polymerizable composition, and volatilization and odor of the photopolymerization initiator that occurs from the polymerizable composition. Accordingly, an object of the present invention is to provide a novel photopolymerization initiator and a polymerizable composition using the photopolymerization initiator for satisfying all these requirements.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention. That is, the present invention is a photopolymerization initiator represented by the following general formula (1), the following general formula (2), or the following general formula (3).

General formula (1)

General formula (2)

General formula (3)

(In the formula, n represents 1 to 4, and m represents 2 to 4.
R ¹ , R ⁶ , R ⁷ , R ¹¹ , and R ¹² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group. Represents a substituted alkenyl group.
R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group when n is 1, and n is 2 If it is, -O -, - S -, - CO -, - N (R 17) -, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic Represents a group, a substituted or unsubstituted alkenylene group, or a combination thereof, or a direct bond. When n is 3, it represents a trivalent linking group. When n is 4, it represents a tetravalent linking group. .
R ¹⁰ and R ¹⁶ are each independently, when m is 2, —O—, —S—, —CO—, —N (R ¹⁷ ) —, a substituted or unsubstituted alkylene group, substituted or unsubstituted Represents a substituted arylene group, a substituted or unsubstituted divalent heterocyclic group, a substituted or unsubstituted alkenylene group, or a combination thereof, or a direct bond. When m is 3, a trivalent linking group is represented. , M represents 4, it represents a tetravalent linking group.
R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle Represents a group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group. R ³ and R ⁴ , R ⁸ and R ⁹ , and R ¹³ and R ¹⁴ may form a ring.
R ⁵ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Substituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted Or an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted arylamino Group, substituted or unsubstituted diarylamino group, substituted or Substituted alkyl arylamino group, or a halogen atom.
R ¹⁷ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.
At least one of R ¹ and R ⁵ , at least one of R ⁶ and R ⁷ , and at least one of R ¹¹ , R ¹² and R ¹⁵ are each a reactive functional group —R ¹⁸ —. ^{OH, -R 18 -COOH, -R 18} -CONH 2, -R 18 -N = C = O, -R 18 -N = C = S, -R 18 -NH 2, -R 18 -NH (R 19 ) Or the following general formula (4).
Ar ¹ , Ar ² , and Ar ³ each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.
A ¹ and A ² each independently represent the following general formula (5), general formula (6), general formula (7), or general formula (8).
A ³ represents the following general formula (9), general formula (10), general formula (11), or general formula (12). )

General formula (4)

(Wherein R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ¹⁸ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a combination thereof, or a direct bond.
R ¹⁹ represents a substituted or unsubstituted alkyl group. )

General formula (5)

General formula (6)

General formula (7)

General formula (8)

Wherein Y ¹ and Z ¹ are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ¹⁷ ) —, —CO—, —CH ₂ —, — CH ₂ CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms or a direct bond;
U ¹ represents —O—, —S—, or —N (R ¹⁷ ) —,
V ¹ and W ¹ represent a nitrogen atom. )

General formula (9)

General formula (10)

Formula (11)

Formula (12)

(Wherein Y ² and U ² each independently represent a nitrogen atom bonded to R ¹⁶ ;
Z ² represents —O—, —S—,>S═O,> SO ₂ , —N (R ¹⁷ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—. Represents an alkylidene group having 2 to 6 carbon atoms or a direct bond,
V ² and W ² represent a nitrogen atom. )

The present invention further, A ¹ is directed to the photopolymerization initiator is a general formula (5).

The present invention further, A ² is directed to the photopolymerization initiator is a general formula (5).

The present invention further, A ³ is directed to the photopolymerization initiator is a general formula (9).

  Furthermore, the present invention relates to a photopolymerization initiator obtained by reacting the photopolymerization initiator with a compound having a group capable of reacting with the reactive functional group of the photopolymerization initiator.

The invention further reactive functional groups are the general formula ^{(4), - R 18 -NH} 2, or to the photopolymerization initiator is -R ¹⁸ -OH.

  Furthermore, the present invention provides the above photopolymerization start wherein the reactive functional group is the general formula (4), and the compound having a group capable of reacting with the reactive functional group of the photopolymerization initiator is a compound having radical polymerizability. It relates to the agent.

Further, in the present invention, the compound having a reactive functional group of —R ¹⁸ —NH ₂ and a group capable of reacting with the reactive functional group of the photopolymerization initiator is an isocyanate group, an epoxy group, a carboxyl group, an alkylsilyl group. The photopolymerization initiator is a compound having a group or an alkoxysilyl group.

Further, in the present invention, the reactive functional group is —R ¹⁸ —OH, and the compound having a group capable of reacting with the reactive functional group of the photopolymerization initiator is an isocyanate group, an epoxy group, a —COCl group, or a carboxyl group. It is related with the said photoinitiator which is a compound which has group.

  Furthermore, this invention relates to the manufacturing method of the photoinitiator obtained by making the said photoinitiator and the compound which has a group which can react with the reactive functional group which the said photoinitiator has reacting.

  The present invention further relates to a polymerizable composition comprising the photopolymerization initiator (A) and the radical polymerizable compound (B).

  Furthermore, this invention relates to the polymeric composition whose said photoinitiator (A) is a photoinitiator which has a radically polymerizable group.

  Furthermore, this invention relates to the manufacturing method of a polymer which irradiates and polymerizes the said polymeric composition by the energy ray containing the light of the wavelength range of 250 nm to 450 nm.

  The photopolymerization initiator of the present invention replaces the benzene ring moiety of a conventionally known α-aminoketone derivative with a group represented by the above general formulas (5) to (12) having an arylcarbonyl group or a heterocyclic carbonyl group. Therefore, it has a good absorption characteristic in the energy region, particularly in a wavelength region of 250 nm to 450 nm, and it has a very high sensitivity photoradical without using a photosensitizer for light irradiation in the wavelength region. It can function as a generator. Therefore, if the photopolymerization initiator of the present invention is used, a polymerization reaction utilizing a radical generated from a photopolymerization initiator of a conventionally known α-aminoketone derivative, a crosslinking reaction, etc. can be realized in a shorter time. As a result, it is possible to realize a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. In addition, since the photopolymerization initiator of the present invention has its specific structure, in the polymerizable composition containing the photopolymerization initiator, coloring after curing by light irradiation or from the polymerizable composition after curing It is possible to suppress the volatilization and odor of the photopolymerization initiator that occurs.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, the photopolymerization initiator of the present invention will be described. The photopolymerization initiator of the present invention has a structure represented by the general formulas (1) to (3), and the benzene ring portion in a conventionally known α-aminoketone derivative is substituted with an arylcarbonyl group or a heterocyclic carbonyl group. It has a characteristic structure replaced by the structure represented by the general formulas (5) to (12). In addition, by introducing this arylcarbonyl group or heterocyclic carbonyl group, the compound of the present invention can have light absorption characteristics suitable for a wavelength region of 250 nm to 450 nm. In addition, by having this structure, the compound of the present invention decomposes very efficiently without using a sensitizer in combination with light irradiation in the wavelength region, and as a result, a large amount of radicals can be efficiently decomposed. It can function as a highly sensitive material that occurs in

General formula (1)

General formula (2)

General formula (3)

(In the formula, n represents 1 to 4, and m represents 2 to 4.
R ¹ , R ⁶ , R ⁷ , R ¹¹ , and R ¹² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group. Represents a substituted alkenyl group.
R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group when n is 1, and n is 2 If it is, -O -, - S -, - CO -, - N (R 17) -, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic Represents a group, a substituted or unsubstituted alkenylene group, or a combination thereof, or a direct bond. When n is 3, it represents a trivalent linking group. When n is 4, it represents a tetravalent linking group. .
R ¹⁰ and R ¹⁶ are each independently, when m is 2, —O—, —S—, —CO—, —N (R ¹⁷ ) —, a substituted or unsubstituted alkylene group, substituted or unsubstituted Represents a substituted arylene group, a substituted or unsubstituted divalent heterocyclic group, a substituted or unsubstituted alkenylene group, or a combination thereof, or a direct bond. When m is 3, a trivalent linking group is represented. , M represents 4, it represents a tetravalent linking group.
R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle Represents a group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group. R ³ and R ⁴ , R ⁸ and R ⁹ , and R ¹³ and R ¹⁴ may form a ring.
R ⁵ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Substituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted Or an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted arylamino Group, substituted or unsubstituted diarylamino group, substituted or Substituted alkyl arylamino group, or a halogen atom.
R ¹⁷ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.
At least one of R ¹ and R ⁵ , at least one of R ⁶ and R ⁷ , and at least one of R ¹¹ , R ¹² and R ¹⁵ are each a reactive functional group —R ¹⁸ —. ^{OH, -R 18 -COOH, -R 18} -CONH 2, -R 18 -N = C = O, -R 18 -N = C = S, -R 18 -NH 2, -R 18 -NH (R 19 ) Or the following general formula (4).
Ar ¹ , Ar ² , and Ar ³ each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.
A ¹ and A ² each independently represent the following general formula (5), general formula (6), general formula (7), or general formula (8).
A ³ represents the following general formula (9), general formula (10), general formula (11), or general formula (12). )

General formula (4)

(Wherein R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ¹⁸ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a combination thereof, or a direct bond.
R ¹⁹ represents a substituted or unsubstituted alkyl group. )

General formula (5)

General formula (6)

General formula (7)

General formula (8)

Wherein Y ¹ and Z ¹ are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ¹⁷ ) —, —CO—, —CH ₂ —, — CH ₂ CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms or a direct bond;
U ¹ represents —O—, —S—, or —N (R ¹⁷ ) —,
V ¹ and W ¹ represent a nitrogen atom. )

General formula (9)

General formula (10)

Formula (11)

Formula (12)

(Wherein Y ² and U ² each independently represent a nitrogen atom bonded to R ¹⁶ ;
Z ² represents —O—, —S—,>S═O,> SO ₂ , —N (R ¹⁷ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—. Represents an alkylidene group having 2 to 6 carbon atoms or a direct bond,
V ² and W ² represent a nitrogen atom. )

  Next, the structure of the photopolymerization initiator (A) of the present invention will be described in detail.

  As shown in the general formulas (1) to (3), the photopolymerization initiator (A) of the present invention can introduce various substituents as long as the properties are not impaired. By introducing a substituent, the photopolymerization initiator (A) of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as the maximum absorption wavelength and transmittance, and the solubility in the resin or solvent used together.

R ¹ , R ⁶ , R ⁷ , R ¹¹ and R ¹² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group Of the alkenyl group.

Here, the substituted or unsubstituted alkyl group in R ¹ , R ⁶ , R ⁷ , R ¹¹ and R ¹² is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms. Or a linear, branched, monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto.

Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —CH ₂ —O—CH ₃ and —CH ₂ —CH. _2— O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _{P 1} —CH ₃ (where P1 is 1 to 8) ), — (CH ₂ —CH ₂ —CH ₂ —O) _{Q 1} —CH ₃ (where Q 1 is an integer of 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH Examples include _2- CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _2, but are not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryl group in R ¹ , R ⁶ , R ⁷ , R ¹¹ and R ¹² include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples include a phenyl group. 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group 2-azurenyl group, 1-acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2, 5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl Nyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like can be mentioned. However, it is not limited to these.

Examples of the substituted or unsubstituted heterocyclic group in R ¹ , R ⁶ , R ⁷ , R ¹¹ and R ¹² include aromatics having 4 to 24 carbon atoms, including nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms, or And aliphatic heterocyclic groups such as 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl. Group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl Group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4 -Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenant Lysinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group Pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholini Nyl group, thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-coumarinyl group, etc. is not.

Examples of the substituted or unsubstituted alkenyl group for R ¹ , R ⁶ , R ⁷ , R ¹¹ and R ¹² include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 2 to 18 carbon atoms. , They may have a plurality of carbon-carbon double bonds in the structure. Specific examples thereof include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl. Group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, Examples include cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group, and the like. There.

R ¹ , R ⁶ , R ⁷ , R ^11, and R ¹² may be bonded to adjacent carbon atoms at substitution positions other than those described above, and these are also R ¹ , R ⁶ , R ⁷ , It is included in the category of substituents represented by R ¹¹ and R ¹² .

R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group when n is 1.

The substituted or unsubstituted alkyl group for R ^{2 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ .

The substituted or unsubstituted aryl group for R ^{2 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ .

The substituted or unsubstituted heterocyclic group for R ^{2 has the same} meaning as the substituted or unsubstituted heterocyclic group described for R ¹ .

The substituted or unsubstituted alkenyl group for R ² has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ .

R ² represents, when n is 2, —O—, —S—, —CO—, —N (R ¹⁷ ) —, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, substituted or unsubstituted It represents a substituted divalent heterocyclic group, a substituted or unsubstituted alkenylene group, a combination thereof, or a direct bond.

Examples of the substituted or unsubstituted alkylene group in R ² include a divalent group formed by removing one hydrogen atom from the same substituent as the substituted or unsubstituted alkyl group described in R ^1. However, it is not limited to these.

Examples of the substituted or unsubstituted arylene group in R ² include a divalent group formed by removing one hydrogen atom from the same substituent as the substituted or unsubstituted aryl group described in R ^1. However, it is not limited to these.

The divalent heterocyclic group substituted or unsubstituted in R ^2, a divalent group formed by removing one hydrogen atom from the same substituents as substituted or unsubstituted heterocyclic group described in R ¹ It can be mentioned, but is not limited to these.

Examples of the substituted or unsubstituted alkenylene group in R ² include a divalent group formed by removing one hydrogen atom from the same substituent as the substituted or unsubstituted alkenyl group described in R ^1. However, it is not limited to these.

R ² represents a trivalent linking group when n is 3.

The trivalent linking group for R ² includes —N <, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or these —N <, substituted or unsubstituted aliphatic. A trivalent linking group comprising a combination of a hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, and —O—, —S—, —CO—, and —N (R ¹⁷ ) — is represented. The aliphatic hydrocarbon group may be linear, branched, monocyclic or condensed polycyclic, and may have an unsaturated bond.

  Specific examples of the trivalent linking group include the following, but are not limited thereto.

R ² represents a tetravalent linking group when n is 4.

The tetravalent linking group for R ² includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aliphatic hydrocarbon group, substituted or unsubstituted. And a tetravalent linking group comprising a combination of —O—, —S—, —CO—, —N <, —N (R ¹⁷ ) —. The aliphatic hydrocarbon group may be linear, branched, monocyclic or condensed polycyclic, and may have an unsaturated bond.

  Specific examples of the tetravalent linking group include the following, but are not limited thereto.

R ¹⁰ and R ¹⁶ are each independently, when m is 2, —O—, —S—, —CO—, —N (R ¹⁷ ) —, a substituted or unsubstituted alkylene group, substituted or unsubstituted. An arylene group, a substituted or unsubstituted divalent heterocyclic group, a substituted or unsubstituted alkenylene group, a combination thereof, or a direct bond.

The substituted or unsubstituted alkylene group for R ¹⁰ and R ¹⁶ has the same meaning as the substituted or unsubstituted alkylene group described for R ² .

The substituted or unsubstituted arylene group for R ¹⁰ and R ¹⁶ has the same meaning as the substituted or unsubstituted arylene group described for R ² .

The substituted or unsubstituted divalent heterocyclic group for R ¹⁰ and R ¹⁶ has the same meaning as the substituted or unsubstituted divalent heterocyclic group described for R ² .

The substituted or unsubstituted alkenylene group for R ¹⁰ and R ¹⁶ has the same meaning as the substituted or unsubstituted alkenylene group described for R ² .

R ¹⁰ and R ¹⁶ represent a trivalent linking group when m is 3.

The trivalent linking group for R ¹⁰ and R ¹⁶ has the same meaning as the trivalent linking group described for R ² .

R ¹⁰ and R ¹⁶ represent a tetravalent linking group when m is 4.

The tetravalent linking group for R ¹⁰ and R ¹⁶ has the same meaning as the tetravalent linking group described for R ² .

R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted complex, A cyclic group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group is represented.

The substituted or unsubstituted alkyl group in R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ has the same meaning as the substituted or unsubstituted alkyl group described for R ¹ .

The substituted or unsubstituted aryl group in R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ has the same meaning as the substituted or unsubstituted aryl group described for R ¹ .

The substituted or unsubstituted heterocyclic group in R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ has the same meaning as the substituted or unsubstituted heterocyclic group described in R ¹ .

The substituted or unsubstituted alkenyl group for R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ .

The substituted or unsubstituted acyl group for R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ is a hydrogen atom or a linear, branched, monocyclic or condensed group having 1 to 18 carbon atoms. A carbonyl group to which a polycyclic aliphatic group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a carbon number of 4 to Examples include a carbonyl group to which 18 monocyclic or condensed polycyclic heterocyclic groups are bonded, and specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, Lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group Crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, etc. It can be mentioned, but is not limited to these. In addition, the aryl group and the carbonyl group, the heterocyclic group and the carbonyl group may be bonded at positions other than those described above, and these are also R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and It is included in the category of the substituent represented by R ¹⁴ .

R ³ and R ⁴ , R ⁸ and R ⁹ , and R ¹³ and R ¹⁴ may be combined to form a ring.

When R ³ and R ⁴ , R ⁸ and R ⁹ , and R ¹³ and R ¹⁴ together form a ring, the formed site includes a substituted or unsubstituted alkylene group, a substituted or unsubstituted group, Examples thereof include an oxaalkylene group, a substituted or unsubstituted thiaalkylene group, and a substituted or unsubstituted azaalkylene group.

  Here, as the ring formed when the substituted or unsubstituted alkylene group is an alkylene group having 2 to 6 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, or the like is formed. Examples can be given, but the present invention is not limited to these examples.

  A substituted or unsubstituted oxaalkylene group having 2 to 6 carbon atoms, a substituted or unsubstituted thiaalkylene group having 2 to 6 carbon atoms, or a substituted or unsubstituted azaalkylene group. The ring formed in the case of an azaalkylene group having 2 to 6 carbon atoms includes morpholine ring, thiomorpholine ring, thiazolidine ring, piperazine ring, homopiperazine ring, propyleneimine ring, pyrrolidine ring, piperidine ring, or pipecoline Forming a ring or the like can be mentioned as an example, but is not limited thereto.

R ⁵ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Substituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted Or an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted arylamino Group, substituted or unsubstituted diarylamino group, substituted or Substituted alkyl arylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group for R ⁵ and R ¹⁵ has the same meaning as the substituted or unsubstituted alkyl group described for R ¹ .

The substituted or unsubstituted aryl group for R ⁵ and R ¹⁵ has the same meaning as the substituted or unsubstituted aryl group described for R ¹ .

The substituted or unsubstituted heterocyclic group for R ⁵ and R ¹⁵ has the same meaning as the substituted or unsubstituted heterocyclic group described for R ¹ .

The substituted or unsubstituted alkenyl group for R ⁵ and R ¹⁵ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ .

The substituted or unsubstituted acyl group for R ⁵ and R ¹⁵ has the same meaning as the substituted or unsubstituted acyl group described for R ³ .

The substituted or unsubstituted alkoxyl group in R ⁵ and R ¹⁵ is a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or one having 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkoxyl groups interrupted by the above -O-. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) P2 -CH 3 (Where P2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _Q2 —CH ₃ (where Q2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted with one or more —O— include the following, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryloxy group in R ⁵ and R ¹⁵ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto. In addition, the aryl group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ and R ¹⁵ of the present invention.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ⁵ and R ¹⁵ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carba A zolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, a 9-acridinyloxy group, and the like can be mentioned, but are not limited thereto. Further, the heterocyclic group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ and R ¹⁵ of the present invention.

As the substituted or unsubstituted acyloxy group in R ⁵ and R ^15, a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, Alternatively, a carbonyloxy group to which a monocyclic or condensed aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom Examples include a carbonyloxy group to which a heterocyclic group is bonded. Specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, a lauroyloxy group, Myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyl group Si group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, Examples include cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, and 5-naphthacenoyloxy group. It is not limited. In addition, the aryl group and the carbonyloxy group, the heterocyclic group and the carbonyloxy group may be bonded at positions other than those described above, and these are also in the category of the substituent represented by R ⁵ and R ¹⁵ of the present invention. included.

Examples of the substituted or unsubstituted alkoxycarbonyl group in R ⁵ and R ¹⁵ include an alkoxycarbonyl group having 2 to 20 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanyl Phenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2 Chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy A carbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. are mentioned. Further, the aryl group and the —OCO— bond may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ and R ¹⁵ of the present invention.

Examples of the substituted or unsubstituted alkylthio group in R ⁵ and R ¹⁵ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylthio group in R ⁵ and R ¹⁵ include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, and 2-naphthylthio group. Groups, 9-anthrylthio groups, 9-phenanthrylthio groups, and the like, but are not limited thereto. In addition, the aryl group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ and R ¹⁵ of the present invention.

Examples of the substituted or unsubstituted heterocyclic thio group in R ⁵ and R ¹⁵ include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group. Group, 4-carbazolylthio group and the like can be mentioned, but not limited thereto. Further, the heterocyclic group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ and R ¹⁵ of the present invention.

Examples of the substituted or unsubstituted alkylamino group in R ⁵ and R ¹⁵ include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, and nonylamino group. Group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1- Damantamino group, and a 2-Adamantamino group, etc., but is not limited thereto.

Examples of the substituted or unsubstituted dialkylamino group in R ⁵ and R ¹⁵ include a dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, Dinonylamino group, didecylamino group, didodecylamino group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, Examples thereof include, but are not limited to, a cyclopropylamino group, a pyrrolidino group, a piperidino group, and a piperazino group.

Examples of the substituted or unsubstituted arylamino group in R ⁵ and R ¹⁵ include an N-arylamino group, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p- Toluino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group, indolino group, etc. It can be mentioned, but is not limited to these.

Examples of the substituted or unsubstituted diarylamino group in R ⁵ and R ¹⁵ include a diarylamino group, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group. However, it is not limited to these.

Examples of the substituted or unsubstituted alkylarylamino group in R ⁵ and R ¹⁵ include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N -Isopropyl, N-pentylanilino group, N-ethylanilino group, N-methyl-1-naphthylamino group and the like can be mentioned, but are not limited thereto.

Examples of the halogen atom in R ⁵ and R ¹⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ¹⁷ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.

The substituted or unsubstituted alkyl group for R ^{17 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ .

The substituted or unsubstituted aryl group for R ^{17 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ .

The substituted or unsubstituted heterocyclic group for R ^{17 has the same} meaning as the substituted or unsubstituted heterocyclic group described for R ¹ .

The substituted or unsubstituted alkenyl group for R ¹⁷ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ .

At least one of R ¹ and R ⁵ , at least one of R ⁶ and R ⁷ , and at least one of R ¹¹ , R ¹² and R ¹⁵ are each a reactive functional group —R ¹⁸ —OH, _{^{-R 18 -COOH, -R 18 -CONH 2}} , -R 18 -N = C = O, -R 18 -N = C = S, -R 18 -NH 2, -R 18 -NH (R 19), Or represents general formula (4).

R ¹⁸ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a combination thereof, or a direct bond.

The substituted or unsubstituted alkylene group for R ¹⁸ has the same meaning as the substituted or unsubstituted alkylene group described for R ² .

The substituted or unsubstituted arylene group for R ¹⁸ has the same meaning as the substituted or unsubstituted arylene group described for R ² .

R ¹⁹ represents a substituted or unsubstituted alkyl group.

The substituted or unsubstituted alkyl group for R ^{19 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ .

R ²⁰ , R ²¹ , and R ²² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.

The substituted or unsubstituted alkyl group for R ²⁰ , R ²¹ , and R ²² has the same meaning as the substituted or unsubstituted alkyl group described for R ¹ .

Ar ¹ , Ar ² , and Ar ³ each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.

The substituted or unsubstituted arylene group in Ar ¹ , Ar ² , and Ar ³ has the same meaning as the substituted or unsubstituted arylene group described for R ² .

The substituted or unsubstituted divalent heterocyclic group in Ar ¹ , Ar ² , and Ar ³ has the same meaning as the substituted or unsubstituted divalent heterocyclic group described for R ² .

A ¹ and A ² each independently represent General Formula (5), General Formula (6), General Formula (7), or General Formula (8).

Examples of the alkylidene group having 2 to 6 carbon atoms in Y ¹ and Z ¹ include an alkylidene group having 2 to 6 carbon atoms, specifically, an ethylidene group, a propylidene group, a butylidene group, an isobutylidene group, a pentylidene group, Examples include a pentylidene group, a hexylidene group, a cyclohexylidene group, and a benzylidene group.

  Specific examples of the general formula (5), the general formula (6), the general formula (7), or the general formula (8) include a substituted or unsubstituted divalent benzofuranyl group, a substituted or unsubstituted 2 Valent benzothienyl group, substituted or unsubstituted divalent indenyl group, substituted or unsubstituted divalent carbazolyl group, substituted or unsubstituted divalent dibenzofuranyl group, substituted or unsubstituted divalent dibenzo Thiophenyl group, substituted or unsubstituted divalent fluorenyl group dibenzo [b, e] [1,4] dioxinyl group, substituted or unsubstituted divalent phenoxathiinyl group, substituted or unsubstituted divalent Phenothiazinyl group, substituted or unsubstituted divalent thiantenyl group, substituted or unsubstituted divalent xanthenyl group, substituted or unsubstituted divalent thioxanthenyl group, substituted Or an unsubstituted divalent phenoxazinyl group, a substituted or unsubstituted divalent benzoxazolyl group, a substituted or unsubstituted divalent benzothiazolyl group, a substituted or unsubstituted divalent benzimidazolyl group, substituted or Unsubstituted divalent indazolyl group, substituted or unsubstituted divalent 1,2-benzisoxazolyl group, substituted or unsubstituted divalent iminostilbenyl group, substituted or unsubstituted divalent divalent Although a xanthonyl group etc. can be mentioned, it is not limited to these.

  Of the general formula (5), general formula (6), general formula (7), or general formula (8), the general formula (5) is preferable in terms of the difficulty of synthesis and sensitivity as a radical generator. 5), a substituted or unsubstituted divalent benzoxazolyl group, a substituted or unsubstituted divalent benzothiazolyl group, a substituted or unsubstituted divalent benzimidazolyl group, substituted or unsubstituted A substituted divalent indazolyl group, more preferably a group represented by the general formula (5), among which a substituted or unsubstituted divalent carbazolyl group, a substituted or unsubstituted divalent phenoxathinyl group Group, substituted or unsubstituted divalent phenothiazinyl group, substituted or unsubstituted divalent thiantenyl group, substituted or unsubstituted divalent xanthenyl group, substituted or unsubstituted divalent thioxa Thenyl group, a divalent phenoxazinyl group substituted or unsubstituted, are particularly preferred.

A ³ in the general formula (3) represents the general formula (9), the general formula (10), the general formula (11), or the general formula (12).

The alkylidene group having 2 to 6 carbon atoms in Y ² and Z ² has the same meaning as the alkylidene group having 2 to 6 carbon atoms described in Y ¹ .

  Specific examples represented by general formula (9), general formula (10), general formula (11), or general formula (12) include general formula (5), general formula (6), and general formula (7). Or it is synonymous with the group demonstrated by General formula (8).

  Of the general formula (9), the general formula (10), the general formula (11), or the general formula (12), the general formula (9) is preferable from the viewpoint of the difficulty of synthesis and the sensitivity as a radical generator. 9) and a substituted or unsubstituted divalent benzoxazolyl group, a substituted or unsubstituted divalent benzothiazolyl group, a substituted or unsubstituted divalent benzimidazolyl group, substituted or unsubstituted A substituted divalent indazolyl group, more preferably a group represented by the general formula (9), among which a substituted or unsubstituted divalent carbazolyl group, a substituted or unsubstituted divalent phenoxathiinyl group Group, substituted or unsubstituted divalent phenothiazinyl group, substituted or unsubstituted divalent thiantenyl group, substituted or unsubstituted divalent xanthenyl group, substituted or unsubstituted divalent thienyl group. Xanthenyl group, a divalent phenoxazinyl group substituted or unsubstituted, are particularly preferred.

R ^{1 to} R ²² , Ar ^{1 to} Ar ³ , or A ^{1 to} A ³ described above may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group and a carboxyl group. , Sulfone group, sulfonyl chloride group, amide group, cyano group, nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group , Arylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzylamino group, dibenzylamino group, alkylsilyl group, alkoxysilyl group, etc. Is mentioned.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms and interrupted by one or more —O—. , Branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —CH ₂ —O—CH ₃ and —CH ₂ —CH. _2— O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _{P 1} —CH ₃ (where P1 is 1 to 8) ), — (CH ₂ —CH ₂ —CH ₂ —O) _{Q 1} —CH ₃ (where Q 1 is an integer of 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH _{2 -CH 3 -, - CH 2} -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, Examples include 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyl group, 2 -Thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

Examples of the alkoxyl group include a straight chain, branched chain, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or a group having 2 to 18 carbon atoms and interrupted by one or more —O—. Examples thereof include a chain, branched chain, monocyclic or condensed polycyclic alkoxyl group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) P2 -CH 3 (Where P2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _Q2 —CH ₃ (where Q2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. It is done.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 2-furanyloxy group. 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group , 4-carbazolyloxy group, 9-acridinyloxy group and the like.

  The acyloxy group includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

  Examples of the arylthio group include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 2-furylthio group. 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, an ethyldimethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, and a trioctylsilyl group.

  Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Can be mentioned.

  Since the photopolymerization initiator of the present invention has at least one reactive substituent, it is further reacted with a compound having a group capable of reacting with the reactive functional group of the photopolymerization initiator. It is also possible to obtain a photopolymerization initiator.

Compounds having a group capable of reacting with the reactive functional groups of the photopolymerization initiator has the present ^{invention, -R 18 -OH, -R 18 -COOH} , -R 18 -CONH 2, -R 18 -N = C = There is no particular limitation as long as it is a compound capable of reacting with O, —R ¹⁸ —N═C═S, —R ¹⁸ —NH ₂ , —R ¹⁸ —NH (R ¹⁹ ), or the above general formula (4). It is possible to use.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —OH include an isocyanate group, an epoxy group, a carboxyl group, an alkylsilyl group, or an alkoxysilyl group.

Examples of the trialkylsilyl group in the group capable of reacting with the reactive functional group —R ¹⁸ —OH include a trimethylsilyl group, a triethylsilyl group, an ethyldimethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, And a trioctylsilyl group.

The trialkoxylsilyl group in the group capable of reacting with the reactive functional group —R ¹⁸ —OH includes a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group, a dimethoxymethylsilyl group, and a diethoxy group. Examples include a methylylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —COOH include a hydroxyl group or an epoxy group.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —CONH ₂ include an isocyanate group, an epoxy group, a —COCl group, or a carboxyl group.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —N═C═O include a hydroxyl group, an amino group, and a carboxyl group.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —N═C═S include a hydroxyl group, an amino group, or a carboxyl group.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —NH ₂ include an isocyanate group, an epoxy group, a —COCl group, or a carboxyl group.

Preferable examples of the group capable of reacting with the reactive functional group —R ¹⁸ —NH (R ¹⁹ ) include an isocyanate group, an epoxy group, a —COCl group, or a carboxyl group.

  Preferable examples of the group capable of reacting with the general formula (4) include a group having an ethylenically unsaturated double bond, and more preferable is a group represented by the general formula (4).

The reactive functional group possessed by the photopolymerization initiator of the present invention is preferably a radical polymerizable group, -R ¹⁸ -OH, -R ¹⁸ -COOH, -R ¹⁸ -N = C in terms of performance such as curability. = O, a -R ¹⁸ -NH _2, or -R ¹⁸ -NH (R ^19), more preferably formula ^{(4), - R 18 -NH} 2, or -R ¹⁸ -OH.

  When the reactive substituent which the photoinitiator of this invention has is General formula (4), As a compound which can react with the reactive functional group which a photoinitiator has, it preferably has other radical polymerizability. A compound.

  The other radically polymerizable compound represents a compound having an ethylenically unsaturated double bond in the molecule, and more preferably a compound having a vinyl group, an acrylic group or a methacryl group at the molecular end.

  Representative of a new photopolymerization initiator obtained by reacting a photopolymerization initiator having a radical polymerizable group as at least one reactive substituent of the present invention with a compound having other radical polymerizability An example is described below.

  Example 1) A photopolymerization initiator (a) having a radical polymerizable group as a reactive substituent of the present invention and another radical polymerizable compound {(b): polypropylene glycol dimethacrylate} By radical polymerization, a new photopolymerization initiator (c) which is a copolymer of (a) and (b) is obtained.

  Example 2) A photopolymerization initiator (d) having a radical polymerizable group as a reactive substituent of the present invention and another radical polymerizable compound {(e): the photopolymerization initiator (d ) And the same compound} are radically polymerized to obtain a new photopolymerization initiator (f).

  Example 3) Radical polymerization of a photopolymerization initiator (g) having a radical polymerizable group as a reactive substituent of the present invention and another radical polymerizable compound (hydroxyethoxyethyl acrylate and propyl acrylate) A new photopolymerization initiator (h) is obtained by polymerization.

  Example 4) The following photopolymerization initiator (i) and the following radical polymerizable compound (j) are radically polymerized to form a new photopolymerization initiator (i) that is a copolymer of (i) and (j) ( k) is obtained.

  A new photopolymerization initiator obtained by reacting a photopolymerization initiator having a radically polymerizable group as at least one reactive substituent with a compound having other known and publicly available radical polymerization properties. Representative examples are shown, but other known and publicly available radically polymerizable compounds can also be reacted, and are not limited to these reaction examples. In addition, the molecular weight, stereoregularity, or composition of the compound to be reacted is not particularly limited, and the photopolymerization initiator obtained by the reaction is appropriately adjusted so as to obtain desired physical properties. I can do it.

When the photopolymerization initiator of the present invention has —R ¹⁸ —OH as at least one reactive substituent, a compound having a group capable of reacting with —R ¹⁸ —OH contained in the photopolymerization initiator; To obtain a new photopolymerization initiator. A typical example is shown below.

Example 5) A photopolymerization initiator (l) having —R ¹⁸ —OH as a reactive substituent of the present invention, and a compound having a group capable of reacting with —R ¹⁸ —OH contained in the photopolymerization initiator ( Hexamethylene diisocyanate) is reacted to obtain a new photopolymerization initiator (m).

Example 6) A photopolymerization initiator (n) having —R ¹⁸ —OH as a reactive substituent of the present invention, and a compound having a group capable of reacting with —R ¹⁸ —OH contained in the photopolymerization initiator ( A new photopolymerization initiator (p) is obtained by reacting with o).

Although the reaction example was shown above, it is also possible to react the compound which has a group which can react with other well-known publicly-used -R < ¹⁸ > -OH, It is not limited to these reaction examples. In addition, when the photopolymerization initiator obtained by the reaction is a polymer, the molecular weight of the photopolymerization initiator obtained by the reaction, stereoregularity, or the composition of the compound to be reacted is not particularly limited, It can be used by appropriately adjusting so as to obtain desired physical properties.

When the photopolymerization initiator of the present invention has —R ¹⁸ —COOH as at least one reactive substituent, a compound having a group capable of reacting with —R ¹⁸ —COOH contained in the photopolymerization initiator; To obtain a new photopolymerization initiator. A typical example is shown below.

Example 7) Compound (q) having —R ¹⁸ —COOH as a reactive substituent of the present invention and a compound having a group capable of reacting with —R ¹⁸ —COOH contained in photopolymerization initiator ( 2,2-bis (4-glycidyloxyphenyl) propane) is reacted to obtain a new photopolymerization initiator (r).

It showed reactivity example above, but it is also possible to react a compound having a group capable of reacting with other known and used -R ¹⁸ -COOH, but is not limited to these reactions examples. In addition, when the photopolymerization initiator obtained by the reaction is a polymer, the molecular weight of the photopolymerization initiator obtained by the reaction, stereoregularity, or the composition of the compound to be reacted is not particularly limited, It can be used by appropriately adjusting so as to obtain desired physical properties.

Photopolymerization initiator in the invention is, when it has -R ¹⁸ -N = C = O as at least one reactive substituent, and -R ¹⁸ -N = C = O with the the photopolymerization initiator A new photopolymerization initiator can be obtained by reacting with a compound having a reactive group. A typical example is shown below.

Example 8) Photopolymerization initiator (s) having —R ¹⁸ —N═C═O as a reactive substituent of the present invention, and —R ¹⁸ —N═C═O having a photopolymerization initiator A new photopolymerization initiator (t) is obtained by reacting with a compound having a reactive group (triethylene glycol).

Example 9) Photopolymerization initiator (u) having —R ¹⁸ —N═C═O as a reactive substituent of the present invention, and —R ¹⁸ —N═C═O having a photopolymerization initiator A new photopolymerization initiator (w) is obtained by reacting the compound (v) having a reactive group.

Example 10) Photopolymerization initiator (x) having —R ¹⁸ —N═C═O as a reactive substituent of the present invention, and —R ¹⁸ —N═C═O having a photopolymerization initiator A new photopolymerization initiator (z) is obtained by reacting the compound (y) having a reactive group.

Although the example of reaction was shown above, it is also possible to react the compound which has a group which can react with other well-known and public use -R < ¹⁸ > -N = C = O, It is not limited to these reaction examples. . In addition, when the photopolymerization initiator obtained by the reaction is a polymer, the molecular weight of the photopolymerization initiator obtained by the reaction, stereoregularity, or the composition of the compound to be reacted is not particularly limited, It can be used by appropriately adjusting so as to obtain desired physical properties.

When the photopolymerization initiator of the present invention has —R ¹⁸ —NH ₂ as at least one reactive substituent, it has a group capable of reacting with —R ¹⁸ —NH ₂ of the photopolymerization initiator. A new photopolymerization initiator can be obtained by reacting with a compound. A typical example is shown below.

With Example 11) a photopolymerization initiator having a -R ¹⁸ -NH ₂ as a reactive substituent present invention and (I), and -R ¹⁸ -NH ₂ having the photopolymerization initiator reactable groups A new photopolymerization initiator (III) is obtained by reacting with compound (II). Further, since the obtained photopolymerization initiator (III) has a radical polymerizable group, it can be reacted with another radical polymerizable compound to obtain a new photopolymerization initiator.

Example 12) Having a photopolymerization initiator (IV) having —R ¹⁸ —NH ₂ as a reactive substituent of the present invention and a group capable of reacting with —R ¹⁸ —NH ₂ of the photopolymerization initiator A new photopolymerization initiator (VI) is obtained by reacting the compound (V).

It showed reactivity example above, but it is also possible to react the compounds having other known and used -R ¹⁸ -NH ₂ reactive groups, but is not limited to these reactions examples. In addition, when the photopolymerization initiator obtained by the reaction is a polymer, the molecular weight of the photopolymerization initiator obtained by the reaction, stereoregularity, or the composition of the compound to be reacted is not particularly limited, It can be used by appropriately adjusting so as to obtain desired physical properties.

Photopolymerization initiator in the invention is, when it has -R ¹⁸ -NH (R ¹⁹⁾ as at least one reactive substituent, -R ¹⁸ -NH possessed by the photopolymerization initiator and (R ¹⁹⁾ A new photopolymerization initiator can be obtained by reacting with a compound having a reactive group. A typical example is shown below.

Example 13) reactive substituents as -R ¹⁸ -NH (photopolymerization initiator having a R ¹⁹⁾ of the present invention and ^{(VII), -R 18 -NH (} R 19 having the photopolymerization initiator) and A new photopolymerization initiator (VIII) is obtained by reacting a compound having a reactive group (suberoyl chloride).

It showed the reaction example above, by reacting a compound having a group capable of reacting with other known and used -R ¹⁸ -NH (R ¹⁹⁾ are also possible, but is not limited to these reactions examples . Moreover, when the photoinitiator obtained by making it react is a polymer, the molecular weight is not specifically limited, It can adjust and use suitably so that a desired physical property may be obtained.

  As described above, in the case of obtaining a new photopolymerization initiator by reacting the reactive functional group of the photopolymerization initiator with a compound having a group capable of reacting, in the general formula (1), n = 1 Yes, it is preferable to use a photopolymerization initiator having only one reactive substituent. This is because the photopolymerization initiator obtained by the reaction can obtain high solubility in various solvents, monomers, or resins.

  Specific examples of particularly preferred photopolymerization initiators described above are shown below, but the structure of the photopolymerization initiator of the present invention is not limited thereto.

  First, an example in the case of n = 1 in the general formula (1) is shown.

  Next, examples other than the above are shown for each corresponding general formula.

  The synthesis method for obtaining the photopolymerization initiator of the present invention is not particularly limited, and the structure can be easily synthesized and confirmed by appropriately combining conventionally known chemical reactions, post-treatment methods, purification methods and analysis methods. Is possible. Examples of methods for synthesizing α-aminoketone derivatives include those described in European Patent Application No. 3002, Japanese Patent Application Laid-Open No. 58-157805, Japanese Patent Application Laid-Open No. 63-264560, and the like. It is possible to synthesize the photopolymerization initiator of the present invention by appropriately replacing the raw materials used.

  The photopolymerization initiator of the present invention functions as a very high sensitivity photopolymerization initiator by irradiation with energy rays, particularly in the wavelength region of 250 nm to 450 nm. Therefore, a conventionally known α-aminoketone derivative-based photopolymerization initiator is used. The polymerization reaction, the crosslinking reaction, etc. to be used can be reliably realized in a shorter time, and as a result, it is possible to realize a significant increase in sensitivity and improvement in characteristics of various uses applying these reactions. Below, the utilization method of the photoinitiator of this invention is described.

  The composition containing the photopolymerization initiator (A) and the radical polymerizable compound (B) of the present invention is cured quickly and reliably by irradiation with energy rays, particularly light in the wavelength region of 250 nm to 450 nm, and has good characteristics. It can be used as a polymerizable composition capable of obtaining a cured product having the above.

  The radical polymerizable compound (B) used in the polymerizable composition of the present invention will be described. The radically polymerizable compound (B) in the present invention means a compound having at least one skeleton capable of radical polymerization in the molecule. In addition, these have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and normal pressure.

  Examples of such radically polymerizable compounds (B) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, acid amides and acid anhydrides. In addition, urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes and the like are exemplified, but the present invention is not limited to these. Absent. Specific examples of the radically polymerizable compound (B) in the present invention are given below.

Examples of acrylates:
Examples of monofunctional alkyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, p Nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate EO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecanedi Methylol diacrylate, isocyanuric acid EO-modified diacrylate.

Examples of trifunctional acrylates:
Glycerin PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, isocyanuric acid EO modified triacrylate, isocyanuric acid EO modified ε-caprolactone modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, cresyl polyethylene glycol methacrylate, p- Cycloalkenyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Bisphenol A dimethacrylate, EO-modified bisphenol A dimethacrylate, PO-modified bisphenol A-dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A dimethacrylate, PO-modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO-modified bisphenol F dimethacrylate, PO-modified bisphenol F dimethacrylate, EO-modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate.

Examples of trifunctional methacrylates:
Glycerin PO-modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone etc.

  Said radically polymerizable compound (B) can be easily obtained as a commercial item of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by KK, "Acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd. "NICHIGO-UV purple light urethane acrylate oligomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. "Carboxylic acid vinyl ester monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd. "Function" manufactured by Kojin Co., Ltd. Monomer "series and the like.

  Moreover, the cyclic compound shown below is also mentioned as a radically polymerizable compound (B).

Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, p. 3169 (1979), vinylcyclopropanes, macromolecular chemi. Rapid Communication (Makromol. Chem. Rapid Commun.), Vol. 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed., Vol. 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. ), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 564 (1985) 2,3-di-vinyl oxiranes described.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Volume 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Volume 21, page 373 (1983), 2-methylene-1,3-dioxepane, polymer pre-prints (Polym. Preprints), No. 34, 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), 20, 361 (1982) ), Macromolecular Chemie, Volume 183, 1913 (1982) and Macromolecular Chemie, Volume 186, 1-Methylene-4-phenyl-1,3-dioxepane described in page 1543 (1985), Macromolecules, Vol. 15, page 1711 (1982) 4,7-dimethyl-2- Methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3-diosepan described in Polymer Prepreprints, Vol. 34, 154 (1985).

  Furthermore, the radically polymerizable compound (B) can also include those described in the following literature. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  The radically polymerizable compound (B) of the present invention may be used alone or in a mixture of two or more at any ratio in order to improve desired properties.

  Further, the polymerizable composition of the present invention may be used by adding a carboxyl group-containing polymer (C) shown below for the purpose of using it for image formation as a so-called alkali development type photoresist material. Since the carboxyl group-containing polymer (C) has solubility in an alkaline aqueous solution, if the film prepared using the photopolymerizable composition of the present invention is partially cured, the so-called negative type is obtained due to the difference in solubility in the alkaline aqueous solution. It is possible to form a resist pattern. Here, the carboxyl group-containing polymer (C) is a copolymer of acrylic acid ester or methacrylic acid ester and acrylic acid, or a copolymer of methacrylic acid ester, methacrylic acid and a vinyl monomer copolymerizable therewith. Is mentioned. These copolymers may be used alone or in combination of two or more.

  Here, as the methacrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, etc. Is mentioned.

  Methacrylic acid ester, methacrylic acid and vinyl monomers copolymerizable therewith include tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3, Examples include 3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

  The photopolymerization initiator (A) of the present invention is preferably used in the range of 0.01 to 60 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). The carboxyl group-containing polymer (C) is preferably used in the range of 20 to 500 parts by weight, more preferably in the range of 50 to 150 parts by weight, based on 100 parts by weight of the radical polymerizable compound (B). .

  The polymerizable composition of the present invention is mixed with a binder such as an organic polymer in order to improve the film formability, and is applied to a polymer film such as glass plate, aluminum plate, other metal plate, polyethylene terephthalate or polyethylene. It is possible to use.

  Examples of binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, Epoxy resins, alkyd resins, etc., supervised by Kiyoshi Akamatsu, "New Technology of Photosensitive Resins" (CMC, 1987) and "10188 Chemical Products", pages 657-767 (Chemical Industry Daily, 198) Year) industry known organic polymer according the like.

  The polymerizable composition of the present invention can be used by adding a solvent as necessary for the purpose of improving the coating suitability including viscosity adjustment. The solvent that can be used by adding to the polymerizable composition of the present invention is not particularly limited, and any solvent can be used as long as it can be uniformly mixed with the polymerizable composition of the present invention. For example, known solvents such as alcohols, ketones, esters, aromatics, hydrocarbons, and halogenated hydrocarbons may be used, but the invention is not limited thereto.

  Further, the polymerizable composition of the present invention has sufficient sensitivity without using other photosensitizers, but for the purpose of further improving the sensitivity and improving the film properties after curing, It can be used in combination with other photopolymerization initiators.

  Photosensitizers that can be used in combination with the polymerizable composition of the present invention include benzophenones, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, etc. Polymethine dye, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative , Triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetra Filin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and the like. Other examples include Ogahara Nobu et al., “Dye Handbook” (1986, Kodansha). The dyes and photosensitivity described in Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Tadasaburo et al., “Special functional materials” (1986, CMC) However, it is not limited to these, and other examples include dyes and photosensitizers that absorb light from the ultraviolet to the near-infrared region. Two or more types may be used. Among the photosensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxy. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'- Examples thereof include bis (diethylamino) benzophenone. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylamino). It can be mentioned coumarin), etc., but is not limited thereto.

  Other photopolymerization initiators that can be used in combination with the polymerizable composition of the present invention include Irgacure 127, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (Ciba Specialty Chemicals), Adeka optomer N1414, Adeka optomer N1717 (Asahi Denka), Esacure 1001M (Lamberti), SHO 59- Triazine derivatives described in Japanese Patent Publication No. 281, Japanese Patent Publication No. 61-9621 and Japanese Patent Publication No. 60-60104, organic peroxides described in Japanese Patent Publication No. 59-1504 and Japanese Patent Publication No. 61-243807, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and US Pat. No. 3,567,453, the diazonium compound publication, USP No. 2,848,328, USP No. 2,852,379, and USP. No. 2940853, organic azide compounds described in Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, and Japanese Patent Publication No. 45-9610. Japanese Patent Publication No. 55-39162, Japanese Patent Publication No. 59-14020 No. 3, and various onium compounds including iodonium compounds described in “MACROMOLECULES”, Vol. 10, page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Volume 30, page 174 ( 1986), titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, 84, 85-277 (1988) and Transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 209477, aluminate complex described in JP-A-2-157760, borate compound described in JP-A-2-157760, 2,4,5-triaryl described in JP-A-55-127550 and JP-A-60-202437 Imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, carbon tetrabromide and JP-A-59-107344 JP-A-5-213861, JP-A-5-255347, JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002 -265512, Japanese Patent Application No. 2004-053009, and Japanese Patent Application No. 2004-263413. Is an oxosulfonium complex, JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, USP3558309 (1971), USP4202697 (1980), oxime ester compounds described in JP-A-61-24558, JP-A-2004-534797, and JP-A-2004-359539, and bifunctional photoinitiation described in JP-A-2002-530372. These photopolymerization initiators are preferably contained in the range of 0.01 to 40 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  In addition, a thermal polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The polymerization inhibitor is preferably added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B).

  Moreover, the polymerization composition of this invention can add the polymerization accelerator represented by amine, thiol, disulfide, etc. and a chain transfer catalyst for the purpose of further promoting superposition | polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, ethyl 4-dimethylaminobenzoate, N-phenylglycine, triethanolamine, N, N-diethylaniline and the like. Amines, thiols described in U.S. Pat. No. 4,414,312 and JP-A 64-13144, disulfides described in JP-A-2-291561, U.S. Pat. No. 3,558,322 and JP-A 64-17048. Examples thereof include thiones described in JP-A No. 2-291560, and O-acylthiohydroxamate and N-alkoxypyridine thiones described in JP-A-2-291560.

  Further, the polymerizable composition of the present invention can be used depending on the purpose, such as dyes, organic and inorganic pigments, phosphine, phosphonate, phosphite and other oxygen scavengers and reducing agents, antifoggants, antifading agents, antihalation agents, fluorescent enhancers. Whitening agents, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, dye precursors, UV absorbers, foaming agents, antifungal agents, antistatic agents, magnetic substances and other various properties You may mix and use the additive to add, a dilution solvent, etc.

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of energy such as ultraviolet rays, visible light, near infrared rays, electron beams, etc. to obtain a desired polymer, As the light source, a light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a main wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Examples of the light source include xenon lamps, deuterium lamps, fluorescent lamps, Nd-YAG triple wave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, and semiconductor-excited solid lasers. The definitions of ultraviolet rays, visible light, near-infrared rays and the like in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, various inks, ink-jet inks, overcoat varnishes, various printing plate materials, photoresists, electrophotography, direct printing plate materials, optical fibers, hologram materials, and other photosensitive materials, microcapsules, etc. It can be applied to various recording media, as well as adhesives, pressure-sensitive adhesives, adhesives, release coating agents, sealants, and various paints.

  The photopolymerization initiator (A) of the present invention functions as a radical polymerization initiator that is sensitive to irradiation light in a wavelength region of 250 to 450 nm. The reason why the photopolymerization initiator (A) of the present invention is more sensitive than the conventionally known α-aminoketone derivatives is not clear so far, but 1) against the photopolymerization initiator (A) of the present invention. When irradiated with light in the ultraviolet region, the process of excitation to radical generation is performed more efficiently than conventionally known α-aminoketone derivatives, or 2) the photopolymerization initiator (A) of the present invention is light Because it has absorption characteristics evenly in the wavelength range of the light source to irradiate, it can be absorbed by a large amount of light energy necessary to generate radicals. It is done.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In addition, unless otherwise indicated, a part shows a weight part in an example. First, the compounds used in Examples and Comparative Examples are shown in Table 1, and synthesis examples are shown for compounds (1) to (21) which are photopolymerization initiators of the present invention.

Table 1

Synthesis example (1)
Photopolymerization initiator: Synthesis of compound (1)

  Synthesis of compound (A)

  A solution in which 97.1 g of N-ethyl-carbazole is dissolved in 300 ml of benzene, 73.4 g of aluminum chloride is further added, and 115.0 g of 2-Bromo-n-butylyl Bromide is dissolved in 500 ml of benzene with stirring at 0 ° C. Was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 3000 g of ice water and extracted with 4 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 1/2 as a developing solvent to obtain 129.0 g of compound (A). Obtained.

  Synthesis of compound (B)

  Dissolve 103.3 g of Compound (A) in 500 ml of benzene, add 94.4 g of aluminum chloride, and stir at 0 ° C., then add a solution of 71.5 g of terephthalic acid monomethyl ester chloride in 300 ml of benzene over 2 hours. And dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 4000 g of ice water and extracted with 4 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 1/1 as a developing solvent to obtain 65.5 g of compound (B). Obtained.

  Synthesis of compound (C)

  32.9 g of compound (B) was dissolved in 200 ml of THF. The solution was cooled to 0 ° C., and 120 ml of 2M dimethylamine THF solution was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 25 ° C. for 24 hours. Next, this solution was poured into 300 ml of ice water and extracted with 1 L of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered and the solvent was distilled off to obtain 27.8 g of compound (C).

  Synthesis of compound (1)

  15.2 g of the compound (C) was dissolved in 350 ml of tetrahydrofuran, and 10.6 g of Allyl bromide was added dropwise over 1 hour. After heating and stirring at 40 ° C. for 12 hours, 11.6 g of 30% aqueous NaOH solution was added to the solution, and the mixture was further stirred for 12 hours. This mixed solution was poured into 400 ml of ice water and extracted with 500 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / hexane = 3/1 as a developing solvent to obtain 9.1 g of compound (1). It was.

Synthesis example (2)
Photopolymerization initiator: Synthesis of compound (2)

  Synthesis of compound (D)

  30.6 g of compound (B) was dissolved in 200 ml of THF. This solution was cooled to 0 ° C., and 100 ml of THF added with 21.5 g of Piperidine was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 25 ° C. for 24 hours. Next, this solution was poured into 300 ml of ice water and extracted with 1 L of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered and the solvent was distilled off to obtain 28.1 g of compound (D).

  Synthesis of compound (E)

  27.0 g of compound (D) was dissolved in 320 ml of tetrahydrofuran, and 10.8 g of Benzyl bromide was added dropwise over 1 hour. After heating and stirring at 40 ° C. for 12 hours, 11.6 g of 30% aqueous NaOH solution was added to the solution, and the mixture was further stirred for 12 hours. This mixed solution was poured into 400 ml of ice water and extracted with 500 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / hexane = 3/1 as a developing solvent to obtain 22.1 g of compound (E). It was.

  Synthesis of compound (2)

  20.6 g of compound (E), 8.9 g of 1,3-Bis (methacryloyloxy) -2-propanol are dissolved in 300 ml of dichloromethane, and then 8.0 g of dicycyclohexylcarbodiimide and 0.9 g of 4- (dimethylamino) pyridine are added at 25 ° C. And stirring was continued for 12 hours. The reaction solution was poured into 400 g of water and extracted with 400 ml of dichloromethane. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 16.2 g of compound (2). Obtained.

Synthesis example (3)
Photopolymerization initiator: Synthesis of compound (3)

  Synthesis of compound (F)

  97.3 g of N-ethyl-carbazole was dissolved in 1200 ml of benzene, 80.4 g of aluminum chloride was further added, and a solution of 99.5 g of terephthalic acid monomethyl ester chloride in 800 ml of benzene was stirred for 2 hours at 0 ° C. It was dripped over. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2500 g of ice water and extracted with 2 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 82.5 g of compound (F). Obtained.

  Synthesis of compound (G)

  78.6 g of compound (F) was dissolved in 700 ml of benzene, 102.4 g of aluminum chloride was further added, and a solution obtained by dissolving 26.5 g of Sebacoyl chloride in 300 ml of benzene was added dropwise over 2 hours while stirring at 0 ° C. . After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 1500 g of ice water and extracted with 1 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 71.4 g of compound (G). Obtained.

  Synthesis of compound (H)

  71.4 g of compound (G) was dissolved in 700 ml of dichloromethane, and 18.8 g of bromine was added dropwise over 30 minutes with stirring at 10 ° C. After completion of the dropping, the temperature of the reaction solution was set to 25 ° C. and stirred for 12 hours. The reaction solution was washed with an aqueous sodium thiosulfate solution and extracted with 1 L of dichloromethane. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 1/1 as a developing solvent to obtain 51.0 g of compound (H). Obtained.

  Synthesis of compound (I)

  45.0 g of compound (H) was dissolved in 400 ml of THF. This solution was cooled to 0 ° C., and 200 ml of 2M dimethylamine THF solution was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 25 ° C. for 24 hours. Next, this solution was poured into 300 ml of ice water and extracted with 1 L of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered and the solvent was distilled off to obtain 37.1 g of Compound (I).

  Synthesis of compound (J)

  Compound (I) 19.1g was dissolved in tetrahydrofuran 250ml, and Benzyl bromide 8.8g was dripped over 1 hour. After heating and stirring at 40 ° C. for 12 hours, 10.0 g of 30% NaOH aqueous solution was added to the solution, and the mixture was further stirred for 12 hours. This mixed solution was poured into 400 ml of ice water and extracted with 500 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / hexane = 3/1 as a developing solvent to obtain 11.9 g of compound (J). It was.

  Synthesis of compound (3)

  11.0 g of compound (J) and 3.2 g of 3-methacryloyloxypropanol were dissolved in 300 ml of dichloromethane, and then 4.5 g of dicycyclohexylcarbodiimide and 2.7 g of 4- (dimethylamino) pyridine were added and stirring was continued at 25 ° C. for 12 hours. The reaction solution was poured into 400 g of water and extracted with 300 ml of dichloromethane. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 10.2 g of compound (3). Obtained.

Synthesis example (4)
Photopolymerization initiator: Synthesis of compound (4)

  Synthesis of compound (K)

  166.3 g of 9H-carbazole was dissolved in 1300 ml of benzene, 146.7 g of aluminum chloride was further added, and a solution obtained by dissolving 252.5 g of 2-Bromoisobutylyl bromide in 850 ml of benzene was added dropwise over 2 hours while stirring at 0 ° C. . After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 4 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 107.3 g of compound (K). Obtained.

  Synthesis of compound (L)

  Dissolve 100.0 g of Compound (K) in 1000 ml of benzene, add 61.7 g of aluminum chloride, and stir at 0 ° C., then add a solution of 36.5 g of o-toluoyl chloride in 500 ml of benzene over 2 hours. And dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 1500 g of ice water and extracted with 2 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 67.7 g of compound (L). Obtained.

  Synthesis of compound (M)

  65.0 g of compound (L), 23.0 g of 4-Bromobutanol, and 750 ml of 30% NaOH aqueous solution were added, heated to 100 ° C. and stirred for 2 days. Thereafter, the reaction solution was cooled to room temperature and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 4/1 as a developing solvent to obtain 62.1 g of compound (M). Obtained.

  Synthesis of compound (N)

  50.0 g of compound (M) and 7.9 g of acrylic acid were dissolved in 500 ml of dichloromethane, and then 23.0 g of dicycyclohexylcarbodiimide and 1.2 g of 4- (dimethylamino) pyridine were added and stirring was continued at 25 ° C. for 12 hours. The reaction solution was poured into 400 g of water and extracted with 400 ml of dichloromethane. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 47.1 g of compound (N). Obtained.

  Synthesis of compound (4)

  Compound (N) 43.0 g was dissolved in THF 300 ml, sodium methoxide 28% methanol solution 16.3 g was added, and the mixture was stirred at 40 ° C. for 6 hours. This solution was extracted with ethyl acetate, dried over sodium sulfate, the desiccant was filtered off, and concentrated to remove the solvent. The morpholine 120.0g and acetonitrile 400mL were added there, and it heated and stirred at 60 degreeC. Further, a solution consisting of 69.2 g of anhydrous lithium perchlorate and 100.0 g of morpholine was added and stirred at 70 ° C. in nitrogen for 6 hours. The reaction mixture was cooled, diluted with water and extracted with 1 L of toluene. The organic layer was dried over magnesium sulfate and the desiccant was filtered. The residue was purified by alumina column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 26.5 g of compound (4). .

Synthesis example (5)
Photopolymerization initiator: Synthesis of compound (5)

  Synthesis of compound (O)

  15.3 g of the compound (D) was dissolved in 250 ml of tetrahydrofuran, and 9.1 g of α-Bromo-o-xylen was added dropwise over 1 hour. After heating and stirring at 40 ° C. for 12 hours, 10.6 g of 30% aqueous NaOH solution was added to the solution, and the mixture was further stirred for 12 hours. This mixed solution was poured into 200 ml of ice water and extracted with 300 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / hexane = 3/1 as a developing solvent to obtain 11.4 g of compound (O). It was.

  Synthesis of compound (5)

  11.4 g of compound (O) and 1.9 g of 3-Amino-1-propanol are dissolved in 300 ml of dichloromethane, and then 5.6 g of dicycyclohexylcarbodiimide and 0.6 g of 4- (dimethylamino) pyridine are added and stirred at 25 ° C. for 12 hours. Continued. The reaction solution was poured into 400 g of water and extracted with 400 ml of dichloromethane. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by reprecipitation with ethyl acetate / hexane to obtain 10.1 g of compound (5).

Synthesis example (6)
Photopolymerization initiator: synthesis of compound (6)

  Synthesis of compound (P)

  Compound (P) was synthesized in the same manner as Compound (K) except that 2-Bromoisobutyryl bromide was replaced with 2-Bromo-n-butyryl bromide in the synthesis of Compound (K).

  Synthesis of compound (Q)

  Dissolve 95.0 g of compound (P) in 1000 ml of benzene, add 84.7 g of aluminum chloride, and stir at 0 ° C., then add a solution of 48.4 g of 2-thenoyl chloride in 500 ml of benzene over 2 hours. And dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 1500 g of ice water and extracted with 2 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 77.7 g of compound (Q). Obtained.

  Synthesis of compound (R)

  Compound (Q) 69.0g, 3-Bromopropanol 19.0g, 30% NaOH aqueous solution 750ml was added, and it heated at 100 degreeC, and stirred for 2 days. Thereafter, the reaction solution was cooled to room temperature and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 63.6 g of compound (R). Obtained.

  Synthesis of compound (S)

  48.4 g of compound (R) was dissolved in 400 ml of THF. This solution was cooled to 0 ° C., and 25.5 g of dimethylamine dissolved in 200 ml of THF solution was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 25 ° C. for 24 hours. Next, this solution was poured into 300 ml of ice water and extracted with 1 L of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered and the solvent was distilled off to obtain 43.3 g of compound (S).

  Synthesis of compound (6)

  23.8 g of compound (S) was dissolved in 340 ml of tetrahydrofuran, and 17.8 g of benzyl bromide was added dropwise over 1 hour. After heating and stirring at 40 ° C. for 12 hours, 10.0 g of 30% NaOH aqueous solution was added to the solution, and the mixture was further stirred for 12 hours. This mixed solution was poured into 400 ml of ice water and extracted with 500 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / hexane = 3/1 as a developing solvent to obtain 17.9 g of compound (6). It was.

Synthesis examples (7) to (18)
Photopolymerization initiator: synthesis of compounds (7) to (18)

  By applying the methods of the above-mentioned compounds (1) to (6), compounds (7) to (18) which are photopolymerization initiators of the present invention could be obtained.

Synthesis example (19)
Photopolymerization initiator: synthesis of compound (19)

  Synthesis of compound (19)

  10.8 g of compound (4) and 3.9 g of 2-ethylhexyl acrylate monomer were dissolved in 240 ml of tetrahydrofuran, 0.8 g of Azobisisobutyronitrile was added, and the mixture was heated and stirred at 60 ° C. for 12 hours. Next, the solvent was removed, and the residue was purified by reprecipitation from ethyl acetate / hexane to obtain 8.2 g of Compound (19). When GPC (gel permeation chromatography, GPC-8020 manufactured by Tosoh Corporation) was measured for the compound (19), the number average molecular weight (polystyrene conversion) was 2700.

Synthesis example (20)
Photopolymerization initiator: synthesis of compound (20)

  Synthesis of compound (20)

  11.0 g of compound (11) and 2.5 g of triethylamine were dissolved in 150 ml of dichloromethane, cooled to 0 ° C. and stirred. Next, 1.9 g of Adipoyl chloride dissolved in 50 ml of dichloromethane was added dropwise over 30 minutes, and after completion of the addition, the reaction solution was returned to room temperature and stirred for 12 hours. The mixed solution was poured into 400 ml of ice water and extracted with 500 ml of dichloromethane. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 10.9 g of compound (20). It was.

Synthesis example (21)
Photopolymerization initiator: synthesis of compound (21)

  Synthesis of compound (21)

  Compound (9) 5.2g, 2-methacryloyloxyethyl isocynate 1.7g, 2,6-Di-tert-butyl-p-cresol 0.1g was dissolved in 240ml of toluene, and heated and stirred at 60 ° C for 12 hours. Next, the solvent was removed, and the residue was purified by reprecipitation from ethyl acetate / hexane to obtain 5.2 g of Compound (19).

  Table 2 shows the results of elemental analysis (2400II elemental analyzer manufactured by Perkin Elmer Co., Ltd.) of the photopolymerization initiator of the present invention synthesized in Synthesis Example (1) to Synthesis Example (21) described above. As for the compound (19), since the compound is a polymer, it is difficult to calculate an accurate number of atoms and elemental analysis calculation values, so only the results are shown.

(1) Curability: Examples 1 to 12 and Comparative Examples 1 to 8
3 parts by weight of a photopolymerization initiator (A), 0 or 1 part by weight of a photosensitizer, 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as a radical polymerizable compound (B), ditrimethylolpropanetetra 85 parts by weight of acrylate was blended and melted by heating to prepare a coating solution. Table 3 shows the photopolymerization initiator and photosensitizer used. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product was irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 lamp), then rubbed with a cotton cloth and judged at a conveyor speed at which the film was not damaged. The results are shown in Table 3. In addition, the larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability.

Table 3

  The photopolymerizable composition using the photopolymerization initiator of the present invention has high curability as compared with a photopolymerizable composition using a photopolymerization initiator that is generally used. It became clear. Furthermore, the photopolymerizable composition using the photopolymerization initiator of the present invention is more than the case where a photopolymerization initiator and a photosensitizer that are generally used are used in combination as a photopolymerization initiator. It was also revealed that it has high curability.

(2) Yellowing: Examples 13-22, Comparative Examples 9-14
5 parts by weight of photopolymerization initiator (A), 0 or 1 part by weight of photosensitizer, 10 parts by weight of Daptot DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.) as radical polymerizable compound (B), ditrimethylolpropanetetra 85 parts by weight of acrylate was blended and melted by heating to prepare a coating solution. Table 4 shows the photopolymerization initiator and photosensitizer used. This coating solution was applied onto a pet film using a bar coater (# 3). The coated product was cut into the coated product under the same conditions as the curability, and 10 panelists relatively determined the yellowing of the coated product. 1 (defect) to 5 (good) ). The results are shown in Table 4.

Table 4

  It has been clarified that the photopolymerizable composition using the photopolymerization initiator of the present invention is excellent in yellowing as compared with a photopolymerizable composition using a photopolymerization initiator that is generally used. .

(3) Odor: Examples 23 to 39, Comparative Examples 15 to 19
5 parts by weight of photopolymerization initiator (A), 0 or 1 part by weight of photosensitizer, 10 parts by weight of Daptot DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.) as radical polymerizable compound (B), ditrimethylolpropanetetra 85 parts by weight of acrylate was blended and melted by heating to prepare a coating solution. Table 5 shows the photopolymerization initiator and photosensitizer used. This coating solution was applied onto a pet film using a bar coater (# 3). In this coating material, the coating material cured under the same conditions as the curability is finely cut and packed in a glass bottle to collect odors. Ten panelists relatively determine odor properties, and 1 (defect) to Evaluation was made on a scale of 5 (good). The results are shown in Table 5.

Table 5

  It turned out that the photopolymerizable composition using the photoinitiator of this invention is excellent in odor compared with the photopolymerizable composition using the photoinitiator generally used. It is presumed that the reason why the photopolymerizable composition of the present invention is excellent in odor is because there is little volatilization of the photopolymerization initiator after curing or its decomposition product.

  The photopolymerizable composition using the photopolymerization initiator of the present invention is more curable than a photopolymerizable composition using a photopolymerization initiator and a photosensitizer that are generally used in combination. It became clear that it was excellent. In addition, the photopolymerizable composition using the photopolymerization initiator of the present invention can suppress coloring and odor after curing of the polymerizable composition as compared with a general photopolymerizable composition. It became clear that all these requirements, which were difficult with a photopolymerizable composition using a photopolymerization initiator, were satisfied.

  The present invention provides a photopolymerization initiator that functions as a radical generator with extremely high sensitivity to irradiation with energy rays, particularly irradiation with light of 250 to 450 nm. Therefore, the photopolymerization initiator of the present invention can rapidly and surely proceed polymerization, crosslinking reaction, etc. using radicals generated by irradiation of energy rays, which have been conventionally used, as a result. It can be expected to increase the sensitivity to energy rays or to improve the characteristics of various applications by sufficiently proceeding the reaction. In addition, the photopolymerization initiator of the present invention is used in various polymerizable compositions containing the photopolymerization initiator, such as coloring after curing by light irradiation and volatilization of the photopolymerization initiator that occurs from the polymerizable composition after curing. It can be expected to suppress odor. Furthermore, even in a hybrid polymerizable composition such as a polymerizable composition having a photopolymerization property and a thermal polymerization property, when the photopolymerization initiator of the present invention is used, it is polymerizable by the reactive functional group of the photopolymerization initiator. Since it is taken into the composition, it can be expected to have a lower odor. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Ink-jet ink, paint, photosensitive resin for printing plates, color proof for printing, resist for color filters, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display, dry film resist, Resist for printed circuit boards, solder resist, photoresist for semiconductor, resist for microelectronics, resist for manufacturing micromachine parts, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat Agent, powder coatings, adhesives, pressure-sensitive adhesives, release agents, optical recording media, adhesive, release coat agent composition for image recording materials using microcapsules, and various devices and the like.

Claims (13)

A photopolymerization initiator represented by the following general formula (1), the following general formula (2), or the following general formula (3).
General formula (1)

General formula (2)

General formula (3)

(In the formula, n represents 1 to 4, and m represents 2 to 4.
R ¹ , R ⁶ , R ⁷ , R ¹¹ , and R ¹² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group. Represents a substituted alkenyl group.
R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group when n is 1, and n is 2 If it is, -O -, - S -, - CO -, - N (R 17) -, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic Represents a group, a substituted or unsubstituted alkenylene group, or a combination thereof, or a direct bond. When n is 3, it represents a trivalent linking group. When n is 4, it represents a tetravalent linking group. .
R ¹⁰ and R ¹⁶ are each independently, when m is 2, —O—, —S—, —CO—, —N (R ¹⁷ ) —, a substituted or unsubstituted alkylene group, substituted or unsubstituted Represents a substituted arylene group, a substituted or unsubstituted divalent heterocyclic group, a substituted or unsubstituted alkenylene group, or a combination thereof, or a direct bond. When m is 3, a trivalent linking group is represented. , M represents 4, it represents a tetravalent linking group.
R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle Represents a group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group. R ³ and R ⁴ , R ⁸ and R ⁹ , and R ¹³ and R ¹⁴ may form a ring.
R ⁵ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Substituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted Or an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted arylamino Group, substituted or unsubstituted diarylamino group, substituted or Substituted alkyl arylamino group, or a halogen atom.
R ¹⁷ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.
At least one of R ¹ and R ⁵ , at least one of R ⁶ and R ⁷ , and at least one of R ¹¹ , R ¹² and R ¹⁵ are each a reactive functional group —R ¹⁸ —. ^{OH, -R 18 -COOH, -R 18} -CONH 2, -R 18 -N = C = O, -R 18 -N = C = S, -R 18 -NH 2, -R 18 -NH (R 19 ) Or the following general formula (4).
Ar ¹ , Ar ² , and Ar ³ each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.
A ¹ and A ² each independently represent the following general formula (5), general formula (6), general formula (7), or general formula (8).
A ³ represents the following general formula (9), general formula (10), general formula (11), or general formula (12). )
General formula (4)

(Wherein R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ¹⁸ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a combination thereof, or a direct bond.
R ¹⁹ represents a substituted or unsubstituted alkyl group. )
General formula (5)

General formula (6)

General formula (7)

General formula (8)

Wherein Y ¹ and Z ¹ are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ¹⁷ ) —, —CO—, —CH ₂ —, — CH ₂ CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms or a direct bond;
U ¹ represents —O—, —S—, or —N (R ¹⁷ ) —,
V ¹ and W ¹ represent a nitrogen atom. )


General formula (9)

General formula (10)

Formula (11)

Formula (12)

(Wherein Y ² and U ² each independently represent a nitrogen atom bonded to R ¹⁶ ;
Z ² represents —O—, —S—,>S═O,> SO ₂ , —N (R ¹⁷ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—. Represents an alkylidene group having 2 to 6 carbon atoms or a direct bond,
V ² and W ² represent a nitrogen atom. ) The photopolymerization initiator according to claim 1, wherein A ¹ is the general formula (5). The photopolymerization initiator according to claim 1, wherein A ² is the general formula (5). The photopolymerization initiator according to claim 1, wherein A ³ is the general formula (9).

  The photoinitiator obtained by making the photoinitiator in any one of Claims 1-4 react with the compound which has a group which can react with the reactive functional group which the said photoinitiator has. Reactive functional group formula ^{(4), - R 18 -NH} 2, or a photopolymerization initiator according to claim 5, wherein -R ¹⁸ -OH.   The photopolymerization according to claim 5 or 6, wherein the reactive functional group is the general formula (4), and the compound having a group capable of reacting with the reactive functional group of the photopolymerization initiator is a compound having radical polymerizability. Initiator. A compound in which the reactive functional group is —R ¹⁸ —NH ₂ and the compound having a group capable of reacting with the reactive functional group of the photopolymerization initiator has an isocyanate group, an epoxy group, a —COCl group, or a carboxyl group The photopolymerization initiator according to claim 5 or 6. A compound having a reactive functional group of —R ¹⁸ —OH and a group capable of reacting with the reactive functional group of the photopolymerization initiator is an isocyanate group, an epoxy group, a carboxyl group, an alkylsilyl group, or an alkoxysilyl group. The photopolymerization initiator according to claim 5 or 6, which is a compound having   The manufacturing method of the photoinitiator obtained by making the photopolymerization initiator in any one of Claims 1-4 react with the compound which has a group which can react with the reactive functional group which the said photoinitiator has.   A polymerizable composition comprising the photopolymerization initiator (A) according to claim 1 and a radical polymerizable compound (B).   The polymerizable composition according to claim 12, wherein the photopolymerization initiator (A) is a photopolymerization initiator having a radical polymerizable group.   A method for producing a polymer, wherein the polymerizable composition according to claim 12 or 13 is polymerized by irradiating with an energy ray containing light in a wavelength region of 250 nm to 450 nm.