TW201900772A - Hardened film forming composition, alignment material, and phase difference material - Google Patents

Abstract

To provide a cured film-forming composition for forming a cured film which exhibits excellent liquid crystal alignment properties and light transmissivity when used as an alignment material with a layer of a polymerizable liquid crystal disposed thereupon. A cured film-forming composition containing (A) a polymer having a photodimerization moiety and a self-crosslinking moiety; an alignment material characterized by being obtained using the composition; and a phase difference material characterized by being obtained using the composition.

Description

Hardened film forming composition, alignment material and retardation material

The present invention relates to a hardened film-forming composition of a liquid crystal alignment agent for photo-alignment by aligning liquid crystal molecules, and an alignment material and a retardation material obtained from the hardened film-forming composition. In particular, the present invention relates to a patterned retardation material used in 3D display of circularly polarized glasses or a retardation material used in the manufacture of a circularly polarizing plate used as an anti-reflection film for an organic EL display. A cured film-forming composition with a liquid crystal alignment agent for photo-alignment, an alignment material and a retardation material obtained from the cured film-forming composition.

In the 3D display of the circularly polarized glasses method, a phase difference material is usually arranged on a display element forming an image such as a liquid crystal panel. This retardation material includes two types of retardation regions having different retardation characteristics, each of which is arranged in a plural number and regularly and constitutes a graphed retardation material. In addition, in the present specification, in order to arrange a plurality of phase difference regions having such different phase difference characteristics, the patterned phase difference material is referred to as a patterned phase difference material.

The patterned retardation material is, for example, disclosed in Patent Document 1, and a retardation material made of a polymerizable liquid crystal can be produced as an optical pattern. The optical patterning of a retardation material made of a polymerizable liquid crystal can use a photo-alignment technique known in the formation of alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated there. A light alignment film is obtained as an alignment material for forming two types of liquid crystal alignment regions with different alignment control directions of the liquid crystal. A solution-like retardation material containing a polymerizable liquid crystal is coated on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is hardened to form a patterned retardation material.

The anti-reflection film of the organic EL display is composed of a linear polarizing plate and a 1/4 wavelength retardation plate. The external light facing the panel surface of the image display panel is converted into linear polarized light by a linear polarizing plate. It is converted into circularly polarized light by a 1/4 wavelength retardation plate. Among them, the light outside the circularly polarized light is reflected on the surface of the image display panel or the like, but the direction of rotation of the polarized surface is reversed during the reflection. As a result, the reflected light is opposite to the arrival, and is converted into linearly polarized light in the direction in which the linearly polarizing plate is blocked by a 1/4 wavelength retardation plate, and then continuously blocked by the linearly polarizing plate. The ejection is significantly suppressed.

Regarding this 1/4 wavelength retardation plate, as described in Patent Document 2, when a 1/4 wavelength retardation plate is formed by combining a 1/2 wavelength plate and a 1/4 wavelength plate, the optical film is caused to be reversely dispersed. The method of characterization. In the case of this method, for a wide wavelength band provided for display of a color image, a liquid crystal material with a positive dispersion characteristic can be used to constitute an optical film with a reverse dispersion characteristic.

Moreover, in recent years, as a liquid crystal material applicable to this retardation layer, those having reverse dispersion characteristics have been proposed (Patent Documents 3 and 4). Based on the liquid crystal material with such inverse dispersion characteristics, a 1 / 2-wavelength plate and a 1 / 4-wavelength plate are combined to form a 1 / 4-wavelength retardation plate with two retardation layers. Instead, the retardation layer can be composed of a single layer. By ensuring the reverse dispersion characteristics, it is possible to ensure that an optical film with a desired phase difference in a wide wavelength band can be simply constructed and realized.

To align the liquid crystal, an alignment layer is used. As a method for forming the alignment layer, for example, a rubbing method or a photo-alignment method is known, and it is useful from the viewpoint that static electricity or dust can be generated without the problems of the rubbing method in the photo-alignment method and a quantitative alignment process can be controlled.

In the formation of alignment materials using the photo-alignment method, acrylic resins or polyimide resins having photodimerization sites such as a cinnamonyl group and a chalcone group on a side chain are known as available photo-alignment materials. Wait. It has been reported that these resins can exhibit the performance of controlling the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by performing polarized UV irradiation (see Patent Documents 5 to 7).

The alignment layer also requires solvent resistance in addition to the liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or solvents during the manufacturing process of the retardation material. When the alignment layer is exposed to a solvent, there is a concern that the alignment of the liquid crystal can be significantly reduced.

Among them, for example, it is described in Patent Document 8 that in order to obtain stable liquid crystal alignment energy, a liquid crystal alignment agent containing a polymer component having a structure that can be crosslinked by photoreaction and a structure that is crosslinked by heat is proposed, and A liquid crystal alignment agent containing a polymer component having a structure that can be crosslinked by light and a compound having a structure that is crosslinked by heat. [Prior Art Literature] [Patent Literature]

[Patent Document 1] JP 2005-49865 [Patent Document 2] JP 10-68816 [Patent Document 3] US Patent No. 8119026 [Patent Document 4] JP 2009-179563 [Patent Document 5] Patent No. 3611342 [Patent Document 6] JP 2009-058584 [Patent Document 7] Special Table 2001-517719 [Patent Document 8] Patent No. 4207430

[Problems Solved by the Invention]

As described above, the retardation material is formed on the photo-alignment film of the alignment material, and a layer of a cured polymer liquid crystal is laminated. Therefore, it is necessary to develop an alignment material having both excellent liquid crystal alignment and solvent resistance.

However, according to the review by the inventors, it was found that the acrylic resin having a photodimerization site such as a cinnamonyl group or a chalcone group in a side chain cannot obtain sufficient characteristics when it is suitable for forming a retardation material. In particular, in order to form an alignment material by irradiating polarized UV to these resins, when using this alignment material to produce a retardation material made of a polymerizable liquid crystal, a large amount of polarized UV exposure is required. The amount of polarized UV exposure must be greater than the amount of polarized UV exposure (for example, about 30 mJ / cm ² ) that is sufficient to align the liquid crystal used for general liquid crystal panels.

As a reason for increasing the amount of polarized UV exposure, when a retardation material is formed, it is different from the liquid crystal used for a liquid crystal panel, and the polymerizable liquid crystal is used in a solution state and is coated on an alignment material.

An alignment material is formed by using an acrylic resin or the like having a photodimerization site such as a cinnamonyl group in a side chain, and when the polymerizable liquid crystal is to be aligned, the acrylic resin or the like is subjected to photocrosslinking by a photodimerization reaction. On the other hand, before exhibiting resistance to a polymerizable liquid crystal solution, it is necessary to perform polarized light irradiation with a large exposure amount. In order to align the liquid crystal of the liquid crystal panel, usually only the surface of the photo-alignment alignment material is subjected to a dimerization reaction. However, when the conventional materials such as the acrylic resin are used, in order to exhibit solvent resistance on the alignment material, it is necessary to react to the inside of the alignment material, and a larger amount of exposure is required. As a result, there has been a very small problem that the alignment sensitivity of materials has changed in the past.

In order to exhibit such solvent resistance on the resin of the conventional material, a technique of adding a crosslinking agent is known. However, it was found that after performing a thermosetting reaction with a cross-linking agent, a three-dimensional structure was formed inside the formed coating film, and photoreactivity was reduced. That is, the alignment sensitivity is greatly reduced, and even if a crosslinking agent is added to a conventional material and used, the desired effect cannot be obtained.

From the above, it is expected that a light alignment technology capable of increasing the alignment sensitivity of the alignment material and reducing the amount of polarized UV exposure and a cured film forming composition for a liquid crystal alignment agent for light alignment for forming the alignment material are expected. A technology that can efficiently provide retardation materials is expected.

The object of the present invention is based on the above findings or review results. That is, an object of the present invention is to provide an alignment material having excellent solvent resistance and capable of aligning polymerizable liquid crystals under high sensitivity, and further provide a cured film-forming composition that is a liquid crystal alignment agent for photo-alignment.

Other objects and advantages of the present invention will be apparent from the following description. [Means for solving problems]

In order to achieve the above object, the present inventors conducted repeated detailed review and found that by selecting a hardened film forming material containing a hardened film forming composition containing a polymer having a photodimerization site and a self-crosslinking site as a base, A hardened film having excellent solvent resistance and capable of orienting a polymerizable liquid crystal under high sensitivity can be formed, thereby completing the present invention.

That is, as a first aspect of the present invention, it relates to a cured film-forming composition containing (A) a polymer having a photodimerization site and a self-crosslinking site. (2) As a second viewpoint, the cured film forming composition according to the first viewpoint is that the self-crosslinking site of the component (A) is methylol or alkoxymethyl. As a third aspect, it is further about (B) having at least two groups selected from the group consisting of methylol, alkoxymethyl, hydroxyl, carboxyl, amido, amine, and alkoxysilyl groups. The cured film forming composition according to the first or second aspect of the monomer or polymer of one group. As a fourth aspect, the cured film-forming composition according to any one of the first to third aspects further containing (C) a cross-linking catalyst. As a fifth aspect, it is about (D) containing at least one polymerizable group having at least one group A selected from the group consisting of a hydroxyl group, a carboxyl group, a amine group, an amine group, and an alkoxysilyl group, The cured film forming composition according to any one of the first to fourth aspects of the compound of at least one group that reacts with the group A. The 6th viewpoint is the hardening film formation composition as described in any one of the 3rd viewpoint-5th viewpoint which contains 1 mass part-400 mass parts of (B) component with respect to 100 mass parts of (A) component. Thing. The seventh aspect is the cured film forming composition according to any one of the fourth aspect to the sixth aspect with respect to 100 parts by mass of the (A) component and containing 0.01 to 20 parts by mass of the (C) component. Thing. The eighth aspect is the cured film forming composition described in any one of the fifth to seventh aspects with respect to 100 parts by mass of the (A) component and containing 1 to 100 parts by mass of the (D) component. Thing. As a ninth aspect, the cured film is characterized by being obtained by curing the cured film-forming composition described in any one of the first to eighth aspects. As a tenth aspect, it is an alignment material characterized by being obtained by curing the cured film-forming composition described in any one of the first to eighth aspects. As an eleventh aspect, the present invention relates to a retardation material characterized by being formed using a cured film obtained by using the cured film-forming composition described in any one of the first to eighth aspects. [Effect of the invention]

According to the present invention, it is possible to provide a cured film having excellent solvent resistance and capable of aligning polymerizable liquid crystals at a high sensitivity, and a cured film forming composition suitable for the formation. According to the present invention, an alignment material having excellent liquid crystal alignment and light transmittance, and a phase difference material capable of achieving high-precision optical mapping can be provided.

<Hard film-forming composition> 硬化 The hard film-forming composition of the present invention contains (A) a polymer having a photodimerization site and a self-crosslinking site. The cured film forming composition of the present invention may further contain, as the component (B), two or more members selected from the group consisting of methylol, alkoxymethyl, hydroxyl, carboxyl, amine, and amine, in addition to the component (A). A monomer or polymer having at least one group formed by a group and an alkoxysilyl group. It may further contain a crosslinking catalyst as a component (C). It may further contain one or more polymerizable groups as the component (D), and at least one group A selected from the group consisting of a hydroxyl group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group, or A compound in which at least one group of groups A reacts. Without impairing the effect of the present invention, other additives may be contained.成分 Each component is explained in detail below.

<(A) component> (A) component is an acrylic copolymer which has a photodimerization site | part and a self-crosslinking site | part.中 In the present invention, as the acrylic copolymer, a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylate, methacrylate, or styrene can be used.

The acrylic copolymer of the component (A) having a photodimerization site and a self-crosslinking site (hereinafter also referred to as a specific copolymer) may be an acrylic copolymer having such a structure. The type of the skeleton and side chains of the chain are not particularly limited.

The photodimerization site is a site that forms a dimer upon irradiation with light. Specific examples of the site include a cinnamyl group, a chalcone group, a coumarin group, and an anthracenyl group. Among these, a cinnamyl group having high transparency in the visible light region and photodimerization reactivity is preferred. The structure of a preferable cinnamyl group is shown by the following formula [1] or [2]. In the above formula, X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. In this case, phenyl and biphenyl may be substituted with any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group. X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms may be bonded to a benzene ring via a single bond, an ether bond, an ester bond, a amide bond, a urea bond, or the like.

The self-crosslinking site is a site that is bonded to each other to form a crosslinked structure, and examples thereof include an alkoxymethylamidino group, a hydroxymethylamidino group, an alkoxysilyl group, and a blocked isocyanate group.

The weight average molecular weight of the acrylic copolymer (A) is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight average molecular weight is more than 200,000, the solubility to the solvent will be reduced, and the handleability will also decrease. If the weight average molecular weight is less than 3,000, the hardening during thermal curing will be changed. Insufficient and solvent resistance and heat resistance may be reduced.

As described above, as the component (A), a method for synthesizing an acrylic copolymer having a photodimerization site and a self-crosslinking site in a side chain is used to separate a monomer having a photodimerization site with a monomer having a self-crosslinkable group. The method of copolymerization of the polymer is simple.

Examples of the monomer having a photodimerization site include monomers having a cinnamyl group, a chalcone group, a coumarin group, or an anthracene group. Among these, a monomer having a cinnamyl group having good transparency and photodimerization reactivity in the visible light region is particularly preferred.

In particular, a cinnamylmer group having a structure represented by the formula [1] or the formula [2] is preferred. Specific examples of such monomers are shown in the following formula [3] or formula [4]. In the foregoing formula, X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. In this case, phenyl and biphenyl may be substituted with any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group. X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms may be bonded to the benzene ring via a single bond, an ether bond, an ester bond, a amide bond, or a urea bond. X ³ and X ⁵ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group, or an aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or linear, or may be substituted by a hydroxyl group, or may be selected from an ether bond, an ester bond, a amine bond, a urea bond, and an amine group. At least one bond of the formate bond is interrupted. X ⁴ and X ⁶ represent polymerizable groups. Specific examples of the polymerizable group include acrylfluorenyl, methacrylfluorenyl, styryl, maleimide, acrylamido, and methacrylamido.

Examples of the monomer having a self-crosslinking site include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl ( (Meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. (meth) acrylamide compounds substituted with hydroxymethyl or alkoxymethyl; 3-trimethoxysilyl Propyl acrylate, 3-triethoxysilylpropylacrylate, 3-trimethoxysilylpropylmethacrylate, 3-triethoxysilylpropylmethacrylate, etc. Monooxysilane-based monomer; 2- (0- (1'-methylpropyleneamino) carboxyamino) ethyl methacrylate, 2- (3,5-dimethylpyridine) A blocked isocyanate-based monomer such as oxazolyl) carbonylamino) ethyl and the like. The (meth) acrylamide refers to both acrylamide and methacrylamide.

In addition, in the present invention, in order to obtain a specific copolymer, in addition to a monomer having a photodimerization site and a self-crosslinking site (hereinafter also referred to as a specific functional group), the monomer may be used in combination with a copolymerizable monomer body.

Specific examples of such a monomer include an acrylate compound, a methacrylate compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

Specific examples of the aforementioned monomers are given below, but are not limited thereto. Examples of the acrylate compound include methacrylate, ethacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2,3-dihydroxy. Propyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (propenyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-propenyloxy-6-hydroxyl Norbornene-2-carboxy-6-lactone, acrylic acid, mono- (2- (propenyloxy) ethyl) phthalate, glycidyl acrylate, isopropyl acrylate, benzoic acid Acrylate, naphthalene acrylate, anthryl acrylate, anthryl methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, Isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate Ester, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8 -Tricyclodecyl acrylate and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylate compound include methmethacrylate, ethylmethacrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, and 4-hydroxybutyl methyl ester. Acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacrylic acid) ethyl ester, 5-methacrylic acid -6-hydroxynorbornene-2-carboxy-6-lactone, glycidyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methyl Acrylate, anthryl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isopropyl Bornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methyl Acrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate Ester, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8- Tricyclodecyl methacrylate and the like.

Examples of the acrylamide compound include acrylamide, methacrylamide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and N- (hydroxybenzene Methacrylamide and N- (hydroxyphenyl) acrylamide.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-vinyl-7-oxo Cyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N- (hydroxyphenyl) maleimide , N- (carboxyphenyl) maleimide and N-cyclohexylmaleimide and the like.

The amount of each monomer used to obtain a specific polymer is based on the total amount of all monomers, a monomer having a photodimerization site of 25 to 90 mole%, and a self-crosslinking of 10 to 75 mole%. The monomer of the linking site is preferably a monomer having no specific functional group of 0 to 65 mole%. When the content of the monomer having a photodimerization site is less than 25 mol%, it is difficult to provide high sensitivity and good liquid crystal alignment. When the content of the monomer having a self-crosslinking portion is less than 10 mol%, it is difficult to impart sufficient thermosetting properties, and it is difficult to maintain high sensitivity and good liquid crystal alignment.

The method for obtaining the specific copolymer used in the present invention is not particularly limited. For example, in a solvent in which a monomer having a specific functional group and a monomer having no specific functional group as required and a polymerization initiator coexist, It is obtained by polymerization at a temperature of 50 to 110 ° C. In this case, the solvent to be used is not particularly limited as long as it can dissolve a monomer having a specific functional group, a monomer having no specific functional group, a polymerization initiator, etc., if necessary. A specific example is described in <solvent> mentioned later.特定 The specific copolymer obtained by the aforementioned method is usually in a solution state dissolved in a solvent.

In addition, the solution of the specific copolymer obtained by the above method is re-precipitated by adding diethyl ether or water under stirring, and the resulting precipitate is filtered and washed, and then the solution is subjected to normal pressure or reduced pressure. Drying at room temperature or drying under heat can make it a powder of specific copolymer. By the foregoing operation, the polymerization initiator and unreacted monomers that coexist with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If sufficient purification cannot be performed in one operation, the obtained powder may be redissolved in a solvent, and the above operations may be repeated.

In the present invention, the specific copolymer can be used in the form of a powder or a solution in which the purified powder is redissolved in a solvent described later.

In the present invention, the specific copolymer of the component (A) may be a mixture of a plurality of specific copolymers.

<(B) component> 硬化 The hardened film forming composition of the present invention may contain, as component (B), two or more members selected from the group consisting of methylol, alkoxymethyl, hydroxyl, carboxyl, amido, and amino groups. A monomer or polymer having at least one group of alkoxysilyl groups.

Examples of the monomer or polymer having two or more methylol groups and alkoxymethyl groups include alkoxymethylated ethylene glycol urea, alkoxymethylated benzoguanamine, and alkoxy groups. Methylated methylol compounds such as melamine.

Specific examples of the alkoxymethylated glycol urea include 1,3,4,6- (methoxymethyl) glycol urea, 1,3,4,6- ( Butoxymethyl) glycol urea, 1,3,4,6- (Hydroxymethyl) glycol urea, 1,3-bis (hydroxymethyl) urea, 1,1,3,3- Silyl (butoxymethyl) urea, 1,1,3,3-silyl (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazoline Ketones, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinones. Examples of commercially available products include compounds such as ethylene glycol urea compounds (trade names: Cymel (registered trademark) 1170, Powder link (registered trademark) 1174) made by Japan Cytec Industries (former Mitsui Cytec (stock)), Methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock) (Formerly Dainippon Ink Chemical Industry Co., Ltd.) made of urea / formaldehyde resin (high condensation type, trade name: Beccamine (registered trademark) J-300S, same as P-955, same as N), etc.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. Examples of commercially available products include Japan Cytec Industries (former Mitsui Cytec (stock)) (trade name: Cymel (registered trademark) 1123), (share) Sanwa Chemical (trade name: Nicarac (registered trademark) ) BX-4000, same as BX-37, same as BL-60, same as BX-55H) and so on.

Specific examples of the alkoxymethylated melamine include hexamethoxymethyl melamine and the like. Examples of commercially available products include methoxymethyl melamine compounds (trade names: Cymel (registered trademark) 300, same 301, same 303, and 350) made by Japan Cytec Industries (former Mitsui Cytec (stock)). ), Butoxymethyl-type melamine compounds (trade name: My coat (registered trademark) 506, same as 508), (share) Sanwa Chemical methoxymethyl-type melamine compounds (trade name: Nicarac (registered trademark) MW-30, same MW-22, same MW-11, same MS-001, same MX-002, same MX-730, same MX-750, same MX-035), butoxymethyl melamine compounds (commodity Name: Nicarac (registered trademark) MX-45 (same as MX-410, same as MX-302), etc.

Moreover, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycol urea compound, and a benzoguanamine compound in which the hydrogen atom of the amine group is replaced by a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in US Patent No. 6323310 can be mentioned. Examples of commercially available products of the melamine compound include a trade name: Cymel (registered trademark) 303, and examples of commercially available products of the benzoguanamine compound include a trade name: Cymel (registered trademark) 1123 (above: Japan Cytec Industries (stock) (made by Former Mitsui Cytec (stock)), etc.

In addition, as a component having a methanol group of (B) and a polymer having two or more alkoxymethyl groups, N-hydroxymethacrylamide and N-methoxymethylmethacrylamine are used. Hydroxymethyl (i.e. hydroxymethyl) or alkoxymethyl substituted acrylamide compounds or methyl groups such as N-ethoxymethacrylamide, N-butoxymethylmethacrylamine, or alkoxymethyl A polymer made from an acrylamide compound.

Examples of such polymers include poly (N-butoxymethacrylamide), a copolymer of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacrylamide Copolymer with methyl methacrylate, copolymer of N-ethoxymethylmethacrylamide and benzylmethacrylate, and N-butoxymethacrylamide with benzyl Copolymers of methacrylate and 2-hydroxypropyl methacrylate, etc.

As such a polymer, a polymer having a polymerizable group containing an N-alkoxymethyl group and a C = C double bond can also be used.

Examples of the polymerizable group containing a C = C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group.

The method for obtaining the polymer as described above is not particularly limited. To give an example, this is an acrylic polymer having a specific functional group by a polymerization method such as radical polymerization in advance. Next, the specific functional group reacts with a compound having an unsaturated bond at its terminal (hereinafter referred to as a specific compound), and a polymerizable group containing a C = C double bond can be introduced into the polymer of the component (B).

Here, the specific functional group means a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amine group having an active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a plurality of functional groups selected from these.

For the above reaction, the preferred combination of the specific functional group and the reaction-related groups of the functional group of the specific compound is a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, and a carboxyl group and an isocyanate group , Amine and isocyanate groups or hydroxyl and acid chloride groups. More preferred combinations are carboxyl and glycidyl methacrylate, or hydroxyl and isocyanate ethyl methacrylate.

The weight average molecular weight (polystyrene equivalent) of the polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and more preferably 3,000 to 50,000.

Further, as the component (B), a monomer or polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amine group, an amine group, and an alkoxysilyl group, and examples thereof include, for example, Acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, Polyalkyleneimines, polyallylamines, celluloses (cellulose or its derivatives), phenol novolac resins, melamine formaldehyde resins and other polymers with linear or branched structures, cyclodextrin, etc. Cyclic polymer and so on.

Preferred examples include acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

A preferred example of the acrylic polymer as the polymer of component (B) is a polymer obtained by polymerizing a monomer having unsaturated double bonds such as acrylic acid, methacrylic acid, styrene, and a vinyl compound. The polymer may be a polymer obtained by polymerizing a monomer or a mixture containing a monomer having a specific functional group, and the type of the backbone and side chain of the main chain of the polymer constituting the acrylic polymer is not particularly limited.

Examples of the monomer having a specific functional group include a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxyl group, and a carboxyl group. Monomers, monomers having an amine group, monomers having an alkoxysilyl group, and a monomer represented by ethoxyethyl.

Examples of the monomer having a polyethylene glycol ester group include a monoacrylate or a monomethacrylate of H- (OCH ₂ CH ₂ ) _n -OH. The n value is 2 to 50, and preferably 2 to 10.

Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl methacrylate. , 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate.

Examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.

Examples of the monomer having an amine group in the side chain include 2-aminoethylacrylate, 2-aminoethylmethacrylate, aminopropylacrylate, and aminopropylmethacrylate .

Examples of the monomer having an alkoxysilyl group in the side chain include 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, and 3-methacryl Alkoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyl Triethoxysilane and the like.

In addition, in the present embodiment, when synthesizing the acrylic polymer as an example of the component (B), the hydroxyl group, carboxyl group, amido group, amine group, and alkoxysilyl group may be used in combination without impairing the effects of the present invention. Monomer of any of the groups shown.

Specific examples of the monomer include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

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

Examples of the methacrylate compound include methmethacrylate, ethylmethacrylate, isopropylmethacrylate, benzylmethacrylate, naphthylmethacrylate, and anthracenemethyl Acrylate, anthryl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isopropyl Bornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate Ester, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tri Cyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate and the like.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

The amount of the monomer having a specific functional group used to obtain the acrylic polymer of the example of the component (B) is based on the total amount of all monomers used to obtain the acrylic polymer of the (B) component. Above 2 mole% is preferred. If the monomer having a specific functional group is too small, the solvent resistance of the obtained cured film tends to be insufficient.

The method for obtaining the acrylic polymer as an example of the component (B) is not particularly limited. For example, a monomer containing a monomer having a specific functional group, a monomer having no specific functional group and a polymerization initiator as required It can be obtained by performing a polymerization reaction at a temperature of 50 ° C to 110 ° C, such as a coexisting solvent. The solvent used at this time is not particularly limited as long as it is capable of dissolving a monomer having a specific functional group, a monomer not having a specific functional group, a polymerization initiator, etc., as required. As a specific example, it will be described in the section of [solvent] described later.

The acrylic polymer as an example of the component (B) obtained by the above method is usually in a solution state dissolved in a solvent.

In addition, the solution of the acrylic polymer of the example of the component (B) obtained by the above method was put into diethyl ether or water under stirring to reprecipitate, and the resulting precipitate was filtered and washed. Then, it is made to dry at normal temperature or heat-dry under normal pressure or reduced pressure, and the powder of the acrylic polymer which is an example of (B) component can be obtained. By the above operation, a polymerization initiator and an unreacted monomer that coexist with the acrylic polymer of the example of the (B) component can be removed. As a result, the purified acrylic polymer of the example of the (B) component can be obtained. Powder. If sufficient purification cannot be performed in one operation, the obtained powder can be dissolved in the solvent again, and the above operations can be repeated.

The weight average molecular weight in the acrylic polymer of a preferable example of the component (B) is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight average molecular weight exceeds 200,000, the solubility to the solvent will be reduced to reduce the handleability. If the weight average molecular weight is less than 3,000, it will become insufficiently hardened during thermal curing and decrease. Solvent resistance occurs. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. The same applies to the following descriptions.

Next, as one of the preferred examples of the component (B), the polyether polyol includes polyethylene glycol, polypropylene glycol, propylene glycol, or polyhydric alcohols such as bisphenol A, triethylene glycol, and sorbitol. Propane or polyethylene glycol, polypropylene glycol, etc. Specific examples of the polyether polyol include Adeka polyetherP series, G series, EDP series, BPX series, FC series, CM series, and UNIOX (registered trademark) HC-40, HC-60, and ST manufactured by ADEKA. -30E, ST-40E, G-450, G-750, UNIOL (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB- 400, non-ion (registered trademark) LT-221, ST-221, OT-221, etc.

Polyester polyols which are preferred examples of the component (B) include polybasic carboxylic acids such as adipic acid, sebacic acid, and isophthalic acid, and ethylene glycol, propylene glycol, butanediol, and polyethylene glycol. Those reacting with diols such as alcohol and polypropylene glycol. Specific examples of polyester polyols include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD- X-2523, OD-X-2555, OD-X-2560, Kuraray polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F- 510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.

As a preferred example of the (B) component, a polycaprolactone polyol includes a ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as a starter. . Specific examples of polycaprolactone polyols include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, manufactured by DIC, Plaxel (registered trademark) 205, manufactured by Daicel Chemical, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc.

As a preferable example of the polycarbonate polyol as the component (B), a polyhydric alcohol such as trimethylolpropane or ethylene glycol, and diethyl carbonate, diphenyl carbonate, and ethyl carbonate are exemplified. Wait for a response. Specific examples of the polycarbonate polyol include Plaxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical, and C-590, C-1050, C-2050, C-2090, C manufactured by Kuraray. -3090 and so on.

Examples of cellulose as a preferred component (B) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl fiber Hydroxyalkyl celluloses such as cellulose, hydroxyethyl ethyl cellulose, and cellulose are preferred, and hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferred.

Examples of the cyclodextrin which is a preferable example of the polymer of the component (B) include cyclodextrin such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, and methyl-α-cyclodextrin. Methylated cyclodextrins such as dextrin, methyl-β-cyclodextrin and methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl -Γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl- α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β- Cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, 2,3- Dihydroxypropyl-γ-cyclodextrin and the like.

As a preferred example of the component (B), the melamine formaldehyde resin is a resin obtained by polycondensing melamine and formaldehyde, which is represented by the following formula.

In the above formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a natural number of the number of repeating units.

From the standpoint of storage stability, the melamine formaldehyde resin is preferably one in which the methylol group formed during the polycondensation of melamine and formaldehyde is alkylated.

The method for obtaining the melamine formaldehyde resin is not particularly limited. Generally, it is synthesized by mixing melamine and formaldehyde, using a weak alkali such as sodium carbonate or ammonia, and heating at 60 ° C to 100 ° C. After further reacting with an alcohol, the methylol group can be alkoxylated.

The weight average molecular weight of the melamine formaldehyde resin is preferably from 250 to 5,000, more preferably from 300 to 4,000, and even more preferably from 350 to 3500. If the weight average molecular weight exceeds 5000, the solubility to the solvent will decrease and handling properties will decrease. If the weight average molecular weight is less than 250, the hardness will be insufficient and cannot be cured during thermal curing. There are cases where the solvent resistance is sufficiently improved.

The melamine formaldehyde resin which is a preferred example of the component (B) according to the embodiment of the present invention can be used in a liquid form or in a solution form in which a purified liquid is redissolved in a solvent described later.

As a preferable example of the (B) component, a phenol novolak resin includes a phenol-formaldehyde polycondensate and the like.

In the cured film-forming composition of this embodiment, the polymer of component (B) can be used in the form of a powder or in the form of a solution in which a purified powder is redissolved in a solvent described later.

In the cured film-forming composition of the present embodiment, the component (B) may be a mixture of a plurality of monomers and polymers exemplified as the component (B).

The content of the component (B) in the cured film-forming composition of the present invention is preferably 400 parts by mass or less, and more preferably 10 parts by mass based on 100 parts by mass of the total amount of the polymer of the component (A). Parts to 380 parts by mass, and more preferably 40 parts to 360 parts by mass. When the content of the component (B) is too large, liquid crystal alignment is liable to decrease.

<(C) component> 硬化 The cured film-forming composition of the present invention may further contain a crosslinking catalyst as the (C) component in addition to the component (A). As a cross-linking catalyst of the component (C), for example, an acid or a thermal acid generator can be applied. This (C) component is effective in accelerating the thermosetting reaction of the cured film-forming composition of the present invention. As the hydrazone (C) component, specific examples of the acid include a compound containing a sulfonic acid group, hydrochloric acid, or a salt thereof. The thermal acid generator is not particularly limited as long as it is a compound that generates an acid after thermal decomposition during heat treatment, that is, a compound that generates an acid by thermal decomposition at a temperature of 80 ° C to 250 ° C.

Specific examples of the acid include hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-toluene. Sulfonic acid, camphor sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, xylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1- The sulfonic acid group such as sulfonic acid and dodecylbenzenesulfonic acid contains a compound or a hydrate or a salt thereof.

Examples of the compound that generates an acid by heat include bis (tosylsulfonyloxy) ethane, bis (tosylsulfonyloxy) propane, and bis (tosylsulfonyloxy) butane. , P-nitrobenzyltoluenesulfonate, o-nitrobenzyltoluenesulfonate, 1,2,3-phenylene ginseng (methanesulfonate), p-pyridinium tosylate Salt, p-toluenesulfonic acid mormonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p -Toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonic acid salt, 2,2,2-trifluoroethyl p-toluenesulfonic acid salt, 2-hydroxybutane Examples of the p-toluenesulfonate and N-ethyl-p-toluenesulfonamide include compounds represented by the following formula:

The content of the component (C) in the cured film-forming composition of the present invention is preferably 0.01 to 20 parts by mass, and more preferably 0.1 part by mass with respect to 100 parts by mass of the polymer of the component (A). 15 mass parts, more preferably 0.5 mass parts to 10 mass parts. When the content of the component (C) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if it is more than 20 parts by mass, the storage stability of the composition may decrease.

<(D) component> 中 In the present invention, the component (D) may contain at least one polymerizable group and at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a fluorenylamino group, an amine group, and an alkoxysilyl group. One group A, or a compound having at least one group that reacts with the group A. This component can improve the adhesiveness of the formed cured film (hereinafter also referred to as an adhesion improving component).

When the cured film formed from the cured film-forming composition of this embodiment containing the (D) component is used as an alignment material, the adhesiveness of the layer between the alignment material and the polymerizable liquid crystal is improved, and the polymerizable functional group of the polymerizable liquid crystal is used. The cross-linking reaction site with the alignment material may be connected by a covalent bond. As a result, the retardation material of this embodiment, which is formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment, can maintain strong adhesion even under conditions of high temperature and high humidity, and can be peeled off. Shows high durability.

The component (D) is preferably a monomer or polymer having a group selected from a hydroxyl group and an N-alkoxymethyl group, and a polymerizable group. Examples of the component (D) include compounds having a hydroxyl group and a (meth) acrylic group, compounds having an N-alkoxymethyl group and a (meth) acrylic group, and compounds having an N-alkoxymethyl group and ( (Meth) acrylic polymer. The following are specific examples.

An example of the component (D) includes a hydroxyl-containing polyfunctional acrylate (hereinafter also referred to as a hydroxyl-containing polyfunctional acrylate). As examples of the (D) component, the polyfunctional acrylate containing a hydroxyl group includes pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like.

As an example of the (D) component, the compound which has one acrylic group and one or more hydroxyl groups can also be mentioned. As such, a preferable example of a compound having one acrylic group and one or more hydroxyl groups can be cited. In addition, the compound of (D) component is not limited to the following compound examples.

(In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10)

Examples of the compound (D) include compounds having at least one polymerizable group containing a C = C double bond in one molecule and at least one N-alkoxymethyl group.

Examples of the polymerizable group containing a C = C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group.

Examples of the N of an N-alkoxymethyl group include a nitrogen atom, a nitrogen atom of amidine, a nitrogen atom of thioamidine, a nitrogen atom of urea, a nitrogen atom of thiourea, and A nitrogen atom, a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocyclic ring, and the like. Therefore, as the N-alkoxymethyl group, a nitrogen atom of amidine, a nitrogen atom of thioamidine, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of carbamate, or A structure in which an alkoxymethyl group is bonded to a nitrogen atom such as a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocyclic ring.

The component (D) may be any compound having the aforementioned group. For example, a compound represented by the following formula (X1) is preferred. (In the formula, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydrogen atom or a linear or branched chain alkyl group having 1 to 10 carbon atoms.)

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2- Methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n -Butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl -n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl -n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl -N-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl -n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1- -N-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl Methyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl Group, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl , 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl 2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl Wait.

Specific examples of the compound represented by the formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl. A hydroxymethyl group such as a methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, or an acrylamide compound or a methacrylamine compound substituted with an alkoxymethyl group. The term "(meth) acrylamide" means both methacrylamide and acrylamide.

As another aspect of the compound having a polymerizable group containing a C = C double bond and an N-alkoxymethyl group as the component (D), for example, a compound represented by the following formula (X2) is preferable. In the formula, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic cyclic group having 5 to 6 carbon atoms, or a monovalent aliphatic group having 5 to 6 carbon atoms in the aliphatic ring, and may also be in the structure Contains ether bonds. R ⁵³ represents a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic cyclic group having 5 to 6 carbon atoms, or a divalent group containing an aliphatic ring having 5 to 6 carbon atoms. The aliphatic group may contain an ether bond in the structure. R ⁵⁴ represents a linear or branched chain divalent to 9-valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9-valent aliphatic cyclic group having 5 to 6 carbon atoms, or contains 5 to 6 carbon atoms A bivalent to 9-valent aliphatic group of the aliphatic ring of 6, one of these groups may be substituted with an methyl group or a non-adjacent plural methyl group may be substituted with an ether bond. Z represents> NCOO- or -OCON <(wherein "-" represents one bond. Also, ">""<" represents two bonds, and an alkoxymethyl group is bonded to any one of the bonds. (I.e. -OR ⁵² base) bonding). r is a natural number of 2 or more and 9 or less.

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ include a bivalent group in which one hydrogen atom is further taken out of the alkyl group having 2 to 20 carbon atoms. In addition, as a specific example of a divalent to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of R ⁵⁴ , an example in which 1 to 8 hydrogen atoms are further taken out of an alkyl group having 1 to 20 carbon atoms Base of 2 to 9 valence.

Examples of the alkyl group having 1 carbon atom are a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, and i-butyl. S-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1 -Dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl -N-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n -Dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hexadecyl, n-octadecyl, n- Undecyl, n-icosyl, cyclopentyl, cyclohexyl, one or more of these groups are bonded in the range of carbon atoms to 20, and are methylated or unphased with one of these groups Examples of groups in which a plurality of ortho-methyl groups may be substituted with an ether bond are given as an example.

Among these, an alkylene group having 2 to 10 carbon atoms is preferred, R ⁵³ represents an ethylene group, and R ⁵⁴ represents an alkylene group which is easily available from a raw material.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² include specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of R ⁵³ and a methyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is particularly preferable.

As r, a natural number of 2 to 9 is mentioned, and 2 to 6 is also preferable.

The content of the component (D) in the cured film-forming composition according to the embodiment of the present invention is preferably 1 part by mass to 100 parts by mass, and more preferably 100 parts by mass of the polymer of the component (A). 5 parts by mass to 70 parts by mass. When the content of the component (D) is 1 part by mass or more, the formed cured film can provide sufficient adhesion. However, if it is more than 100 parts by mass, the alignment of the liquid crystal is liable to decrease.

In the cured film-forming composition of the present embodiment, the component (D) may be a mixture of a plurality of types of compounds of the component (D).

<Solvent> The hardened film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at this time can only dissolve the component (A) and optionally (B) component, (C) component, (D) component and / or other additives described later, and there is no particular limitation on the type and structure thereof. limited.

Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone , Isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropionic acid Ethyl acetate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate Esters, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, Ethyl lactate, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethyl As acetamide, and N- methyl-2-pyrrolidone, and the like.

The hardened film forming composition of the present invention is used to form a hardened film on a resin film. When manufacturing an alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, and 2-methyl-1-butane are used. Alcohol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, etc. are From the viewpoint of a solvent in which the resin film exhibits resistance, it is preferable.

These solvents can be used individually by 1 type or in combination of 2 or more types.

<Other additives> Without impairing the effect of the present invention in the cured film-forming composition of the present invention, it may contain an adhesion upward agent, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, and storage stability as necessary. Agents, defoamers, antioxidants, etc.

<Preparation of hardened film-forming composition> 硬化 The hardened film-forming composition of the present invention is a polymer containing the component (A), and may optionally contain a polymer of the component (B), a crosslinking catalyst of the component (C), and ( D) The component adhesion promoter may further contain a composition containing other additives without impairing the effects of the present invention. These are usually used in the form of a solution dissolved in a solvent.

Preferred examples of the cured film-forming composition of the present invention are shown below. [1]: A cured film-forming composition containing the component (A). [2]: A hardened film-forming composition containing the component (A), the component (B) in an amount of 1 to 400 parts by mass based on 100 parts by mass of the component (A), and a solvent. [3]: The component (B) containing (A) component, 1 to 400 parts by mass based on 100 parts by mass of (A) component, and 0.01 to 20 parts by mass for 100 parts by mass of polymer of (A) component (C) component, a cured film forming composition of a solvent. [4]: (A) component, 1 to 400 parts by mass of (B) component based on 100 parts by mass of (A) component, 0.01 to 20 parts by mass for 100 parts by mass of polymer of (A) component The cured film forming composition of the component (C), the component (D) of 1 to 100 parts by mass with respect to 100 parts by mass of the polymer of the component (A), and the solvent.

The compounding ratio and preparation method when the cured film-forming composition of the present invention is used as a solution will be described in detail below. The proportion of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as it can dissolve each component uniformly in a solvent, but it is preferably 1% to 60% by mass, and more preferably 2% by mass. % To 50% by mass, and more preferably 2% to 20% by mass. Herein, the so-called solid content means that the solvent is removed from all the components of the cured film-forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, in a solution in which the component (A) is dissolved in a solvent, the components (B), (C), (D), etc. are mixed in a predetermined ratio as necessary to obtain a homogeneous solution. An appropriate stage of the preparation method is a method in which other additives can be further added and mixed as necessary.

For the preparation of the cured film-forming composition of the present invention, a solution of a specific copolymer (polymer) obtained by a polymerization reaction in a solvent can be used directly. At this time, for example, in the solution of the component (A), as described above, the components (B), (C), and (D) are added as necessary to obtain a uniform solution. In this case, for the purpose of concentration adjustment, an additional solvent may be added. At this time, the solvent used in the production process of the component (A) and the solvent used for the concentration adjustment of the cured film-forming composition may be the same or different.

The solution of the prepared hardened film-forming composition can be used after filtering using a filter having a pore size of about 0.2 μm or the like.

<Hardened film, alignment material, and retardation material> The solution of the hardened film forming composition of the present invention is coated on a substrate (such as a silicon / diacid-coated substrate, a silicon nitride substrate, a metal, such as aluminum, molybdenum, chromium, etc. Substrate, glass substrate, quartz substrate, ITO substrate, etc.) or film substrate (e.g. triethyl cellulose (TAC) film, polycarbonate (PC) film, cyclic olefin polymer (COP) film, cyclic olefin copolymer (COC ) Film, resin film such as polyethylene terephthalate (PET) film, acrylic film, polyethylene film, etc.) Rod coating, spin coating, flow coating, roll coating, slit coating, slitting continue A coating film is formed after coating by spin coating, inkjet coating, printing, etc., and then a heating plate or an oven is used for drying to form a cured film. This hardened film can be used directly as an alignment material.

As a condition for heating and drying, only a component of the cured film (alignment material) can be subjected to a cross-linking reaction with a cross-linking agent to the extent that it does not dissolve in the polymerizable liquid crystal solution after being coated on it, for example, at a temperature of 60 ° A heating temperature and a heating time appropriately selected are used in the range of -200 ° C and the time is 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70 ° C to 160 ° C, and 0.5 minutes to 10 minutes.

The film thickness of the cured film (alignment material) formed using the curable composition of the present invention, for example, 0.05 μm to 5 μm, may be appropriately selected in consideration of the step difference, optical properties, and electrical properties of the substrate used.

In order to make the alignment material formed of the cured film composition of the present invention have solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having vertical alignment is coated on the alignment material, and the alignment material can be aligned. When the phase difference material in the aligned state is directly hardened, a phase difference material as a layer having optical anisotropy can be formed. When the substrate forming the alignment material is a thin film, it can be used as a retardation film.

In addition, after using the two substrates having the alignment material of the present invention formed as described above, the alignment materials on the two substrates are bonded to face each other via a spacer, and then liquid crystal is injected between these substrates. Can be used as an aligned liquid crystal display element. In this way, the cured film-forming composition of the present invention can be applied to the production of various retardation materials (phase retardation films), liquid crystal display elements, and the like. [Example]

Examples of the present invention will be given below to specifically explain the present invention, but the present invention is not limited to these and is explained.

[Abbreviations used in the examples] The meanings of abbreviations used in the following examples are as follows. ＜ raw materials ＞ CIN1 CIN2 CIN3 CIN4 GMA: glycidyl methacrylate AIBN: α, α'-azobisisobutyronitrile BMAA: N-butoxymethacrylamide HEMA: 2-hydroxyethyl methacrylate MMA: methylformyl Acrylate <B component> HCM: Melamine cross-linking agent represented by the following structural formula [Cymel (CYMEL) (registered trademark) 303 (Mitsui Cytec (stock))] <Component C> PTSA: p-Toluenesulfonic acid hydrazone monohydrate <Component D> D-1: Compound having a hydroxyl group and an acrylic group represented by the following structural formula D-2: Compound having N-alkoxymethyl and acrylic group represented by the following structural formula <Solvent> Each resin composition of an Example and a comparative example contains a solvent, and propylene glycol monomethyl ether (PM) and cyclohexanone (CH) are used as this solvent.

<Measurement of Molecular Weight of Polymer> The molecular weight of the acrylic copolymer used in the polymerization examples is a room temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Shodex, and a column (KD) manufactured by Shodex. -803, KD-805) were measured as follows. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene. Column temperature: 40 ° C Dissolved liquid: tetrahydrofuran Flow rate: 1.0 mL / min 曲线 Standard curve preparation standard sample: Standard polystyrene manufactured by Showa Denko Corporation (molecular weight: approximately 197,000, 55, 100, 12,800, 3,950, 1,260,580).

<Reference Example 1> Synthesis of CIN1 CIN1 was synthesized according to the synthesis method described in Japanese Patent Application Publication No. 2013-514449.

<Reference Example 2> CIN2 synthesis mixed GMA 8.3g (58.4mmol), 4-methoxycinnamic acid 20.7g (116.2mmol), dibutylhydroxytoluene 0.2g, triphenylethylphosphonium bromide 0.3g, 80 mL of dioxane was heated at 90 ° C for 3 days. After the reaction was completed, dioxane was distilled off under reduced pressure, and 150 mL of ethyl acetate was added. After the insoluble matter was separated by filtration, 100 mL of sodium bicarbonate water was added and washed three times to remove excess methoxycinnamic acid. Ethyl acetate was distilled off under reduced pressure to obtain 16.5 g (yield: 88%) of the desired product CIN2.

<Reference Example 3> Synthesis of CIN3 CIN3 was synthesized according to the synthesis method described in International Publication WO2013 / 191251.

<Reference Example 4> Synthesis of CIN4 CIN4 was synthesized according to the synthesis method described in Macromolecules, 39,9357-9364 (2006).

<Synthesis of Component A> <Polymerization Example 1> Dissolved 15.0 g of CIN1, 1.7 g of BMAA, and 0.4 g of AIBN as a polymerization catalyst in 123.4 g of PM and 30.9 g of CH, and reacted at 80 ° C for 20 hours to obtain acrylic acid containing acrylic acid. 10% by weight solution of copolymer (PA-1). The obtained acrylic copolymer had Mn of 10,000 and Mw of 29,000.

<Polymerization Example 2> 15.0 g of CIN2, 1.7 g of BMAA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 155.9 g of PM and reacted at 80 ° C for 20 hours to obtain 10% by weight of an acrylic copolymer (PA-2). Its solution. The obtained acrylic copolymer had a Mn of 8,400 and a Mw of 18,000.

<Polymerization Example 3> Dissolved 15.0 g of CIN3, 1.4 g of BMAA, and 0.4 g of AIBN as a polymerization catalyst in 120.3 g of PM and 30.1 g of CH, and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer (PA-3 ) 10% by weight solution. The obtained acrylic copolymer had a Mn of 18,000 and a Mw of 55,000.

<Polymerization Example 4> 溶解 Dissolved 15.0 g of CIN4, 1.8 g of BMAA, and 0.9 g of AIBN as a polymerization catalyst in 111.5 g of PM and 47.8 g of CH, and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer (PA-4). ) 10% by weight solution. The obtained acrylic copolymer had a Mn of 9,000 and a Mw of 20,000.

<Polymerization Example 5> 溶解 10.0 g of CIN3, 3.0 g of BMAA, and 0.4 g of AIBN as a polymerization catalyst were dissolved in 96.6 g of PM and 24.2 g of CH, and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer (PA-5 ) 10% by weight solution. The obtained acrylic copolymer had Mn of 8,000 and Mw of 20,000.

<Polymerization Example 6> Dissolved 15.0 g of CIN3, 0.9 g of BMAA, 0.7 g of HEMA, and 0.4 g of AIBN as a polymerization catalyst in 122.4 g of PM and 30.6 g of CH, and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer. (PA-6) 10% by weight solution. The obtained acrylic copolymer had Mn of 11,000 and Mw of 32,000.

<Polymerization Example 7> Dissolved 15.0 g of CIN3, 1.2 g of HEMA, and 0.4 g of AIBN as a polymerization catalyst in 118.4 g of PM and 29.6 g of CH, and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer (PA-7). ) 10% by weight solution. The obtained acrylic copolymer had Mn of 10,000 and Mw of 35,000.

<Polymerization Example 8> 15.0g of CIN2, 1.5g of HEMA, and 0.5g of AIBN as a polymerization catalyst were dissolved in 122.4g of PM and 30.6g of CH, and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer (PA-8 ) 10% by weight solution. The obtained acrylic copolymer had a Mn of 8,700 and a Mw of 28,000.

<Synthesis of Component B> <Polymerization Example 9> (100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM and reacted at 90 ° C for 20 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had an Mn of 2,700 and an Mw of 3,900. The acrylic polymer solution was slowly dropped into 2000.0 g of hexane, and a solid was precipitated. The polymer (PB-1) was obtained by filtration and drying under reduced pressure.

<Polymerization Example 10> 3 30.0 g of MMA, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 146.0 g of PM and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane, and a solid was precipitated. The acrylic copolymer (PB-2) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had a Mn of 18,000 and a Mw of 32,800.

<Preparation of polymerizable liquid crystal solution> Add 29.0 g of polymerizable liquid crystal LC242 (manufactured by BASF), 0.9 g of IRGACURE907 (manufactured by BASF) as a polymerization initiator, and BYK-361N (manufactured by BYK) 0.2 as a leveling agent. g. Cyclopentanone as a solvent to obtain a polymerizable liquid crystal solution (RM-1) having a solid content concentration of 30% by mass.

<Example 1> A solution containing the acrylic copolymer (PA-1) obtained in the above polymerization example 1 was equivalent to 100 parts by mass in terms of acrylic copolymer (PA-1), and was monohydrated with p-toluenesulfonic acid hydrazone. 5 parts by mass of the product, PM and CH were added here, and the solvent composition was a solution of PM: CH = 80: 20 (mass ratio) and a solid content concentration of 5.0% by mass. This solution was filtered through a filter having a pore size of 1 μm, and then a composition A-1 for a liquid crystal alignment agent was prepared. <Examples 2 to 10 and Comparative Examples 1 to 3> The types and amounts of the acrylic copolymer of component A, and other components were as described in Table 1, and the same steps as in Example 1 were performed to prepare liquid crystal alignments. Compositions A-2 to A-13.

<Examples 11 to 20 and Comparative Examples 4 to 6> [Evaluation of Orientation] The compositions for each of the alignment agents of Examples 1 to 10 and Comparative Examples 1 to 3 were applied on a TAC film to a Wet film using a rod coating 4 μm thick. Each was heated and dried in a thermal cycle oven at a temperature of 110 ° C. for 120 seconds to form each cured film on the TAC film. On each of the cured films, linearly polarized light of 313 nm was irradiated in a vertical direction at an exposure amount of 20 mJ / cm ² to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution (RM-1) was applied with a rod coating to a Wet film thickness of 6 μm. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds, and then exposed at 300 mJ / cm ² to produce a retardation material. The phase difference material on the produced substrate was sandwiched by a pair of polarizing plates, and the performance of the phase difference characteristics in the phase difference material was observed. Those who did not show defects in the phase difference were evaluated as ○, and those who did not show phase difference were evaluated as × , And recorded in the column of "alignment". The evaluation results are summarized in Table 2 described later.

As shown in Table 2, the retardation materials obtained in Examples 11 to 20 showed good alignment. In contrast, the phase difference materials obtained in Comparative Examples 4 to 6 did not obtain good alignment. [Industrial availability]

The cured film-forming composition obtained by the present invention is very useful as a material for forming a liquid crystal alignment film for a liquid crystal display element, or as an alignment material when an optically anisotropic film is provided inside or outside the liquid crystal display element, and is particularly useful. The circularly polarizing plate used as an anti-reflection film of an IPS-LCD or an organic EL display is preferably a material mainly composed of a retardation material.

Claims (11)

A cured film-forming composition comprising a polymer having (A) a photodimerization site and a self-crosslinking site. The cured film-forming composition according to claim 1, wherein the self-crosslinking site of the component (A) is methylol or alkoxymethyl. The hardened film-forming composition according to claim 1 or 2, further comprising (B) two or more selected from the group consisting of methylol, alkoxymethyl, hydroxyl, carboxyl, amido, amino, and alkoxysilyl A monomer or polymer having at least one group in which the groups are grouped. The cured film-forming composition according to any one of claims 1 to 3, further comprising (C) a crosslinking catalyst. The hardened film-forming composition according to any one of claims 1 to 4, further comprising (D) one or more polymerizable groups and a member selected from the group consisting of a hydroxyl group, a carboxyl group, a amine group, an amine group, and an alkoxysilyl group. Compounds of at least one group A or at least one group that react with the group A. The cured film-forming composition according to any one of claims 3 to 5, wherein 100 parts by mass of the (A) component contains 1 to 400 parts by mass of the (B) component. The cured film-forming composition according to any one of claims 4 to 6, which contains 0.01 to 20 parts by mass of the (C) component for 100 parts by mass of the (A) component. The cured film-forming composition according to any one of claims 5 to 7, wherein 100 parts by mass of the (A) component contains 1 to 100 parts by mass of the (D) component. A cured film obtained by curing the cured film-forming composition according to any one of claims 1 to 8. An alignment material characterized by being obtained by hardening the hardened film-forming composition according to any one of claims 1 to 8. A retardation material characterized by being formed using a cured film obtained from the cured film-forming composition according to any one of claims 1 to 8.