KR20210148158A - Polymer composition and single-layer retardation material - Google Patents

Abstract

(A) The polymer composition containing the side chain polymer which has a side chain which has a photoreactive site|part represented by following formula (a), (B) a silane coupling agent, and (C) organic solvent is provided.

Description

Polymer composition and single-layer retardation material

The present invention relates to a composition containing a polymer and a single-layer retardation material. Specifically, a material having optical properties suitable for applications such as display devices and recording materials, in particular, liquid crystal polymers that can be preferably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, containing the polymer It relates to a composition and the single-layer retardation material obtained from the composition.

As an optical compensation film such as a polarizing plate or a retardation plate, the demand for a polymer film in which the internal molecular alignment structure is controlled is increasing from the demands for improvement of display quality and weight reduction of the liquid crystal display device. In order to respond to this request|requirement, development of the film using the optical anisotropy which a polymeric liquid crystal compound has is made|formed. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural moiety (a structural moiety having a spacer moiety and a mesogen moiety), and an acryl group is widely used as the polymerizable group.

Generally, such a polymerizable liquid crystal compound turns into a polymer (film) by the method of irradiating radiation, such as an ultraviolet-ray, and superposing|polymerizing. For example, a method in which a specific polymerizable liquid crystal compound having an acryl group is supported between supports and irradiated with radiation while maintaining the compound in a liquid crystal state to obtain a polymer (Patent Document 1), or two types of polymerizable liquid crystal compounds having an acryl group The method (patent document 2) of adding a photoinitiator to the mixture of the liquid crystal compound, or the composition which mixed the chiral liquid crystal with this mixture, and irradiating an ultraviolet-ray to obtain a polymer is known.

Moreover, various single-layers, such as an orientation film using the polymeric liquid crystal compound or polymer which do not require a liquid crystal aligning film (patent documents 3, 4), and the orientation film using the polymer containing a photocrosslinking site|part (patent document 5, 6), etc. A coating type oriented film has been reported. However, the film manufacturing process is difficult, or it is necessary to use a solvent having excellent dissolving power such as NMP, chloroform, chlorobenzene, etc. as a solvent for the polymer to be used, and there is a problem such as low solubility of the polymer. Materials to solve the problem have not been found so far.

Japanese Patent Laid-Open No. 62-70407 Japanese Patent Laid-Open No. 9-208957 Specification of European Patent Application Publication No. 1090325 International Publication No. 2008/031243 Japanese Laid-Open Patent Publication No. 2008-164925 Japanese Laid-Open Patent Publication No. 11-189665

The present invention has been made in view of the above problems, and provides a novel polymer capable of producing a single-layer retardation material having a high retardation value by a simpler process, a composition containing the polymer, and a single-layer retardation material obtained from the composition aim to do

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination in order to solve the said subject, this inventor does not use a liquid crystal aligning film by using the composition containing a specific polymer and a specific additive, The single-layer retardation material which has high refractive index anisotropy ((DELTA)n) is obtained Moreover, it discovered that a single-layer retardation material with a high retardation value and no haze can be manufactured under low-temperature conditions, and completed this invention.

Accordingly, the present invention provides the following polymer composition and a single layer retardation material.

1. (A) side chain polymer which has a side chain which has a photoreactive site|part represented by following formula (a);

(B) a silane coupling agent, and

(C) a polymer composition comprising an organic solvent.

[Formula 1]

(Wherein, R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom or an organic group. In addition, -CH ₂ CH ₂ - ^{in R 1} may be substituted with -CH=CH-, and -CH ₂ ^{- in R 1} is, -O-, -NH-C(=O)-, -C(=O)-NH-, -C(= It may be substituted with a group selected from the group consisting of O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH-, and -C(=O)-. , -CH ₂ adjacent - is is not substituted at the same time, these groups also, -CH ₂ -. is, -CH ₂ of the terminal of R ¹ - or may be.

R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group.

R ³ is a single bond, -O-, -C(=O)-O-, -OC(=O)-, or -CH=CH-C(=O)-O-.

R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and when c ≥ 2, each R may be the same as or different from each other.

a is 0, 1 or 2.

b is 0 or 1.

c is an integer satisfying 0≤c≤2b+4.

The broken line is the bonding hand.)

2. The polymer composition of 1 whose side chain which has the said photoreactive site|part is represented by following formula (a1).

[Formula 2]

(In the formula, R ¹ , R ² and a are the same as above.

R ^3A is a single bond, -O-, -C(=O)-O-, or -OC(=O)-.

The benzene ring in the formula (a1) is a substituent selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. may be substituted with

The broken line is the bonding hand.)

3. (A) The polymer composition of 1 or 2 in which a side chain type polymer has a side chain which expresses only liquid crystal further.

4. The polymer composition of 3 whose side chain which expresses only the said liquid crystal is a liquid crystalline side chain represented by any one of following formula (1) - (13).

[Formula 3]

[Formula 4]

(Wherein, A ¹ , A ² are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-.

R ¹¹ is -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and 1 to 12 carbon atoms of an alkyl group or an alkyloxy group having 1 to 12 carbon atoms.

R ¹² is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining them; hydrogen atoms binding to these, -NO _2, -CN, an alkoxy group a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms may be substituted for.

R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing hetero a cyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

E is -C(=O)-O- or -O-C(=O)-.

d is an integer of 1-12.

Although k1-k5 is each independently an integer of 0-2, the sum total of k1-k5 is 2 or more.

Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more.

m1, m2, and m3 are each independently an integer of 1-3.

n is 0 or 1.

Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ O-, -CH=N-, or -CF ₂ -.

The broken line is the bonding hand.)

5. The polymer composition of 4 whose side chain expressing only the said liquid crystal is a liquid crystalline side chain represented by any one of Formulas (1) - (11).

6. (I) the step of applying the polymer composition of any one of 1 to 5 on a substrate to form a coating film;

(II) a step of irradiating the coating film with polarized ultraviolet rays, and

(III) Heating the coating film irradiated with the said ultraviolet-ray, The manufacturing method of a single-layer retardation material including the process of obtaining retardation material.

7. Single layer retardation material obtained from the composition in any one of 1-5.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a thin film, it can provide the single-layer retardation material with high retardation value, and the polymer which provides it.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor came to complete this invention by obtaining the following knowledge.

The polymer composition of the present invention has a photosensitive side chain polymer (hereinafter also simply referred to as a side chain polymer) capable of expressing liquid crystallinity, and the coating film obtained using the polymer composition is capable of expressing liquid crystallinity. It is a film having a photosensitive side chain type polymer that can be It orientation-processes by polarized light irradiation, without giving a rubbing process to this coating film. And it becomes the film (henceforth single-layer retardation material) to which optical anisotropy was provided through the process of heating the side chain type polymer film after polarized light irradiation. At this time, the minute anisotropy expressed by polarized light irradiation becomes a driving force, and liquid crystalline side chain type polymer itself is reorientated efficiently by self-organization. As a result, highly efficient orientation processing is implement|achieved, and the single-layer retardation material to which high optical anisotropy was provided can be obtained.

Moreover, the polymer composition of this invention contains a silane coupling agent as (B) component with the side chain type polymer of (A) component. Thereby, as for the retardation material obtained from the polymer composition of this invention, a silane coupling agent floats at the time of film-forming. That is, it is unevenly distributed on the surface not in contact with the substrate. Thereby, since the aggregation of the polymer|macromolecule in the surface is suppressed, the flatness of the retardation material obtained becomes high. As a result, haze is suppressed. In addition, they include the views of the inventors regarding the mechanism of the present invention and do not limit the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

[Polymer composition]

The polymer composition of the present invention is characterized by containing (A) a side chain polymer having a side chain having a photoreactive moiety, (B) a silane coupling agent, and (C) an organic solvent.

[(A) side chain polymer]

(A) A component is a photosensitive side chain type polymer which expresses liquid crystallinity in a predetermined|prescribed temperature range, Comprising: The side which has a side chain (henceforth a side chain a) which has a photoreactive site|part represented by following formula (a) It is a chain polymer.

[Formula 5]

In formula (a), R<^1> is a C1-C30 alkylene group, and one or several hydrogen atom of this alkylene group may be substituted by the fluorine atom or an organic group. Further, R ¹ in the -CH ₂ CH ₂ - is, optionally substituted with -CH = CH-, and, R ¹ of the -CH ₂ - is, -O-, -NH-C (= O) -, -C ( consisting of =O)-NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)- You may be substituted by the group chosen from the group. However, adjacent -CH ₂ - is not simultaneously substituted with these groups. Moreover, -CH ₂ - may be _{-CH 2} - of the terminal in R ^{1 .} R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group. R ³ is a single bond, -O-, -C(=O)-O-, -OC(=O)-, or -CH=CH-C(=O)-O-. R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and when c ≥ 2, each R may be the same as or different from each other. a is 0, 1 or 2. b is 0 or 1. c is an integer satisfying 0≤c≤2b+4. The broken line is a bonding hand.

The ^{alkylene group having 1 to 30 carbon atoms represented by R 1 may} be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane group. -1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9- A diyl group, a decane-1, 10- diyl group, etc. are mentioned.

A phenylene group, a biphenylrylene group, etc. are mentioned as a divalent aromatic group represented by R<^2>. Examples of the divalent alicyclic group represented by R ^{2 include a cyclohexanediyl group.} Examples of the divalent heterocyclic group represented by ^{R 2 include a furandiyl group.} Examples of the divalent condensed cyclic group represented by ^{R 2 include a naphthylene group.}

As side chain a, what is represented by a following formula (a1) (it is also mentioned side chain a1 hereafter) is preferable.

[Formula 6]

In formula (a1), R ¹ , R ² and a are the same as above. R ^3A is a single bond, -O-, -C(=O)-O-, or -OC(=O)-. The benzene ring in the formula (a1) is a substituent selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. may be substituted with The broken line is a bonding hand.

As side chain a1, what is represented by a following formula (a1-1) is preferable, for example.

[Formula 7]

In formula (a1-1), L is a linear or branched C1-C16 alkylene group. X is a single bond, -O-, -C(=O)-O-, or -O-C(=O)-.

(A) It is preferable that a side chain type polymer reacts with the light of a 250-400 nm wavelength range, and shows liquid crystallinity in the temperature range of 100-300 degreeC. (A) It is preferable that a side chain type polymer has a photosensitive side chain which reacts with the light of the 250-400 nm wavelength range.

(A) The side chain which has photosensitivity is couple|bonded with the principal chain, and the side chain type polymer can sensitize light and raise|generate a crosslinking reaction or isomerization reaction. Although the structure of the photosensitive side chain type polymer which can express liquid crystallinity will not be specifically limited if such a characteristic is satisfy|filled, It is preferable to have a rigid mesogenic component in a side chain structure. When the said side chain type polymer is made into a single|mono layer retardation material, stable optical anisotropy can be acquired.

More specific examples of the structure of the photosensitive side chain polymer capable of expressing liquid crystallinity include (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl It is preferable that it is a structure which has the principal chain comprised by at least 1 sort(s) chosen from the group which consists of radically polymerizable groups, such as maleimide and norbornene, and siloxane, and a side chain a.

Moreover, since (A) side chain type polymer shows liquid crystallinity in the temperature range of 100-300 degreeC, it is preferable to have a side chain (henceforth side chain b) which expresses only liquid crystallinity further. In addition, here, the polymer which has only side chain b with "expresses only liquid crystal property" does not show photosensitivity in the manufacturing process of the retardation material of this invention (namely, process (I)-(III) mentioned later), but only liquid crystallinity here. means to express

As side chain b, any 1 type of liquid crystalline side chain chosen from the group which consists of following formula (1)-(13) is preferable.

[Formula 8]

[Formula 9]

In formulas (1) to (13), A ¹ and A ² are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. R ¹¹ is -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and 1 to 12 carbon atoms of an alkyl group or an alkyloxy group having 1 to 12 carbon atoms. R ¹² is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining them; hydrogen atoms binding to these, -NO _2, -CN, an alkoxy group a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms may be substituted for. R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing hetero a cyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. E is -C(=O)-O- or -OC(=O)-. d is an integer of 1-12. Although k1-k5 is each independently an integer of 0-2, the sum total of k1-k5 is 2 or more. Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more. m1, m2, and m3 are each independently an integer of 1-3. n is 0 or 1. Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ O-, -CH=N-, or -CF ₂ -. The broken line is a bonding hand.

Among these, as side chain b, what is represented by any one of Formulas (1)-(11) is preferable.

(A) The side chain type polymer of a component can be obtained by superposing|polymerizing the monomer which has a structure which expresses only liquid crystallinity as needed and the monomer which has a structure shown by Formula (a).

As a monomer (hereinafter also referred to as a monomer M1) having a structure represented by the formula (a), a compound represented by the following formula (M1) is exemplified.

[Formula 10]

(wherein, R ¹ , R ² , R ³ , R, a, m and n are the same as above)

As monomer M1, what is represented by a following formula (M1A) is preferable.

[Formula 11]

(wherein R ¹ , R ² , R ^3A , R and a are the same as above)

Among the monomers M1A, those represented by the following formula (M1B) are more preferable.

[Formula 12]

(wherein L and X are the same as above)

In formulas (M1), (M1A), and (M1B), PL is a polymerizable group represented by any of the following formulas (PL-1) to (PL-5).

[Formula 13]

In formulas (PL-1) to (PL-5), Q ¹ , Q ² and Q ³ are a hydrogen atom, a linear or branched C1-C10 alkyl group, or a halogen-substituted straight-chain, or It is a branched C1-C10 alkyl group. A broken line is a bond with ^{R 1 or L .} Among these monomers, some are commercially available, and some can be prepared from known materials by known production methods.

Preferred examples of the monomer M1 include those represented by the following formulas (M1-1) to (M1-5).

[Formula 14]

(Wherein, PL is the same as above. p is an integer of 2 to 9.)

The monomer (henceforth monomer M2) which has a structure which expresses only liquid crystallinity refers to the monomer which the polymer derived from the monomer expresses liquid crystallinity, and the polymer can form a mesogenic group in a side chain site|part.

As a mesogenic group which a side chain has, it may contribute to become a mesogenic structure independently, such as biphenyl and phenyl benzoate, and may also contribute to become a mesogenic structure by hydrogen bonding of side chains like benzoic acid. As a mesogenic group which a side chain has, the following structure is preferable.

[Formula 15]

More specific examples of the monomer M2 include radical polymerization of hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene. It is preferable that it is a structure which has a structure which consists of a polymeric group derived from at least 1 type selected from the group which consists of a sexual group and siloxane, and at least 1 type of Formula (1)-(13). In particular, it is preferable that the monomer M2 has (meth)acrylate as a polymeric group, and it is preferable that the terminal of a side chain is -COOH.

Preferred examples of the monomer M2 include those represented by the following formulas (M2-1) to (M2-11).

[Formula 16]

[Formula 17]

(wherein PL and p are the same as above)

Moreover, other monomers can be copolymerized in the range which does not impair the expression ability of photoreactivity and/or liquid crystallinity. Examples of the other monomer include an industrially available monomer capable of a radical polymerization reaction. As a specific example of another monomer, an unsaturated carboxylic acid, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 ,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate , tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylic and 8-ethyl-8-tricyclodecyl acrylate.

As a methacrylic acid ester compound, For example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- and propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example. As a styrene compound, styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene etc. are mentioned, for example. As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

From a photoreactive point, 20-99.9 mol% is preferable, as for content of the side chain a in the side chain type polymer of this invention, 30-95 mol% is more preferable, 40-90 mol% is still more preferable. do.

From a viewpoint of retardation value, 0.1-80 mol% is preferable, as for content of the side chain b in the side chain type polymer of this invention, 5-70 mol% is more preferable, 10-60 mol% is still more preferable. do.

As above-mentioned, the side chain type polymer of this invention may contain the other side chain. Content of another side chain is the remainder, when the sum total of content of side chain a and side chain b does not reach 100 mol%.

(A) The manufacturing method of the side chain type polymer of a component is not specifically limited, The general-purpose method handled industrially can be used. Specifically, it can manufacture by radical polymerization, cationic polymerization, or anionic polymerization using the vinyl group of the monomer M1 and the monomer M2 mentioned above, and another monomer as needed. Among these, radical polymerization is particularly preferable from the viewpoint of easiness of reaction control and the like.

As the polymerization initiator of the radical polymerization, a known compound such as a radical polymerization initiator (a radical thermal polymerization initiator, a radical photopolymerization initiator) and a reversible addition-cleavage type chain transfer (RAFT) polymerization reagent can be used.

A radical thermal polymerization initiator is a compound which generate|occur|produces a radical by heating more than decomposition temperature. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), and Sulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) can be heard A radical thermal polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

A radical photoinitiator will not be specifically limited if it is a compound which starts radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthiok. Santhone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, Isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl; 4-dimethylaminobenzoic acid isoamyl, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4 ,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxy Styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine , 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl )-s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl) -5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylamino Styryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o -Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole, 2,2'-bis (2,4-dibromo Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5, 5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H) -Pyrrol-1-yl)-phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexyl) Silperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl) )-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone , 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, 2-(3-methyl-1,3-benzothiazole-2(3H) -ylidene)-1-(2-benzoyl)ethanone etc. are mentioned. A radical photoinitiator may be used individually by 1 type, and may mix and use 2 or more types.

It does not specifically limit as a radical polymerization method, An emulsion polymerization method, suspension polymerization method, dispersion polymerization method, a precipitation polymerization method, a block polymerization method, a solution polymerization method, etc. can be used.

The organic solvent used for the polymerization reaction is not particularly limited as long as the produced polymer is dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-ε-caprolactam. , dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene Glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate , Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, Butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene Carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate, 3 -Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutylpropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3 -Methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-part and oxy-N,N-dimethylpropanamide.

The said organic solvent may be used individually by 1 type, and may mix and use 2 or more types. Moreover, even if it is a solvent which does not dissolve the produced|generated polymer, you may use it, mixing with the organic solvent mentioned above in the range in which the produced|generated polymer does not precipitate. Moreover, in radical polymerization, since oxygen in the organic solvent inhibits the polymerization reaction, it is preferable to use the organic solvent degassed to the extent possible.

Although the polymerization temperature at the time of radical polymerization can select the arbitrary temperature of 30-150 degreeC, Preferably it is the range of 50-100 degreeC. In addition, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. , Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The reaction initial stage can be performed at high concentration, and an organic solvent can be added after that.

In the radical polymerization reaction described above, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer becomes small, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer becomes large. It is preferable that it is mol%. In addition, at the time of polymerization, various monomer components, a solvent, an initiator, etc. can also be added.

In order to recover the polymer produced|generated from the reaction solution obtained by the said reaction, what is necessary is just to pour the reaction solution into a poor solvent, and to precipitate these polymers. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. can be heard The polymer charged and precipitated in the poor solvent can be collected by filtration, and then dried under normal pressure or reduced pressure at room temperature or by heating. Moreover, when the recovered polymer is redissolved in an organic solvent and the operation of reprecipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons, and the use of three or more poor solvents selected from these is preferable because the purification efficiency further increases.

When the (A) side chain type polymer of this invention considers the intensity|strength of the coating film obtained, workability|workability at the time of coating film formation, and the uniformity of a coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is 2,000-2,000,000 It is preferable that it is 2,000-1,000,000, it is more preferable, and it is still more preferable that it is 5,000-200,000.

[(B) Silane Coupling Agent]

The polymer composition of this invention contains (B) a silane coupling agent. As said silane coupling agent, the silane compound represented by a following formula (B) is preferable.

[Formula 18]

In formula (B), R ²¹ is a reactive functional group. R ²² is a hydrolysable group. R ²³ is a methyl group or an ethyl group. x is an integer of 0-3. y is an integer of 1-3.

Examples ^{of the reactive functional group represented by R 21} include an amino group, a ureide group, a (meth)acryloxy group, a vinyl group, an epoxy group, a mercapto group, and a group having an oxetane structure, and an amino group, a ureide group, ( A group having a meth)acryloyloxy group and an oxetane structure are preferable. Particularly preferably, it is a group having an oxetane structure.

As a hydrolysable group represented by R<^22> , a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxyalkoxy group, etc. are mentioned. As said halogen atom, a chlorine atom, a bromine atom, etc. are mentioned. The alkoxy group having 1 to 3 carbon atoms is preferably a linear or branched group, and specifically, a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group. Moreover, as a C2-C4 alkoxyalkoxy group, they are a methoxymethoxy group, 2-methoxyethoxy group, an ethoxymethoxy group, and 2-ethoxyethoxy group.

(B) Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl Methyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propyltrimethoxysilane, 3-(3- Ethyloxetan-3-ylmethyloxy)propyltriethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propylmethyldimethoxysilane, 3-(3-ethyloxetan-3-ylmethyl oxy) propylmethyl diethoxy silane etc. are mentioned.

Among these, 3-(3-ethyloxetan-3-ylmethyloxy)propyltrimethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propyltriethoxysilane, 3-(3- Ethyloxetan-3-ylmethyloxy)propylmethyldimethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propylmethyldiethoxysilane, and the like are particularly preferred. A commercial item can be used as said silane coupling agent.

In the polymer composition of this invention, 0.001-10 mass parts is preferable with respect to 100 mass parts of polymers (B), as for content of a silane coupling agent, 0.01-5 mass parts is more preferable, 0.05-1 mass part is still more preferable.

[(C) organic solvent]

(C) The organic solvent of component will not be specifically limited if it is an organic solvent in which a polymer component is dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, N-ethyl -2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N- Dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethylamylketone, methylnonylketone , methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol Monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether , dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. can be heard These may be used individually by 1 type, and may mix and use 2 or more types.

[Other Ingredients]

The polymer composition of this invention may also contain components other than (A)-(C)component. Examples include, but are not limited to, solvents and compounds that improve film thickness uniformity and surface smoothness when a polymer composition is applied, and compounds that improve adhesion between retardation materials and substrates.

Specific examples of the solvent (poor solvent) for improving film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl cellosolve. Solve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate , propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, di Hexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate , n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate, 3-methoxyethyl propionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, 3-methoxypropyl propionate, 3-methoxybutyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypro Foxy) solvents with low surface tension, such as propanol, etc. can be heard

These poor solvents may be used individually by 1 type, and may mix and use 2 or more types. When using the said poor solvent, it is preferable that it is 5-80 mass % in a solvent, and, as for the content, it is more preferable that it is 20-60 mass % in a solvent so that the solubility of the whole solvent contained in a polymer composition may not be reduced remarkably. .

As a compound which improves film thickness uniformity and surface smoothness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. Specific examples thereof include Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapac (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 ( 3M Co., Ltd.), Asahigard (registered trademark) AG710 (manufactured by AGC), Sufflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Semi Chemical), etc. can 0.01-2 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of these surfactant, 0.01-1 mass part is more preferable.

Moreover, in addition to the improvement of the adhesiveness of a board|substrate and retardation material, in order to prevent the fall of the characteristic by the backlight when a polarizing plate is comprised, etc., you may add a phenoplast type compound and an epoxy group containing compound to a polymer composition.

Although the specific example of a phenoplast type additive is shown below, it is not limited to these.

[Formula 19]

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5 ,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidyl) aminomethyl) cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. are mentioned.

When using the compound which improves adhesiveness with a board|substrate, 0.1-30 mass parts is preferable with respect to 100 mass parts of polymer components contained in a polymer composition, and, as for the content, 1-20 mass parts is more preferable. When content is less than 0.1 mass part, the effect of an adhesive improvement cannot be anticipated, and when it increases more than 30 mass parts, the orientation of a liquid crystal may worsen.

As an additive, a photosensitizer can also be used. As a photosensitizer, a colorless sensitizer and a triplet sensitizer are preferable.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, aromatic 2 -Hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, Thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothia Zoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene)-3 -Methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline, etc.), oxazoline (2-benzoylmethylene-3-methyl-β-naphthooxazoline) , 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxa Zoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-(p-fluoro robenzoylmethylene)-3-methyl-β-naphthooxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline, etc.), nitroacenaphthene (5-nitro acenaphthene, etc.), 2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethanone, etc.) ), naphthalene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, etc.), anthracene (9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, merocumarin, and the like. Of these, preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketal.

In the polymer composition of the present invention, as long as the effects of the present invention are not impaired in the polymer composition other than those described above, in order to change electrical properties such as dielectric constant and conductivity of the retardation material, dielectric or conductive material, furthermore, retardation material You may add a crosslinking|crosslinked compound in order to raise the hardness and density of the film|membrane at the time of doing it.

[Preparation of polymer composition]

It is preferable that the polymer composition of this invention is prepared as a coating liquid so that it may become suitable for formation of a single layer retardation material. That is, the polymer composition used for this invention is (A) component and (B) component, and the solvent and compound which improve the above-mentioned film thickness uniformity and surface smoothness, the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, etc. It is preferable to prepare as a solution melt|dissolved in the organic solvent of this (C)component. Here, as for content of (A) component, 1-20 mass % is preferable in the composition of this invention, More preferably, it is 3-15 mass %, Especially preferably, it is 3-10 mass %.

The polymer composition of this invention may contain other polymers other than the polymer of (A) component in the range which does not impair liquid-crystal expression ability and photosensitive performance. In that case, content of the other polymer in a polymer component becomes like this. Preferably it is 0.5-80 mass %, More preferably, it is 1-50 mass %. As for another polymer, the polymer etc. which are not the photosensitive side chain type polymer which can express liquid crystals, such as poly(meth)acrylate, a polyamic acid, and a polyimide, are mentioned, for example.

[Single-layer retardation material]

The single-layer retardation material of this invention can be manufactured by the method containing the following processes (I)-(III).

(I) a step of applying the composition of the present invention on a substrate to form a coating film;

(II) a step of irradiating polarized ultraviolet light to the coating film, and

(III) The process of heating the coating film irradiated with the said ultraviolet-ray, and obtaining a phase difference material.

[Process (I)]

Process (I) is a process of apply|coating the composition of this invention on a board|substrate, and forming a coating film. More specifically, the composition of the present invention is applied to a substrate (eg, silicon/silicon dioxide-coated substrate, silicon nitride substrate, metal (eg, aluminum, molybdenum, chromium, etc.) coated substrate, glass substrate, quartz substrate, ITO substrate, etc.) or film (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), bar coat, spin coat, flow coat , roll coating, slit coating, spin coating followed by slit coating, inkjet method, or printing method. After coating, the solvent is evaporated at 50 to 200°C, preferably 50 to 150°C, by a heating means such as a hot plate, heat circulation type oven, IR (infrared) type oven, and a coating film can be obtained.

[Process (II)]

At a process (II), the ultraviolet-ray which polarized to the coating film obtained by the process (I) is irradiated. When irradiating a polarized ultraviolet ray to the film surface of a coating film, the polarized ultraviolet ray is irradiated through a polarizing plate from a fixed direction with respect to a board|substrate. As said ultraviolet-ray, the ultraviolet-ray with a wavelength of 100-400 nm can be used. Preferably, an optimal wavelength is selected through a filter or the like according to the type of coating film to be used. And, for example, in order to selectively induce a photocrosslinking reaction, an ultraviolet ray having a wavelength of 290 to 400 nm can be selected and used. As the ultraviolet, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet-ray depends on the coating film to be used. The irradiation amount is within the range of 1 to 70% of the amount of polarized ultraviolet light that realizes the maximum value of ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the perpendicular direction in the coating film. It is preferable to do it, and it is more preferable to set it as 1 to 50 % of range.

[Process (III)]

In process (III), the coating film to which the ultraviolet-ray polarized in process (II) was irradiated is heated. By heating, orientation control ability can be provided to a coating film.

Heating can use heating means, such as a hotplate, a heat circulation type oven, and an IR (infrared) type|mold oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film to be used is expressed.

It is preferable that heating temperature exists in the temperature range of the temperature at which the polymer of (A) component contained in the composition of this invention expresses liquid crystal (henceforth liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature of the coating film surface is expected to be lower than the liquid crystal expression temperature at the time of observing the polymer of (A) component in bulk. For this reason, as for heating temperature, it is more preferable to exist in the temperature range of the liquid-crystal expression temperature on the surface of a coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet light is a temperature 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the polymer of component (A) as a lower limit, and a temperature 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range made into the upper limit. When the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy by heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the state of the coating film is in an isotropic liquid state (isotropic top), and in this case, it may be difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is above the liquid crystal transition temperature at which the polymer or coating film surface undergoes a phase transition from a solid phase to a liquid crystal phase, and below the isotropic phase transition temperature (Tiso) at which a phase transition occurs from a liquid crystal phase to an isotropic phase (isotropic phase). refers to the temperature of For example, to express liquid crystallinity at 130° C. or less means that the liquid crystal transition temperature at which a phase transition occurs from a solid to a liquid crystal phase is 130° C. or less.

The thickness of the coating film formed after heating can consider the level|step difference and optical and electrical properties of the board|substrate to be used, and can select it suitably, For example, 0.5-3 micrometers is preferable.

The single-layer retardation material of the present invention thus obtained is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as optical compensation films such as polarizing plates and retardation plates for liquid crystal displays.

Example

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

M1 is shown as a monomer which has a photoreactive group used in the Example, and M2 is shown below as a monomer which has a liquid crystalline group. M1 was synthesized according to the synthesis method described in International Publication No. 2011/084546. M2 was synthesized according to the synthesis method described in Japanese Patent Application Laid-Open No. 9-118717. Moreover, the side chain derived from M1 expresses photoreactivity and liquid crystallinity, and the side chain derived from M2 expresses only liquid crystallinity.

[Formula 20]

In addition, the abbreviation of the reagent used in this Example is shown below.

(organic solvent)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS : Butyl Cellosolve

BCA: Butyl Cellosolve Acetate

PGME: propylene glycol monomethyl ether

(Polymerization Initiator)

AIBN: 2,2'-azobisisobutyronitrile

(additive)

TESOX: 3-ethyl-3-[[3-(triethoxysilyl)propoxy]methyl]oxetane

MPMS: 3-methacryloxypropyltrimethoxysilane

S-1: 3-(phenylamino)propyltrimethoxysilane

S-2: 3-glycidoxypropyltriethoxysilane

[Formula 21]

[1] Synthesis of methacrylate polymer powder P1

[Synthesis Example]

M1 (13.3 g, 0.04 mol) and M2 (18.4 g, 0.06 mol) were dissolved in THF (128.7 g) and degassed with a diaphragm pump, after which AIBN (0.49 g) was added and degassed again. Then, it was made to react at 60 degreeC for 8 hours, and the methacrylate polymer solution was obtained. This polymer solution was dripped at methanol (1,000 ml), and the obtained deposit was filtered. Methacrylate polymer powder P1 was obtained by wash|cleaning this deposit with methanol and drying it under reduced pressure.

[2] Preparation of polymer solution

[Comparative Example 1]

Methacrylate polymer powder P1 (1.5 g) was added to NMP (3.25 g), and the mixture was dissolved by stirring at room temperature for 1 hour. Polymer solution CT1 was obtained by adding and stirring PGME (1.5g), BCS (3.0g), and BCA (0.75g) to this solution. This polymer solution CT1 was used as a material for forming the retardation film as it was.

[Example 1-1]

Polymer solution T1 was obtained by adding TESOX (0.075 g) as an additive to polymer solution CT1 (10.0g), and making it melt|dissolve by stirring at room temperature for 1 hour. The polymer solution T1 was used as a material for forming the retardation film as it was.

[Example 1-2]

Polymer solution T2 was obtained by adding MPMS (0.075g) as an additive to polymer solution CT1 (10.0g), and making it melt|dissolve by stirring at room temperature for 1 hour. This polymer solution T2 was used as a material for forming the retardation film as it was.

[Example 1-3]

Polymer solution T3 was obtained by adding S-1 (0.075g) as an additive to polymer solution CT1 (10.0g), and making it melt|dissolve by stirring at room temperature for 1 hour. This polymer solution T3 was used as a material for forming the retardation film as it was.

[Example 1-4]

Polymer solution T4 was obtained by adding S-2 (0.075g) as an additive to polymer solution CT1 (10.0g), stirring at room temperature for 1 hour, and making it melt|dissolve. This polymer solution T4 was used as a material for forming the retardation film as it was.

[3] Evaluation of polymer solution-1

[Example 2, Comparative Example 2]

(1) Preparation of evaluation substrate

After filtering polymer solution T1 with a 0.45 micrometer filter, it spin-coated on the glass substrate with a transparent electrode, and it dried for 90 second on a 70 degreeC hotplate, and formed the retardation film with a film thickness of 1.5-5.0 micrometers. Then, after irradiating 10 mJ/cm<2> of 313 nm ultraviolet-ray to the coating film surface through a polarizing plate, it heated for 20 minutes on a 150 degreeC hotplate, and obtained the board|substrates T1-1 - T1-5 with retardation film. Similarly, using the polymer solution CT1, substrates CT1-1 to CT1-5 with a retardation film were manufactured. Table 1 shows the film thickness of the obtained substrate.

(2) Phase difference evaluation

The phase difference value in 550 nm of board|substrates T1-1 - T1-5 and board|substrate CT1-1 - CT1-5 was evaluated using AxoScan by Axometrics. The results are shown in Table 1.

(3) HAZE evaluation

The retardation value in 550 nm of board|substrates T1-1 - T1-5 and board|substrate CT1-1 - CT1-5 was evaluated using the HAZE Meter HZ-V3 by Suga Test Instruments. A result is shown in Table 1.

As shown in Table 1, from the comparison between Example 2 and Comparative Example 2, in the solution containing only polymethacrylate, the HAZE value increased due to thickening (whitening), while the retardation value decreased ( By introducing the silane coupling agent of B) component, the increase (whitening) of HAZE value was suppressed significantly, and the result of maintaining a high phase difference value was obtained.

[4] Evaluation of polymer solution-2

[Examples 3-1 to 3-4, Comparative Example 3]

After each of the polymer solutions T1 to T4 and CT1 were filtered with a filter of 0.45 µm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 °C for 90 seconds to form a retardation film with a thickness of 2.5 µm did Subsequently, the coating film surface was irradiated with 313 nm ultraviolet rays at 10 mJ/cm 2 through a polarizing plate, and then heated on a hot plate at 150° C. for 20 minutes to obtain substrates T1 to T4 and CT1 with a retardation film.

By the method similar to Example 1, retardation evaluation and HAZE evaluation of the obtained board|substrate were implemented. A result is shown in Table 2.

As shown in Table 2, from the comparison between Examples 3-1 to 3-4 and Comparative Example 3, the polymethacrylate solution alone had a high HAZE value (whitening) and a low retardation value, but was introduced in any additive. By doing this, while the HAZE value was suppressed low, the result showing a high phase difference value was obtained.

Claims (7)

(A) side chain type polymer which has a side chain which has a photoreactive site|part represented by following formula (a);
(B) a silane coupling agent, and
(C) a polymer composition comprising an organic solvent.

(Wherein, R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom or an organic group. In addition, -CH ₂ CH ₂ - ^{in R 1} may be substituted with -CH=CH-, and -CH ₂ ^{- in R 1} is, -O-, -NH-C(=O)-, -C(=O)-NH-, -C(= It may be substituted with a group selected from the group consisting of O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH-, and -C(=O)-. , -CH ₂ adjacent - is is not substituted at the same time, these groups also, -CH ₂ -. is, -CH ₂ of the terminal of R ¹ - or may be.
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group.
R ³ is a single bond, -O-, -C(=O)-O-, -OC(=O)-, or -CH=CH-C(=O)-O-.
R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and when c ≥ 2, each R may be the same as or different from each other.
a is 0, 1 or 2.
b is 0 or 1.
c is an integer satisfying 0≤c≤2b+4.
The broken line is the bonding hand.) The method of claim 1,
The polymer composition in which the side chain which has the said photoreactive site|part is represented by following formula (a1).

(In the formula, R ¹ , R ² and a are the same as above.
R ^3A is a single bond, -O-, -C(=O)-O-, or -OC(=O)-.
The benzene ring in the formula (a1) is a substituent selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. may be substituted with
The broken line is the bonding hand.) 3. The method according to claim 1 or 2,
(A) The polymer composition in which a side chain type polymer has a side chain which expresses only liquid crystal further. 4. The method of claim 3,
The polymer composition whose side chain which expresses only the said liquid crystal is a liquid crystalline side chain represented by any one of following formula (1) - (13).

(wherein, A ¹ , A ² are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-.
R ¹¹ is -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and 1 to 12 carbon atoms of an alkyl group or an alkyloxy group having 1 to 12 carbon atoms.
R ¹² is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining them; hydrogen atoms binding to these, -NO _2, -CN, an alkoxy group a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms may be substituted for.
R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing hetero a cyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
E is -C(=O)-O- or -OC(=O)-.
d is an integer of 1-12.
Although k1-k5 is each independently an integer of 0-2, the sum total of k1-k5 is 2 or more.
Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more.
m1, m2, and m3 are each independently an integer of 1-3.
n is 0 or 1.
Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ O-, -CH=N-, or -CF ₂ -.
The broken line is the joining hand.) 5. The method of claim 4,
The polymer composition whose side chain which expresses only the said liquid crystal is a liquid crystalline side chain represented by any one of Formula (1)-(11). (I) the step of applying the polymer composition according to any one of claims 1 to 5 on a substrate to form a coating film;
(II) a step of irradiating the coating film with polarized ultraviolet rays, and
(III) Heating the coating film irradiated with the said ultraviolet-ray, The manufacturing method of a single-layer retardation material including the process of obtaining retardation material. The single-layer retardation material obtained from the composition in any one of Claims 1-5.