CN110461887B - Composition for forming cured film, alignment material, and phase difference material - Google Patents

Composition for forming cured film, alignment material, and phase difference material Download PDF

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CN110461887B
CN110461887B CN201880020992.0A CN201880020992A CN110461887B CN 110461887 B CN110461887 B CN 110461887B CN 201880020992 A CN201880020992 A CN 201880020992A CN 110461887 B CN110461887 B CN 110461887B
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CN110461887A (en
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伊藤润
菅野裕太
畑中真
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention provides a composition for forming a cured film, which is used as an alignment material and shows excellent liquid crystal alignment property and light transmission property when a layer of polymerizable liquid crystal is arranged on the composition. The solution is a composition for forming a cured film, an alignment material characterized by being formed using the composition, and a phase difference material characterized by having a cured film obtained using the composition, wherein the composition for forming a cured film comprises: (A) A reaction product of a polymer having an epoxy group and a cinnamic acid derivative represented by the following formula (1); and (B) a crosslinking agent (in the formula (1), A 1 And A 2 Each independently represents a hydrogen atom or a methyl group, R 1 Represents a hydrogen atom, a halogen atom or the like, R 2 Represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group, R 3 Represents a single bond, an oxygen atom or the like, R 4 ～R 7 Each independently represents a hydrogen atom, a halogen atom or the like, and n is an integer of 0 to 3. ).

Description

Composition for forming cured film, alignment material, and phase difference material
Technical Field
The present invention relates to a composition for forming a cured film, an alignment material, and a retardation material which can be used as a liquid crystal alignment agent for photo-alignment for aligning liquid crystal molecules. In particular, the present invention relates to a cured film-forming composition, an alignment material, and a retardation material that can be used as a liquid crystal alignment agent for optical alignment that is useful as a patterned retardation material used for producing a circularly polarized light glasses-type 3D display or a retardation material used for a circularly polarized light plate used as an antireflection film for an organic EL display.
Background
In the case of a circularly polarized glasses type 3D display, a phase difference material is generally disposed on a display element such as a liquid crystal panel on which an image is formed. In this phase difference material, a plurality of 2 phase difference regions having different phase difference characteristics are regularly arranged, and a patterned phase difference material is configured. In the present specification, a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is hereinafter referred to as a patterned retardation material.
The patterned retardation material can be produced by optically patterning a retardation material formed of polymerizable liquid crystal, for example, as disclosed in patent document 1. Optical patterning of a phase difference material formed of polymerizable liquid crystal utilizes a known photo-alignment technique for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and 2 kinds of polarized light having different polarization directions are irradiated thereto. Then, an alignment material in which 2 liquid crystal alignment regions having different alignment control directions of liquid crystals were formed was prepared, and a photo alignment film was obtained. A phase difference material in a solution state containing a polymerizable liquid crystal is applied to the photo-alignment film to align the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.
An antireflection film of an organic EL display is composed of a linear polarizer and a 1/4 wavelength phase difference plate, and external light directed toward a panel surface of an image display panel is converted into linear polarized light by the linear polarizer and then converted into circular polarized light by the 1/4 wavelength phase difference plate. Here, the external light based on the circularly polarized light is reflected on the surface of the image display panel, and the rotation direction of the polarizing surface is reversed at the time of the reflection. As a result, the reflected light is converted into linearly polarized light in a direction shielded by the linearly polarizing plate by the 1/4 wavelength phase difference plate, and then shielded by the linearly polarizing plate, contrary to the arrival time, and as a result, the emission to the outside is remarkably suppressed.
Regarding the 1/4 wavelength phase difference plate, patent document 2 proposes a method of forming the optical film by inverse dispersion characteristics by forming a 1/4 wavelength phase difference plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. In the case of this method, the optical film can be configured by the inverse dispersion characteristic using the liquid crystal material based on the positive dispersion characteristic in a wide wavelength band for color image display.
In recent years, materials having inverse dispersion characteristics have been proposed as liquid crystal materials that can be applied to the retardation layer (patent documents 3 and 4). According to such a liquid crystal material having inverse dispersion characteristics, instead of forming a 1/4 wavelength retardation plate by a 2-layer retardation layer by combining a 1/2 wavelength plate and a 1/4 wavelength plate, an optical film capable of securing a desired retardation in a wide wavelength band can be realized by a simple configuration by forming the retardation layer by a single layer to secure inverse dispersion characteristics.
An alignment layer is used to align the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method and a photo alignment method are known, and the photo alignment method is useful in that it is free from generation of static electricity and dust which are problems of the rubbing method and can perform quantitative alignment treatment control.
As a material having photo-alignment properties that can be used for formation of an alignment material using a photo-alignment method, an acrylic resin, a polyimide resin, or the like having a photo-dimerization site such as a cinnamoyl group or a chalcone group in a side chain is known. These resins have been reported to exhibit a property of controlling the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment properties) by polarized UV irradiation (see patent documents 5 to 7).
In addition, the alignment layer is required to have solvent resistance in addition to liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or a solvent during the production of the retardation material. If the alignment layer is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.
For example, patent document 8 proposes a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure capable of undergoing crosslinking by heat, and a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a compound having a structure capable of undergoing crosslinking by heat, in order to obtain a stable liquid crystal aligning capability.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2005-49865
Patent document 2: japanese patent laid-open publication No. 10-68816
Patent document 3: specification of U.S. Pat. No. 8119026
Patent document 4: japanese patent laid-open publication No. 2009-179563
Patent document 5: japanese patent No. 3611342
Patent document 6: japanese laid-open patent publication No. 2009-058584
Patent document 7: japanese Kohyo publication No. 2001-517719
Patent document 8: japanese patent No. 4207430
Disclosure of Invention
Problems to be solved by the invention
As described above, the retardation material is formed by laminating a layer of cured polymerizable liquid crystal on a photo alignment film as an alignment material. Therefore, it is necessary to develop an alignment material that can combine excellent liquid crystal alignment properties and solvent resistance.
However, according to the studies of the present inventors, it was found that an acrylic resin having a photodimerization site such as a cinnamoyl group or a chalcone group in a side chain does not have sufficient characteristics when applied to the formation of a phase difference material. In particular, in order to form an alignment material by irradiating these resins with polarized UV light and to produce a retardation material made of a polymerizable liquid crystal using the alignment material, a large amount of polarization is requiredLight UV exposure. The polarized UV exposure amount is equal to a normal polarized UV exposure amount (for example, 30 mJ/cm) sufficient for aligning liquid crystals for a liquid crystal panel 2 Left and right. ) Much more so than it is.
The reason why the amount of polarized UV exposure is increased is that, when a retardation material is formed, a polymerizable liquid crystal is used in a solution state and applied to an alignment material, unlike a liquid crystal for a liquid crystal panel.
When an alignment material is formed using an acrylic resin or the like having a photo-dimerization site such as a cinnamoyl group in a side chain and a polymerizable liquid crystal is aligned, photo-crosslinking by a photo-dimerization reaction is performed in the acrylic resin or the like. Therefore, until resistance to the polymerizable liquid crystal solution is exhibited, it is necessary to irradiate polarized light with a large exposure amount. In order to align the liquid crystal of the liquid crystal panel, generally, only the surface of the photo-alignment material may be subjected to dimerization reaction. However, if the solvent resistance of the alignment material is to be expressed by using the conventional materials such as the acrylic resin, the reaction must be performed until the inside of the alignment material, and a larger amount of exposure is required. As a result, there is a problem that the orientation sensitivity of the conventional material becomes very small.
In addition, in order to make the resin as the conventional material exhibit such solvent resistance, a technique of adding a crosslinking agent is known. However, after the thermosetting reaction by the crosslinking agent, a 3-dimensional structure is formed in the interior of the formed coating film, and there is a problem that the photoreactivity is lowered. That is, the alignment sensitivity is greatly lowered, and the desired effect cannot be obtained even when a crosslinking agent is added to a conventional material and used.
Therefore, a photo-alignment technique capable of improving the alignment sensitivity of an alignment material and reducing the polarized UV exposure amount, and a composition for forming a cured film which can be used as a liquid crystal alignment agent for photo-alignment used for forming the alignment material are required. Further, a technique capable of efficiently providing a retardation material is required.
The object of the present invention is to provide a method for producing a light emitting device. That is, an object of the present invention is to provide a composition for forming a cured film which can be used as a liquid crystal aligning agent for photo-alignment for providing an alignment material which has excellent solvent resistance and can align a polymerizable liquid crystal with high sensitivity.
Other objects and advantages of the present invention will become apparent from the following description.
Means for solving the problems
The present inventors have made intensive studies in order to achieve the above object, and as a result, have found that a cured film (alignment material) having excellent solvent resistance and capable of aligning polymerizable liquid crystals with high sensitivity can be formed by selecting a material for forming a cured film based on (a) a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative and (B) a crosslinking agent, and have completed the present invention.
That is, the present invention relates to, as a 1 st aspect, a composition for forming a cured film, comprising:
(A) A reaction product of a polymer having an epoxy group and a cinnamic acid derivative represented by the following formula (1),
Figure BDA0002214195200000051
(in the formula (1), A 1 And A 2 Each independently represents a hydrogen atom or a methyl group, R 1 Represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a halocycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, a haloalkenyl group having 3 to 8 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a haloalkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, an alkyl) carbonyl group having 1 to 6 carbon atoms, a haloalkyl) carbonyl group having 1 to 6 carbon atoms, an alkoxy (alkoxy) carbonyl group having 1 to 6 carbon atoms, a haloalkoxy) carbonyl group having 1 to 6 carbon atoms, an alkylamino) carbonyl group having 1 to 6 carbon atoms, a haloalkyl) aminocarbonyl group having 1 to 6 carbon atoms, a di (alkyl) carbonyl group having 1 to 6 carbon atomsAlkyl of a number of 1 to 6) substituents in aminocarbonyl, cyano and nitro radicals, R 2 Represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group, R 3 Represents a single bond, an oxygen atom, -COO-or-OCO-, R 4 ～R 7 Each independently represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, 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, and n is an integer of 0 to 3. ) (ii) a And
(B) A crosslinking agent.
In a 2 nd aspect, the composition for forming a cured film according to the 1 st aspect, wherein the crosslinking agent (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
A 3 rd aspect of the present invention relates to the cured film forming composition according to the 1 st or 2 nd aspect, further comprising (C) a polymer having at least 1 group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.
The 4 th aspect of the present invention relates to the cured film forming composition according to any one of the 1 st to 3 rd aspects, further comprising (D) a crosslinking catalyst.
A 5 th aspect of the present invention provides the cured film forming composition according to any one of the 1 st to 4 th aspects, which comprises (E) a compound having 1 or more polymerizable groups and at least 1 group a selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least 1 group reactive with the group a.
The 6 th aspect of the present invention provides the cured film forming composition according to any one of the 1 st to 5 th aspects, wherein the component (B) is contained in an amount of 1 to 500 parts by mass based on 100 parts by mass of the component (a).
A 7 th aspect of the present invention relates to the cured film forming composition according to any one of the 3 rd to 6 th aspects, wherein the component (C) is contained in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of the components (a) and (B).
An 8 th aspect of the present invention relates to the cured film forming composition according to any one of the 4 th to 7 th aspects, wherein the component (D) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the components (a) and (B).
A 9 th aspect of the present invention relates to the cured film forming composition according to any one of the 5 th to 8 th aspects, wherein the component (E) is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total amount of the components (a) and (B).
The 10 th aspect relates to a cured film obtained by using the composition for forming a cured film according to any one of the 1 st to 9 th aspects.
The 11 th aspect relates to an alignment material formed using the cured film-forming composition according to any one of the 1 st to 9 th aspects.
The 12 th aspect relates to a phase difference material having a cured film obtained by using the composition for forming a cured film according to any one of the 1 st to 9 th aspects.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a cured film which has excellent solvent resistance and can align polymerizable liquid crystals with high sensitivity, and a composition for forming a cured film suitable for forming the cured film can be provided.
According to the present invention, it is possible to provide an alignment material having excellent liquid crystal alignment properties and light transmittance, and a phase difference material capable of forming an optical pattern with high accuracy.
Detailed Description
< composition for Forming cured film >
The composition for forming a cured film of the present invention comprises: (A) A reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative; and (B) a crosslinking agent. The composition for forming a cured film of the present invention may further contain, as component (C), a polymer having at least 1 group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, in addition to component (a) and component (B). Further, a crosslinking catalyst may be contained as the component (D). The component (E) may further contain a compound having 1 or more polymerizable groups and at least 1 group a selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least 1 group reactive with the group a. Further, other additives may be contained as long as the effects of the present invention are not impaired.
The details of each component are described below.
< component (A) >
The component (a) contained in the cured film forming composition of the present invention is a reaction product of a polymer having an epoxy group and a cinnamic acid derivative represented by the above formula (1).
< polymers having epoxy groups >
The polymer having an epoxy group may be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.
Specific examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α -ethacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 3, 4-epoxybutyl acrylate, 3, 4-epoxybutyl methacrylate, 6, 7-epoxyheptyl acrylate, 6, 7-epoxyheptyl methacrylate, 6, 7-epoxyheptyl α -ethacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.
Examples of the other polymerizable unsaturated compounds include alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl methacrylates, aryl acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, and polymerizable unsaturated compounds other than these compounds.
Specific examples thereof include alkyl methacrylates such as hydroxymethyl methacrylate2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2, 3-dihydroxypropyl methacrylate, 2-methacryloyloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc.; examples of the alkyl acrylate include methyl acrylate, isopropyl acrylate, and the like; examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo [5.2.1.0 ] methacrylate 2,6 ]Decan-8-yl ester, tricyclo [5.2.1.0 ] methacrylate 2,6 ]Decane-8-yloxyethyl ester, isobornyl methacrylate, cholesteryl methacrylate, etc.; examples of the cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, and tricyclo [5.2.1.0 ] acrylate 2,6 ]Decane-8-yl ester, acrylic acid tricyclo [5.2.1.0 2,6 ]Decane-8-yloxyethyl ester, isobornyl acrylate, cholesteryl acrylate, etc.; examples of the aryl methacrylate include phenyl methacrylate, benzyl methacrylate and the like; examples of the aryl acrylate include phenyl acrylate, benzyl acrylate and the like; examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate;
as a class of the bicyclic unsaturated compounds, examples thereof include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, and mixtures thereof 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like; examples of the maleimide compounds include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like; examples of the unsaturated aromatic compound include styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrenes, and the like; examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like; examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and the like; examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; examples of the unsaturated dicarboxylic acid anhydride include the respective anhydrides of the above unsaturated dicarboxylic acids; examples of the polymerizable unsaturated compounds other than those mentioned above include acrylonitrile, methacrylonitrile, vinyl chloride, 1-dichloroethylene, acrylamide, methacrylamide, and vinyl acetate.
The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, and more preferably 50% by mass or more.
The synthesis of the polymer having an epoxy group can be carried out by a known radical polymerization method preferably in a solvent in the presence of an appropriate polymerization initiator.
As the polymer having an epoxy group, commercially available products can be used. Examples of such commercially available products include those of the groups described above, such as EHPE3150, EHPE3150CE (described above (strain) 12452124751252370, UG-4010, UG-4035, UG-4040, UG-4070 (described above, ARUFON series, manufactured by Tokya synthesis (strain)), ECN-1299 (manufactured by Asahi Kasei (strain)), DEN431, DEN438 (described above, 12412454651251159), JER-152 (manufactured by Tokya 12572971251251251251251255612512497, tokya 124611251255612512461125125125561251251255612563, tokyn 12461102, tokyo patent publication No. (described above, chemical patent publication No. 125125125125125125125125125125125102.
< cinnamic acid derivatives having carboxyl group >
The cinnamic acid derivative having a carboxyl group is a compound represented by the above formula (1).
Examples of the halogen atom in the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the present specification, the expression "halo" also means these halogen atoms.
The expression "alkyl group having a to b carbon atoms" in the formula (1) denotes a straight-chain or branched-chain hydrocarbon group having a to b carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-dimethylbutyl, 1, 3-dimethylbutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, and these are selected from the ranges of the respective specified carbon atoms.
The expression "haloalkyl group having carbon atoms a to b" in the above formula (1) means a linear or branched hydrocarbon group having carbon atoms a to b, in which a hydrogen atom bonded to a carbon atom is optionally substituted by a halogen atom, and in this case, when the alkyl group is substituted by 2 or more halogen atoms, these halogen atoms may be the same as each other or may be different from each other. <xnotran> , , , , , , , , , , , , , , ,2- ,2- ,2- ,2,2- ,2- -2- ,2,2- ,2- -2- ,2,2,2- ,2- -2,2- ,2,2- -2- ,2,2,2- ,2- -2,2- ,2- -2- -2- ,2- -2,2- ,1,1,2,2- , ,1- -1,2,2,2- ,2- -1,1,2,2- ,1,2- -1,2,2- ,2- -1,1,2,2- ,2- ,2- ,2- ,2- -2- ,2,3- ,2- -3- ,3- -2- ,2,3- ,3,3,3- ,3- -3,3- ,2,2,3,3- ,2- -3,3,3- ,2,2,3,3,3- ,1,1,2,3,3,3- , , </xnotran> <xnotran> 2,3- -1,1,2,3,3- ,2- -1- ,2- -1- ,2- -1- ,2,2,2- -1- ( ) ,1,2,2,2- -1- ( ) ,2,2,3,3,4,4- ,2,2,3,4,4,4- ,2,2,3,3,4,4,4- ,1,1,2,2,3,3,4,4- , ,4- -1,1,2,2,3,3,4,4- ,2- -2- ,2- -1,1- ,2- -1,1- ,5- -2,2,3,4,4,5,5- , , . </xnotran>
The expression "cycloalkyl group having a to b carbon atoms" in the formula (1) represents a cyclic hydrocarbon group having a to b carbon atoms, and may have a monocyclic or complex ring structure having 3 to 6 membered rings. In addition, each ring may be optionally substituted with an alkyl group within the specified range of the number of carbon atoms. Examples thereof include cyclopropyl, 1-methylcyclopropyl, 2-dimethylcyclopropyl, 2, 3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, bicyclo [2.2.1] heptan-2-yl, etc., and these are selected from the ranges of the respective specified carbon atoms.
The expression "halocycloalkyl group having carbon atoms a to b" in the above formula (1) represents a cyclic hydrocarbon group consisting of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and may have a monocyclic or complex ring structure of 3-to 6-membered rings. Further, each ring may be optionally substituted with an alkyl group within the specified number of carbon atoms, and the substitution with a halogen atom may be a cyclic structure portion, may be a side chain portion, or may be both of them, and further, in the case of being substituted with 2 or more halogen atoms, these halogen atoms may be the same as each other, or may be different from each other. Examples thereof include 2, 2-difluorocyclopropyl group, 2-dichlorocyclopropyl group, 2-dibromocyclopropyl group, 2-difluoro-1-methylcyclopropyl group, 2-dichloro-1-methylcyclopropyl group, and specific examples thereof include 2, 2-dibromo-1-methylcyclopropyl group, 2, 3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group and 4- (trifluoromethyl) cyclohexyl group, selected within the range of the number of carbon atoms specified for each.
The expression "alkenyl group having carbon atoms a to b" in the formula (1) denotes a linear or branched unsaturated hydrocarbon group having 1 or 2 or more double bonds in the molecule and having a carbon atom number a to b, and examples thereof include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 2-butenyl, 1-methyl-2-propenyl, 2-pentenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 2-ethyl-2-propenyl, 1-dimethyl-2-propenyl, 2-hexenyl, 2-methyl-2-pentenyl, 2, 4-dimethyl-2, 6-heptadienyl, 3, 7-dimethyl-2, 6-octadienyl and the like, and these are selected from the ranges of the respective specified carbon atoms.
The expression "haloalkenyl group having carbon atoms a to b" in the formula (1) denotes a linear or branched unsaturated hydrocarbon group having 1 or 2 or more double bonds in the molecule, wherein the hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and the unsaturated hydrocarbon group has a carbon atom number of a to b. At this time, in the case of being substituted by 2 or more halogen atoms, these halogen atoms may be the same as each other, or may be different from each other. <xnotran> 2,2- ,2- -2- ,2- -2- ,3- -2- ,2- -2- ,3- -2- ,3,3- -2- ,2,3- -2- ,3,3- -2- ,2,3- -2- ,2,3,3- -2- ,2,3,3- -2- ,1- ( ) ,3- -2- ,3- -2- ,4,4- -3- ,3,4,4- -3- ,3- -4,4,4- -2- ,3- -2- -2- , . </xnotran>
The expression "cycloalkenyl group having carbon atoms a to b" in the formula (1) denotes an unsaturated hydrocarbon group having 1 or 2 or more double bonds and having a cyclic structure consisting of a to b carbon atoms, and may form a single ring or a composite ring structure having 3 to 6 membered rings. Further, each ring may be optionally substituted with an alkyl group within the specified range of the number of carbon atoms, and further, the double bond may be in any form of endo-) or exo- (exo-). Specific examples thereof include 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, bicyclo [2.2.1] -5-hepten-2-yl, etc., and they are selected from the specified ranges of the number of carbon atoms.
The expression "halocycloalkenyl group having carbon atoms a to b" in the formula (1) denotes an unsaturated hydrocarbon group which is cyclic and has 1 or 2 or more double bonds, wherein a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and which has 1 to 2 carbon atoms, and which may form a 3-to 6-membered ring having a single ring or a composite ring structure. Further, each ring may be optionally substituted with an alkyl group within the specified range of the number of carbon atoms, and further, the double bond may be in any form of endo- "or exo-". Further, the substitution of the halogen atom may be a ring structure portion, may be a side chain portion, or may be both of them, and in the case of substitution with 2 or more halogen atoms, these halogen atoms may be the same as each other, or may be different from each other. Specific examples thereof include 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group and the like, and they are selected from the specified ranges of the number of carbon atoms.
The expression "alkynyl group having a to b carbon atoms" in the formula (1) denotes a linear or branched unsaturated hydrocarbon group having 1 or 2 or more triple bonds in the molecule and having a to b carbon atoms, and examples thereof include ethynyl, 1-propynyl, 2-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 1-methyl-2-butynyl, 1-dimethyl-2-propynyl, and 2-hexynyl, and they are selected from the range of the respective specified carbon atoms.
The expression "haloalkynyl group having carbon atoms a to b" in the formula (1) denotes an unsaturated hydrocarbon group which is a linear or branched chain having carbon atoms a to b and in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and which has 1 or 2 or more triple bonds in the molecule. At this time, in the case of being substituted by 2 or more halogen atoms, these halogen atoms may be the same as each other, or may be different from each other. Specific examples thereof include 2-chloroethynyl, 2-bromoethynyl, 2-iodoethynyl, 3-chloro-2-propynyl, 3-bromo-2-propynyl, and 3-iodo-2-propynyl, and they are selected from the specified ranges of the number of carbon atoms.
The expression "alkoxy group having a to b carbon atoms" in the formula (1) represents an alkyl-O-group having the above meaning consisting of a to b carbon atoms, and examples thereof include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, and n-hexyloxy group, which are selected from the ranges of the respective specified carbon atoms.
<xnotran> (1) a ～ b a ～ b -O- , , , , ,2- ,2- ,2,2,2- ,1,1,2,2- ,2- -1,1,2- ,2- -1,1,2- , ,2,2- -1,1,2- ,2,2,2- -1,1- ,2- -1,1,2,2- ,2,2,3,3- ,1,1,2,3,3,3- ,2,2,2- -1- ( ) , ,2- -1,1,2,3,3,3- , . </xnotran>
The expression of the (alkyl group having a to b carbon atoms) carbonyl group in the formula (1) represents an alkyl-C (O) -group having the above meaning consisting of a to b carbon atoms, and examples thereof include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, 2-methylbutyryl, pivaloyl, hexanoyl, heptanoyl, and the like, and are selected from the ranges of the respective specified carbon atoms.
The expression (haloalkyl group having a carbon number a to b) carbonyl group in the formula (1) represents a haloalkyl-C (O) -group having the above meaning consisting of a carbon number a to b, and examples thereof include fluoroacetyl group, chloroacetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutyryl group, 3-chloro-2, 2-dimethylpropionyl group, and the like, and are selected from the ranges of the respective specified carbon numbers.
The expression (alkoxy group having a to b carbon atoms) carbonyl group in the formula (1) represents an alkyl-O-C (O) -group having the above meaning consisting of a to b carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, tert-butyloxycarbonyl and the like, which are selected from the ranges of the respective specified carbon atoms.
The expression of the (haloalkoxy having a to b carbon atoms) carbonyl group in the formula (1) represents a haloalkyl-O-C (O) -group having the above meaning consisting of a to b carbon atoms, and examples thereof include a 2-chloroethoxycarbonyl group, a 2, 2-difluoroethoxycarbonyl group, a 2, 2-trifluoroethoxycarbonyl group, a 2, 2-trichloroethoxycarbonyl group and the like, and are selected from the ranges of the respective specified carbon atoms.
The expression of (alkylamino having a to b carbon atoms) carbonyl in the above formula (1) denotes a carbamoyl group in which one of hydrogen atoms is substituted with an alkyl group having the above meaning consisting of a to b carbon atoms, and examples thereof include methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, tert-butylcarbamoyl and the like, and are selected within the range of the respective specified carbon atoms.
The expression (haloalkyl group having a to b carbon atoms) aminocarbonyl group in the above formula (1) represents a carbamoyl group in which one of hydrogen atoms is substituted with a haloalkyl group having the above meaning consisting of a to b carbon atoms, and examples thereof include a 2-fluoroethylcarbamoyl group, a 2-chloroethylcarbamoyl group, a 2, 2-difluoroethylcarbamoyl group, a 2, 2-trifluoroethylcarbamoyl group and the like, and are selected from the ranges of the respective specified carbon atoms.
The expression "di (alkyl group having a to b carbon atoms) aminocarbonyl group" in the above formula (1) represents a carbamoyl group in which both hydrogen atoms are substituted by an alkyl group having the above meaning composed of a to b carbon atoms, which may be the same or different from each other, and examples thereof include N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N-diethylcarbamoyl group, N-di-N-propylcarbamoyl group, N-di-N-butylcarbamoyl group and the like, which are selected from the ranges of the respective specified carbon atoms.
As a substituent R of a cinnamic acid derivative represented by the formula (1) 1 、R 4 、R 5 、R 6 And R 5 Among them, preferred are substituents each independently selected from the group consisting of a hydrogen atom, a halogen atom, 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.
Further, as the substituent R 1 In the above definition, a substituent other than a hydrogen atom is preferable in view of orientation sensitivity, and more preferable is a substituent selected from the group consisting of a halogen atom, 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.
As substituents R 2 Examples of the 2-valent aromatic group in (b) include 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, 2,3,5, 6-tetrafluoro-1, 4-phenylene, and the like; as R 2 Examples of the 2-valent alicyclic group in (b) include 1, 2-cyclopropyl, 1, 3-cyclobutyl, 1, 4-cyclohexylidene and the like; as R 2 Examples of the 2-valent heterocyclic group in (1) include a 1, 4-pyridylene group, a 2, 5-pyridylene group, a 1, 4-furanylene group and the like; as R 2 Examples of the 2-valent condensed ring group include a 2, 6-naphthylene group and the like. As R 2 Preferably 1, 4-phenylene.
Preferable examples of the compound represented by the formula (1) include cinnamic acid derivatives represented by the following formulae (1-1) to (1-5).
Figure BDA0002214195200000151
(in the above formula, R 1 Respectively with R in the above formula (1) 1 The meaning is the same. )
The cinnamic acid derivative represented by the above formula (1) can be synthesized by appropriately combining general methods of organic chemistry.
< reaction of Polymer having epoxy group with specific cinnamic acid derivative >
The reaction product of the polymer having an epoxy group and the specific cinnamic acid derivative contained in the cured film forming composition of the present invention can be synthesized by reacting the polymer having an epoxy group and the specific cinnamic acid derivative as described above, preferably in the presence of a catalyst, preferably in an appropriate organic solvent.
The ratio of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1.3 mol, and still more preferably 0.1 to 1.1 mol, based on 1 mol of the epoxy group contained in the epoxy group-containing polymer.
The ratio of the epoxy group to be reacted with the cinnamic acid derivative is preferably within the range in which the above-described result of the use ratio is achieved, but from the viewpoint of photo-alignment properties, it is particularly preferably 80 to 100 mol% of the total epoxy groups.
As the organic catalyst that can be used here, an organic base or a compound known as a so-called curing accelerator that accelerates the reaction of an epoxy compound and an acid anhydride can be used.
Examples of the organic base include primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine are preferable; quaternary organic amines such as tetramethylammonium hydroxide.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4, 5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4, 5-bis [ (2' -cyanoethoxy) methyl ] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole
Figure BDA0002214195200000161
Trimellitic acid salt, 1- (2-cyanoethyl) -2-phenylimidazole->
Figure BDA0002214195200000162
Trimellitic acid salt, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole->
Figure BDA0002214195200000163
Imidazole compounds such as trimellitic acid salt, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- (2 '-n-undecylimidazolyl) ethyl-s-triazine, 2, 4-diamino-6- [ 2' -ethyl-4 '-methylimidazolyl- (1') ] -ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, isocyanuric acid adduct of 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine, and the like; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite;
benzyltriphenylphosphonium chloride
Figure BDA00022141952000001720
Tetra-n-butylbromide->
Figure BDA00022141952000001721
Methyl triphenyl bromination->
Figure BDA00022141952000001722
Ethyltriphenylphosphonium bromide->
Figure BDA0002214195200000174
(ethyltriphenylphosphonium bromide->
Figure BDA0002214195200000175
Onium), n-butyltriphenylphosphonium bromide->
Figure BDA00022141952000001723
Tetraphenyl bromide based on>
Figure BDA00022141952000001724
Ethyltriphenyliodination->
Figure BDA00022141952000001725
Ethyltriphenylacetic acid->
Figure BDA00022141952000001726
Tetra-n-butyl-based device>
Figure BDA00022141952000001710
o, o-diethyldithiophosphate tetra-n-butyl->
Figure BDA00022141952000001711
Benzotriazolate, tetra-n-butyl->
Figure BDA00022141952000001712
Tetrafluoroborate, tetra-n-butyl->
Figure BDA00022141952000001713
Tetraphenylborate, tetraphenyl->
Figure BDA00022141952000001714
Quaternary ammonium salts of tetraphenylborate or the like>
Figure BDA00022141952000001715
Salt; 1, 8-diazabicyclo [5.4.0 ]]Diazabicycloalkenes such as undecene-7 and organic acid salts thereof; organic metal compounds such as zinc octoate, tin octoate, and aluminum acetylacetonate complexes; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, benzyltriethylammonium chloride, and the like; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin chloride; high-melting-point dispersible latent curing accelerators such as amine addition accelerators including dicyandiamide and adducts of amines and epoxy resins; mixing the imidazole compound, organophosphorus compound, and quaternary phosphonium compound>
Figure BDA00022141952000001716
A microcapsule-type latent curing accelerator in which the surface of a curing accelerator such as a salt is coated with a polymer; an amine salt type latent curing agent accelerator; and latent curing accelerators such as high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.
Among them, ethyltriphenylphosphonium bromide is preferable
Figure BDA00022141952000001717
(ethyltriphenylphosphonium bromide->
Figure BDA00022141952000001718
Onium) and the like>
Figure BDA00022141952000001719
And quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, and benzyltriethylammonium chloride.
The amount of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer having an epoxy group.
Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Among them, ether compounds, ester compounds, ketone compounds and alcohol compounds are preferable from the viewpoint of solubility of raw materials and products and easiness of purification of products. The solvent is used in an amount such that the solid content concentration (the ratio of the mass of the components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1 mass% or more, more preferably 5 to 50 mass%.
The reaction temperature is preferably 0 to 200 ℃ and more preferably 50 to 150 ℃. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
A solution containing a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative is obtained by the above operation. The solution may be directly supplied to the preparation of the composition for forming a cured film, may be supplied to the preparation of the composition for forming a cured film after the reaction product contained in the solution is separated, or may be supplied to the preparation of the composition for forming a cured film after the separated reaction product is purified.
< ingredient (B) >
The component (B) in the cured film-forming composition of the present invention is a crosslinking agent.
The crosslinking agent as component (B) is preferably a compound having 2 or more groups that form crosslinks with the thermally crosslinkable functional groups of component (a), and is preferably a crosslinking agent having 2 or more groups such as hydroxymethyl groups or alkoxymethyl groups. Examples of the compound having such a group include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
Specific examples of alkoxymethylated glycolurils include 1,3,4, 6-tetrakis (methoxymethyl) glycoluril, 1,3,4, 6-tetrakis (butoxymethyl) glycoluril, 1,3,4, 6-tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetrakis (butoxymethyl) urea, 1, 3-tetrakis (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Examples of commercially available products include a glycoluril compound manufactured by the general formula (glatiramer) disclosed in japanese patent publication nos. \1246912452\12486\12463\124731258812512512540\\\ (1247474) (old mitsui \124691245212412486 (strain) (trade name; 124693 (registered trademark) 18, 18 (1241251251251251251251251251251251251251259754 (1251251253163 (registered trademark) 1174), compounds such as methylated urea resin (trade names: UFR (registered trademark) 65), butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11 HV), DIC (strain) (manufactured by chemical industries (jp patent) wo (124521251251251251251251251251251251 (wt) \\/formaldehyde resins (high condensation model) 1241 (trade names: 1241251251251251251251251251251251251251251251251251255905wt) \\.
Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzguanamine. 20 as commercially available products, e.g. the groups mentioned in (1) Nos.2121245912420, 20 (198124) Nos.21245912412412412412412412412412412412412412412412412412419820.
Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. <xnotran> , サイテック · インダストリーズ () ( サイテック ()) (: サイメル ( ) 300, サイメル 301, サイメル 303, サイメル 350), (: マイコート ( ) 506, マイコート 508), () ケミカル (: ニカラック ( ) MW-30, ニカラック MW-22, ニカラック MW-11, ニカラック MS-001, ニカラック MX-002, ニカラック MX-730, ニカラック MX-750, ニカラック MX-035), (: ニカラック ( ) MX-45, ニカラック MX-410, ニカラック MX-302) . </xnotran>
The crosslinking agent may be a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound, in which a hydrogen atom of an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. Examples thereof include a high molecular weight compound produced from a melamine compound and a benzoguanamine compound as described in U.S. Pat. No. 6323310. Examples of commercially available products of the melamine compound include trade names: \124693, 12513and/or 12523303 (registered trademarks), and commercially available products of the benzoguanamine compound include trade names: \\ 124523 (registered trademark) 1123 (above, japanese patent publication No. 12469\124124521248612412412463\124125318012473124 (strain 12412412474 (strain 12412412412469870).
Further, as the crosslinking agent of the component (B), there can be used: and polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group (i.e., a hydroxymethyl group) or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, and N-butoxymethylmethacrylamide.
Examples of such polymers include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate.
As such a polymer, a polymer having an N-alkoxymethyl group and a polymerizable group containing a C = C double bond may be used.
Examples of the polymerizable group containing a C = C double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a maleimide group.
The method for obtaining the polymer as described above is not particularly limited. For example, an acrylic polymer having a specific functional group is produced in advance by a polymerization method such as radical polymerization. Next, by reacting a specific functional group of the acrylic polymer with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound), a polymerizable group containing a C = C double bond can be introduced into the polymer as the component (B).
The specific functional group here means a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a plurality of functional groups selected from these.
In the above reaction, preferable combinations of the specific functional group of the acrylic polymer and the group which reacts with the functional group of the specific compound are a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, a hydroxyl group and an acid chloride group, and the like. Further, a more preferable combination is a carboxyl group and an epoxy group in glycidyl methacrylate, or a hydroxyl group and an isocyanate group in isocyanatoethyl methacrylate.
The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.
These crosslinking agents may be used alone or in combination of 2 or more.
The content of the crosslinking agent of component (B) in the composition for forming a cured film of the present invention is preferably 1 to 500 parts by mass, more preferably 5 to 400 parts by mass, based on 100 parts by mass of the reaction product of component (a). When the content of the crosslinking agent is too small, the solvent resistance of a cured film obtained from the composition for forming a cured film is lowered, and the liquid crystal alignment property is lowered. On the other hand, when the content is too large, the liquid crystal alignment property and the storage stability may be lowered.
< ingredient (C) >
The cured film-forming composition of the present invention may contain, as the component (C), a polymer having at least 1 group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.
Examples of the polymer as the component (C) include polymers having a linear or branched structure such as acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkylene imines, polyallylamines, celluloses (cellulose or derivatives thereof), phenol novolac resins, melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.
Preferred examples of the polymer as the component (C) include acrylic polymers, cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.
The acrylic polymer, which is a preferable example of the polymer of the component (C), is not particularly limited as far as it is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, a vinyl compound, and the like, and is a polymer obtained by polymerizing a monomer or a mixture thereof including a monomer having a specific functional group 2[ a group selected from a hydroxyl group, a carboxyl group, an amide group, an aminoalkoxysilyl group, and a group represented by the following formula (2) ], and the kind of the skeleton and the side chain of the main chain of the polymer constituting the acrylic polymer is not particularly limited.
Examples of the monomer having the specific functional group 2 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, a monomer having a carboxyl group, a monomer having an amino group, a monomer having an alkoxysilyl group, and a monomer having a group represented by the following formula (2).
Figure BDA0002214195200000211
(in the formula, R 41 Represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a phenyl group. )
Examples of the monomer having a polyethylene glycol ester group include H- (OCH) 2 CH 2 ) Monoacrylates or monomers of n-OHA methacrylic acid ester. The value of n is 2 to 50, preferably 2 to 10.
Examples of the above-mentioned monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and 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 vinylbenzoic acid.
Examples of the monomer having an amino group include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
Examples of the alkoxysilyl group-containing monomer include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
In the above formula (2), R is 41 Examples of the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms in (b) include the corresponding groups having carbon atoms among the above-exemplified alkyl groups and alkoxy groups.
Examples of the monomer having a group represented by the formula (2) include monomers having groups represented by the following formulae [2-1] to [2-5], and the like.
Figure BDA0002214195200000221
In the present embodiment, when an acrylic polymer as an example of the component (C) is synthesized, a monomer having no hydroxyl group, carboxyl group, amide group, amino group, alkoxysilyl group, or any of the groups represented by the above formula (2) may be used in combination as long as the effect of the present invention is not impaired.
Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, phenyl acrylate, 2-trifluoroethyl acrylate, t-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 acrylate, and 8-ethyl-8-tricyclodecyl acrylate.
Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, 2-trifluoroethyl methacrylate, t-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-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
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 the specific functional group 2 used to obtain the acrylic polymer as an example of the component (C) is preferably 2 mol% or more based on the total amount of all the monomers used to obtain the acrylic polymer as the component (C). When the amount of the monomer having the specific functional group 2 is too small, the solvent resistance of the resulting cured film tends to be insufficient.
The method for obtaining the acrylic polymer as an example of the component (C) is not particularly limited, and for example, it is obtained by a polymerization reaction in a solvent in which a monomer containing a monomer having the specific functional group 2, a monomer having no specific functional group 2 as needed, a polymerization initiator, and the like are coexistent at a temperature of 50 to 110 ℃. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer having the specific functional group 2, the monomer having no specific functional group 2 and the polymerization initiator which are used as necessary, and the like. Specific examples thereof are described in the section of [ solvent ] described later.
The acrylic polymer as an example of the component (C) obtained by the above method is usually in a state of a solution dissolved in a solvent.
Further, the solution of the acrylic polymer as an example of the component (C) obtained by the above method may be put into diethyl ether, water or the like under stirring to reprecipitate, and the formed precipitate may be filtered/washed, and then dried at normal temperature or under reduced pressure or dried by heating to obtain a powder of the acrylic polymer as an example of the component (C). By the above-described operation, the polymerization initiator and the unreacted monomer which coexist with the acrylic polymer as the component (C) can be removed, and as a result, a purified powder of the acrylic polymer as the component (C) can be obtained. In the case where the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
The weight average molecular weight of the acrylic polymer as a preferable example of the component (C) is preferably 3000 to 200000, more preferably 4000 to 150000, and further preferably 5000 to 100000. If the weight average molecular weight is too large exceeding 200000, the solubility in a solvent may be lowered and the handling properties may be lowered, while if the weight average molecular weight is too small below 3000, the curing may be insufficient during thermal curing and the solvent resistance may be lowered. The weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a standard sample. Hereinafter, the same is also applied to the present specification.
Next, as a preferable example of the polyether polyol as the polymer of the component (C), a polyether polyol obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol, or the like to a polyol such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol a, triethylene glycol, or sorbitol, or the like can be cited. Specific examples of the polyether polyol include those described in the formulae ADEKA \/5012559091251250912512523P, G, EDP, BPX, FC, CM, nichio oil \/125919158 (registered trademark) TG 12440, HC-60, ST-30E, ST-40E, G-450, G-750, D1251918 (registered trademark) TG 1254012512458, TG-1000, TG-633000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, 124919458 (registered trademark), and others.
As a preferable example of the polyester polyol as the polymer of the component (C), there can be mentioned a polyester polyol obtained by reacting a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, or the like with a polycarboxylic acid such as adipic acid, sebacic acid, isophthalic acid, or the like. Specific examples of the polyester polyol include 12509125521245220, 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 and OD 12463125211251252454, P-1010, P-3010, P-5014010, P-6010, F-3011010, F-12540404040400, F-1252011252010, P-2016, and the like.
As a preferable example of the polycaprolactone polyol as the polymer of the component (C), there can be mentioned a polycaprolactone polyol obtained by ring-opening polymerization of e-caprolactone using a polyol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include those obtained by the methods described in the methods disclosed in the patent documents Nos. 2A, \ 1250912521\\ 1245288 (registered trademark) and 2B, \\ 12488205 (registered trademark) and 4,220.
Examples of the polycarbonate polyol which is a preferable example of the polymer of the component (C) include polycarbonate polyols obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, or the like. Specific examples of the polycarbonate polyols include C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by methods of patent Nos. 4,220, 1252363, (125031252112463.
Examples of preferable celluloses as the polymer of the component (C) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and preferable examples thereof include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.
Preferred examples of the cyclodextrin as the polymer of the component (C) include cyclodextrins such as α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin, methylated cyclodextrins such as methyl- α -cyclodextrin, 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 and 2, 3-dihydroxyalkyl-cyclodextrin.
A melamine-formaldehyde resin, which is a preferred example of the polymer of the component (C), is a resin obtained by polycondensation of melamine and formaldehyde.
From the viewpoint of storage stability, the melamine-formaldehyde resin of component (C) is preferably one in which a methylol group formed in the polycondensation of melamine and formaldehyde is alkylated, and examples of such a melamine-formaldehyde resin include compounds represented by the following formulae.
Figure BDA0002214195200000261
In the above formula, R 21 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units.
The method for obtaining the melamine formaldehyde resin as component (C) is not particularly limited, and it is generally synthesized by mixing melamine with formaldehyde, making weak alkalinity with sodium carbonate, ammonia, or the like, and then heating at 60 to 100 ℃. The methylol group may be further alkoxylated by reaction with an alcohol.
(C) The melamine formaldehyde resin of component (b) preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and still more preferably 350 to 3500. If the weight average molecular weight is too large in excess of 5000, the solubility in a solvent may be lowered and the workability may be lowered, while if the weight average molecular weight is too small in excess of 250, the curing may be insufficient at the time of thermal curing, and the effect of improving solvent resistance may not be sufficiently exhibited.
In the embodiment of the present invention, the melamine formaldehyde resin of component (C) may be used in the form of a liquid or a solution prepared by redissolving a purified liquid in a solvent described later.
As a preferable example of the polymer of the component (C), a phenol novolac resin is exemplified by a phenol-formaldehyde condensation polymer and the like.
In the composition for forming a cured film of the present embodiment, the polymer of component (C) may be used in the form of a powder or a solution prepared by redissolving a purified powder in a solvent described later.
In the cured film-forming composition of the present embodiment, the component (C) may be a mixture of a plurality of polymers exemplified as the component (C).
The content of the component (C) in the cured film-forming composition of the present invention is usually 400 parts by mass or less, preferably 1 to 400 parts by mass, more preferably 10 to 380 parts by mass, and still more preferably 40 to 360 parts by mass, based on 100 parts by mass of the total amount of the reaction product as the component (a) and the crosslinking agent as the component (B). When the content of the component (C) is too large, the liquid crystal alignment property is liable to be lowered.
< ingredient (D) >
The composition for forming a cured film of the present invention may further contain a crosslinking catalyst as the component (D) in addition to the components (A) and (B).
As the crosslinking catalyst of the component (D), for example, an acid or a thermal acid generator can be suitably used. The component (D) is effective in promoting the thermosetting reaction of the cured film-forming composition of the present invention.
As the component (D), specific examples of the acid include a compound having a sulfonic acid group, hydrochloric acid, and salts thereof. The thermal acid generator is not particularly limited as long as it is a compound that thermally decomposes to generate an acid during heat treatment, that is, a compound that thermally decomposes at a temperature of 80 to 250 ℃ to generate an acid.
Specific examples of the acid include, for example, hydrochloric acid or a salt thereof; sulfonic acid group-containing compounds such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, hydrates, and salts thereof.
Examples of the compound which generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methylsulfonate), and pyridine p-toluenesulfonate
Figure BDA0002214195200000271
Salt, morpholine p-toluenesulfonate->
Figure BDA0002214195200000272
Salts, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and compounds represented by the following formulae.
Figure BDA0002214195200000281
/>
Figure BDA0002214195200000291
/>
Figure BDA0002214195200000301
The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the reaction product as the component (a) and the crosslinking agent as the component (B). By setting the content of the component (D) to 0.01 part by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, when the amount is more than 20 parts by mass, the storage stability of the composition may be lowered.
< ingredient (E) >
In the present invention, a component for improving the adhesiveness of the formed cured film (hereinafter, also referred to as adhesion improving component) may be contained as the component (E).
When the cured film formed from the composition for forming a cured film of the present embodiment containing the component (E) is used as an alignment material, the polymerizable functional group of the polymerizable liquid crystal and the crosslinking reaction site of the alignment material can be linked by a covalent bond, thereby improving the adhesion between the alignment material and the layer of the polymerizable liquid crystal. As a result, the retardation material of the present embodiment obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under high-temperature and high-humidity conditions, and can exhibit high durability against peeling and the like.
As the component (E), a compound having 1 or more polymerizable groups and at least 1 group a selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least 1 group reactive with the group a can be used.
The component (E) is preferably a monomer or a polymer having a group selected from a hydroxyl group and an N-alkoxymethyl group and a polymerizable group.
Examples of the component (E) include a compound having a hydroxyl group and a (meth) acryloyl group, a compound having an N-alkoxymethyl group and a (meth) acryloyl group, and a polymer having an N-alkoxymethyl group and a (meth) acryloyl group. Specific examples are shown below.
An example of the component (E) is a hydroxyl group-containing polyfunctional acrylate (hereinafter, also referred to as hydroxyl group-containing polyfunctional acrylate).
Examples of the hydroxyl group-containing polyfunctional acrylate as the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
An example of the component (E) is a compound having 1 (meth) acryloyl group and 1 or more hydroxyl groups. Preferred examples of such a compound having 1 (meth) acryloyl group and 1 or more hydroxyl groups are mentioned. The compound of component (E) is not limited to the following compound examples.
Figure BDA0002214195200000321
/>
(in the above formula, R 11 Represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10. )
Further, as the compound of the component (E), a compound having 1 molecule which has at least 1 polymerizable group containing a C = C double bond and at least 1N-alkoxymethyl group is exemplified.
Examples of the polymerizable group containing a C = C double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a maleimide group.
Examples of the N, i.e., nitrogen atom of the N-alkoxymethyl group include an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a carbamate nitrogen atom, and a nitrogen atom bonded to a position adjacent to a nitrogen atom of a nitrogen-containing heterocyclic ring. Thus, examples of the N-alkoxymethyl group include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from the group consisting of an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a carbamate nitrogen atom, a nitrogen atom bonded to a nitrogen atom adjacent to a nitrogen atom of a nitrogen-containing heterocyclic ring, and the like.
The component (E) may be any component having the above-mentioned group, and preferably includes, for example, a compound represented by the following formula (X1).
Figure BDA0002214195200000331
(in the formula, R 31 Represents a hydrogen atom or a methyl group, R 32 Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)
<xnotran> , , , , , , , , , , ,1- - ,2- - ,3- - ,1,1- - ,1,2- - ,2,2- - ,1- - , ,1- - ,2- - ,3- - ,4- - ,1,1- - ,1,2- - ,1,3- - ,2,2- - ,2,3- - ,3,3- - ,1- - ,2- - ,1,1,2- - ,1,2,2- - ,1- -1- - ,1- -2- - , ,1- - ,2- - ,3- - ,1,1- - ,1,2- - ,1,3- - ,2,2- - ,2,3- - ,3,3- - ,1- - , </xnotran> 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1-dimethyl-n-hexyl, 1, 2-dimethyl-n-hexyl, 1, 3-dimethyl-n-hexyl, 2-dimethyl-n-hexyl, 2, 3-dimethyl-n-hexyl, 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-n-pentyl, 3-ethyl-n-nonyl, n-decyl and the like.
Specific examples of the compound represented by the formula (X1) include an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. The term (meth) acrylamide refers to both methacrylamide and acrylamide.
As another embodiment of the compound having a polymerizable group containing a C = C double bond and an N-alkoxymethyl group of the component (E), a compound represented by the following formula (X2) is preferably exemplified.
Figure BDA0002214195200000341
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 1-valent aliphatic ring group having 5 to 6 carbon atoms, or a 1-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in its structure.
R 53 Represents a linear or branched alkylene group having 2 to 20 carbon atoms, a 2-valent aliphatic ring group having 5 to 6 carbon atoms, or a 2-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure.
R 54 Represents a linear or branched aliphatic group having 1 to 20 carbon atoms and a valence of 2 to 9, a 2 to 9 aliphatic ring group having 5 to 6 carbon atoms or a 2 to 9 aliphatic ring group containing an aliphatic ring having 5 to 6 carbon atoms, and one methylene group or a plurality of non-adjacent methylene groups of these groups may be replaced by an ether bond.
Z represents > NCOO-, OR-OCON < (where "-" represents 1. Bond,. Sup. Sup. > "<" represents 2 bonds, and represents 1 bond and an alkoxymethyl group (i.e., -OR)) 52 Group) are combined. ).
r is a natural number of 2 to 9.
As R 53 Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of (1) above include a 2-valent group obtained by further removing 1 hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
Furthermore as R 54 Specific examples of the 2-to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of (a) include 2-to 9-valent groups obtained by further removing 1 to 8 hydrogen atoms from an alkyl group having 1 to 20 carbon atoms.
Examples of the alkyl group having 1 carbon atom are a methyl group, and further, an alkyl group having 2 to 20 carbon atoms include an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1, 1-dimethyl-n-propyl group, a n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 1, 1-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 1, 2-trimethyl-n-propyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, a n-eicosyl group, a cyclopentyl group, a cyclohexyl group, a group, and a group in which one or plural kinds of these groups are bonded to 20 carbon atoms, and the like.
Among them, alkylene groups having 2 to 10 carbon atoms are preferable, and R is particularly preferable from the viewpoint of availability of raw materials 53 Is ethylene and R 54 In the case of hexamethylene.
As R 52 Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of (1) include R 53 Specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of (1) and a methyl group. Among them, 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.
R is a natural number of 2 to 9 inclusive, and preferably a natural number of 2 to 6.
The content of the component (E) in the cured film-forming composition according to the embodiment of the present invention is preferably 1 to 100 parts by mass, and more preferably 5 to 70 parts by mass, based on 100 parts by mass of the total amount of the reaction product as the component (a) and the crosslinking agent as the component (B). When the content of the component (E) is 1 part by mass or more, sufficient adhesion can be provided to the formed cured film. However, when the amount is more than 100 parts by mass, the liquid crystal alignment property tends to be lowered.
In the cured film-forming composition of the present embodiment, the component (E) may be a mixture of a plurality of compounds of the component (E).
< solvent >
The composition for forming a cured film of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used in this case is not particularly limited in kind, structure and the like as long as it can dissolve the component (A), the component (B), and if necessary, the component (C), the component (D), the component (E) and/or other additives described later.
<xnotran> , , , , , , , ,2- -1- , , , , , , , , , , , , , , , , , , , , ,2- ,3- -2- ,2- ,2- , γ - ,2- ,2- -2- , , ,2- -3- ,3- ,3- ,3- ,3- , , , , , , , , N, N- , N, N- , N- -2- . </xnotran>
When the alignment material is produced by forming a cured film on a resin film using the composition for forming a cured film of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like are preferable from the viewpoint of a solvent which exhibits resistance to the resin film.
These solvents may be used alone in 1 or in a combination of 2 or more.
< other additives >
Further, the composition for forming a cured film of the present invention may contain an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant, and the like as necessary, as long as the effects of the present invention are not impaired.
< preparation of composition for Forming cured film >
The composition for forming a cured film of the present invention is a composition containing a reaction product of the component (A) and a crosslinking agent of the component (B), and may contain a polymer of the component (C), a crosslinking catalyst of the component (D) and a compound of the component (E) if necessary, and further may contain other additives as long as the effects of the present invention are not impaired. In general, they are used in the form of a solution dissolved in a solvent.
Preferred examples of the composition for forming a cured film of the present invention are as follows.
[1]: a composition for forming a cured film, which comprises a component (A) and 1 to 500 parts by mass of a component (B) per 100 parts by mass of the component (A).
[2]: a composition for forming a cured film, which comprises (A) component, 1 to 500 parts by mass of (B) component based on 100 parts by mass of (A) component, and 1 to 400 parts by mass of (C) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component.
[3]: a composition for forming a cured film, which comprises a component (A), a component (B) in an amount of 1 to 500 parts by mass based on 100 parts by mass of the component (A), and a solvent.
[4]: a composition for forming a cured film, which comprises (A) component, 1 to 500 parts by mass of (B) component based on 100 parts by mass of (A) component, 1 to 400 parts by mass of (C) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component, and a solvent.
[5]: a composition for forming a cured film, which comprises (A) component, 1 to 500 parts by mass of (B) component based on 100 parts by mass of (A) component, 1 to 400 parts by mass of (C) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component, 0.01 to 20 parts by mass of (D) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component, and a solvent.
[6]: a composition for forming a cured film, which comprises (A) component, 1 to 500 parts by mass of (B) component based on 100 parts by mass of (A) component, 1 to 400 parts by mass of (C) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component, 0.01 to 20 parts by mass of (D) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component, 1 to 100 parts by mass of (E) component based on 100 parts by mass of the total amount of a reaction product of (A) component and a crosslinking agent of (B) component, and a solvent.
The mixing ratio, the preparation method, and the like in the case of using the cured film-forming composition of the present invention in the form of a solution will be described in detail below.
The proportion of the solid component in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1 to 60 mass%, preferably 2 to 50 mass%, and more preferably 2 to 20 mass%. Here, the solid component refers to a component obtained by removing a solvent from all components of the cured film-forming composition.
The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which the component (B), the component (C), the component (D), the component (E) and the like are mixed at a predetermined ratio in a solution of the component (a) dissolved in a solvent to prepare a uniform solution; alternatively, other additives may be added and mixed as necessary at an appropriate stage of the preparation method.
In the preparation of the composition for forming a cured film of the present invention, a solution of a specific copolymer (polymer) obtained by polymerization reaction in a solvent may be used as it is. In this case, for example, the component (B), the component (C), the component (D), the component (E), and the like are added to the solution of the component (a) in the same manner as described above to prepare a uniform solution. In this case, a solvent may be further additionally charged for the purpose of concentration adjustment. In this case, the solvent used in the process of producing the component (a) may be the same as or different from the solvent used for adjusting the concentration of the cured film-forming composition.
The solution of the prepared cured film-forming composition is preferably filtered using a filter or the like having a pore size of about 0.2 μm and then used.
< cured film, alignment material and retardation material >
A cured film can be formed by applying a solution of the composition for forming a cured film of the present invention on a substrate (e.g., a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.), a film substrate (e.g., a resin film such as a triacetyl cellulose (TAC) film, a Polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, a polyethylene film, etc.) or the like by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by spin coating, inkjet coating, printing, or the like, to form a coating film, and then, heating and drying with an electric hot plate, an oven, or the like. The cured film can be directly applied as an alignment material.
The conditions for the heat drying may be such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the component of the cured film (alignment material) does not dissolve in the polymerizable liquid crystal solution applied thereon, and for example, a heating temperature and a heating time appropriately selected from the range of 60 ℃ to 200 ℃ for 0.4 to 60 minutes can be used. The heating temperature and the heating time are preferably 70 to 160 ℃ and 0.5 to 10 minutes.
The thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 to 5 μm, and can be appropriately selected in consideration of the step difference, optical properties, and electrical properties of the substrate to be used.
Since the alignment material formed of the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment properties can be applied to the alignment material to align the alignment material. Further, by directly curing the retardation material in the aligned state, the retardation material can be formed as a layer having optical anisotropy. Further, when the substrate on which the alignment material is formed is a film, the retardation film is useful.
Further, a liquid crystal display element in which liquid crystal is aligned can be produced by using 2 substrates having the alignment material of the present invention formed as described above, bonding the alignment materials on the two substrates to face each other via a spacer, and then injecting liquid crystal between the substrates.
The composition for forming a cured film of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display devices, and the like.
Examples
The present invention will be described specifically with reference to examples of the present invention, but the present invention is not limited to these examples.
[ shorthand notations used in examples ]
The meanings of the shorthand symbols used in the following examples are as follows.
< raw materials >
GMA: glycidyl methacrylate
M100: 3, 4-epoxycyclohexylmethyl methacrylate
AIBN: alpha, alpha' -azobisisobutyronitrile
BMAA: n-butoxymethylacrylamide
MMA: methacrylic acid methyl ester
HEMA: 2-Hydroxyethyl methacrylate
< ingredient B >
HMM: melamine crosslinking agents of the following structural formula [ \12469\1245212513 (CYMEL) (registered trademark) 303 (mitsui 1246938 (manufactured by strain 124521241248612463
Figure BDA0002214195200000391
PL: tetramethoxymethyl glycoluril [ POWDERLINK (registered trademark) 1174 (Tri well \1246912452\1248612463
Figure BDA0002214195200000401
< ingredient D >
PTSA: p-toluenesulfonic acid monohydrate
< ingredient E >
E-1: a compound having a hydroxyl group and an acryloyl group represented by the following structural formula
Figure BDA0002214195200000402
E-2: a compound having an N-alkoxymethyl group and an acryloyl group represented by the following structural formula
Figure BDA0002214195200000403
< solvent >
Each of the resin compositions of examples and comparative examples contains a solvent, and propylene glycol monomethyl ether (PM) was used as the solvent.
< determination of the molecular weight of the Polymer >
The molecular weight of the acrylic copolymer in the polymerization example was measured by the following procedure using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) manufactured by Shodex corporation and a column (KD-803, KD-805) manufactured by Shodex corporation.
The number average molecular weight (hereinafter referred to as mn.) and the weight average molecular weight (hereinafter referred to as mw.) described below are expressed in terms of polystyrene.
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Standard sample for standard curve preparation: standard polystyrene (molecular weight: about 197,000, 55,100, 12,800,3,950,1,260, 580, manufactured by Showa Denko K.K.).
< Synthesis of component A >
< polymerization example 1 >
GMA (15.0 g) and AIBN (0.5 g) as a polymerization catalyst were dissolved in tetrahydrofuran (46.4 g), and the mixture was reacted under heating and refluxing conditions for 20 hours to obtain an acrylic polymer solution. The resulting acrylic polymer solution was slowly dropped into 500.0g of hexane to precipitate a solid, and filtration and drying under reduced pressure were performed to obtain an acrylic polymer (P1) having an epoxy group. The resulting acrylic polymer had an Mn of 25,000,mw of 9,800.
< polymerization example 2 >
M100.0 g and AIBN 0.5g as a polymerization catalyst were dissolved in tetrahydrofuran 46.4g and reacted under heating and reflux for 20 hours to obtain an acrylic polymer solution. The resulting acrylic polymer solution was slowly dropped into 500.0g of hexane to precipitate a solid, and filtration and drying under reduced pressure were performed to obtain an acrylic polymer having an epoxy group (P2). The resulting acrylic polymer had an Mn of 35,000,Mw of 15,000.
< Synthesis example 1 >
10.0g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 11.3g of 4-methoxycinnamic acid, and 0.4g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 50.8g of PMs, and the mixture was reacted at 120 ℃ for 20 hours. The solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
< Synthesis example 2 >
10.0g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 12.0g of 4-propoxycinnamic acid, and 0.4g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 50.8g of PMs, and the mixture was reacted at 120 ℃ for 20 hours. The solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PA-2). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
Synthesis example 3
10.0g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 14.5g of 3- (1, 1' -biphenyl-4-yl) acrylic acid, and 0.4g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 58.8g of PM, and the mixture was reacted at 120 ℃ for 20 hours. This solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PA-3). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
< Synthesis example 4 >
10.0g of the epoxy group-containing acrylic polymer (P2) obtained in polymerization example 2, 8.2g of 4-methoxycinnamic acid, and 0.3g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM43.2g, and the mixture was reacted at 120 ℃ for 20 hours. The solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-4). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
< Synthesis example 5 >
10.0g of an epoxy group-containing polymer UG-4035 (ARUFON series, manufactured by Toyo Seiya Kabushiki Kaisha Co., ltd.), 3.1g of 4-methoxycinnamic acid, and 0.1g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 52.7g of PM, and the mixture was reacted at 120 ℃ for 20 hours. This solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
< Synthesis example 6 >
10.0g of an epoxy group-containing polymer EHPE3150 (manufactured by strain: v 12480v 12452v 12475v 12523), 9.9g of 4-methoxycinnamic acid, and 0.4g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM 47.2g, and reacted at 120 ℃ for 20 hours. The solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-6). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
< Synthesis example 7 >
10.0g of an epoxy group-containing polymer ECN-1299 (manufactured by Asahi Kasei corporation), 10.3g of 4-methoxycinnamic acid, and 0.3g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 61.9g of PM, and the mixture was reacted at 120 ℃ for 20 hours. The solution was slowly added dropwise to 700g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-7). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
< Synthesis example 8 >
10.0g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 7.3g of 4-methoxycinnamic acid, 1.3g of acrylic acid, 0.2g of dibutylhydroxytoluene, and ethyltriphenylphosphonium bromide as a reaction catalyst were reacted with each other
Figure BDA0002214195200000431
0.2g of PM was dissolved in 44.6g of PM, and the mixture was reacted at 90 ℃ for 20 hours. The solution was slowly added dropwise to 500g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-8). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared. The proportion of epoxy groups that reacted with 4-methoxycinnamic acid among the epoxy groups of the polymer (PA-8) was 70 mol%.
< Synthesis of component B >
< polymerization example 3 >
100.0g of BMAA and 4.2g of AIBN as a polymerization catalyst were dissolved in 193.5g of PM, and the resulting solution was reacted at 90 ℃ for 20 hours to obtain an acrylic polymer solution. The acrylic polymer solution was slowly dropped into 2000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PB-1). The Mn of the resulting acrylic polymer was 2,700 and the Mw was 3,900.
< polymerization example 4 >
32.0g of BMAA, 8.0g of GMA and 0.8g of AIBN as a polymerization catalyst were dissolved in 204.0g of tetrahydrofuran, and the resulting solution was reacted at 60 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (P-3). The resulting acrylic copolymer had Mn of 7,000,Mw of 18,000.
< synthetic example 9 >
10.0g of the acrylic copolymer (P-3) obtained in polymerization example 4, 2.2g of acrylic acid, 0.2g of dibutylhydroxytoluene, and 10mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60g of PM, and the mixture was reacted at 90 ℃ for 20 hours. This solution was slowly dropped into 500g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure, thereby obtaining a polymer (PB-2) having an acryloyl group. To carry out 1 H-NMR analysis confirmed that the polymer (PB-2) had an acryloyl group.
Synthesis of < C component >
< polymerization example 5 >
MMA 30.0g, HEMA 3.0g, and AIBN 0.3g as a polymerization catalyst were dissolved in PM 146.0g, and the resulting solution was reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (PC-1). The resulting acrylic copolymer had an Mn of 18,000,Mw of 32,800.
< preparation of polymerizable liquid Crystal solution >
< preparation example 1 >
29.0g of a polymerizable liquid crystal LC242 (manufactured by BASF corporation), 0.9g of a polymerization initiator (124521252360907, a stirrer (manufactured by BASF corporation), 0.2g of BYK-361N (manufactured by BYK corporation) as a leveling agent, and methyl isobutyl ketone as a solvent were added to obtain a polymerizable liquid crystal solution (RM-1) having a solid content concentration of 30 mass%.
< preparation example 2 >
29.0g of a polymerizable liquid crystal LC242 (manufactured by BASF corporation), 0.9g of a polymerization initiator (124521252360907, BYK-361N (manufactured by BYK corporation) as a leveling agent, 0.2g of a solvent (cyclopentanone) were added to the mixture, and a polymerizable liquid crystal solution (RM-2) having a solid content concentration of 30 mass% was obtained.
< examples, comparative examples >
Each of the cured film-forming compositions of examples and comparative examples was prepared in the composition shown in Table 1. Next, a cured film was formed using each of the cured film forming compositions, and the alignment of each of the obtained cured films was evaluated.
[ Table 1]
Figure BDA0002214195200000451
[ evaluation of orientation ]
Each of the cured film-forming compositions of examples and comparative examples was coated on a TAC film at a wet film thickness of 4 μm using a bar coater. The cured films were formed on the TAC films by heating and drying in a thermal cycle oven at 90 ℃ or 110 ℃ for 60 seconds, respectively. To each cured film at a rate of 5mJ/cm 2 Or 30mJ/cm 2 The exposure dose of (2) was perpendicular to the light of 313nm linear polarization to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution (RM-1) or (RM-2) was coated at a wet film thickness of 6 μm using a bar coater. The coating was dried on a hot plate at 90 ℃ for 60 seconds and then dried at 300mJ/cm 2 Exposing to produce the phase difference material. The retardation material on the substrate thus produced was sandwiched between a pair of polarizers, the state of expression of the retardation characteristics in the retardation material was observed, and the column of "orientation" is described with the case where the retardation was expressed without defect as o and the case where the retardation was not expressed as x. The evaluation results are summarized in table 2 below.
[ Table 2]
TABLE 2
Figure BDA0002214195200000471
As shown in Table 2, the phase difference materials obtained by using the cured film-forming compositions of examples 1 to 18 exhibited a polarized light exposure of 5mJ/cm 2 The liquid crystal molecules also exhibit good liquid crystal alignment properties.
In contrast, the retardation materials obtained using the cured film-forming compositions of comparative examples 1 to 3 exhibited a polarization exposure of 30mJ/cm 2 Good liquid was not obtainedCrystal orientation.
Industrial applicability
The composition for forming a cured film according to the present invention is very useful as a material for forming an alignment material for forming a liquid crystal alignment film used for forming a liquid crystal display device and an optically anisotropic film provided inside or outside the liquid crystal display device, and is particularly suitable as a material for a retardation material for a circularly polarizing plate used as an antireflection film of an IPS-LCD or an organic EL display.

Claims (10)

1. A cured film-forming composition comprising:
(A) A reaction product of a polymer having an epoxy group and a cinnamic acid derivative represented by the following formula (1); and
(B) A crosslinking agent (B) which is a crosslinking agent having a methylol group or an alkoxymethyl group,
contains 1 to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A),
Figure FDA0003885873660000011
in the formula (1), A 1 And A 2 Each independently represents a hydrogen atom or a methyl group, R 1 Represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a halocycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, a haloalkenyl group having 3 to 8 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a haloalkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, an alkyl) carbonyl group having 1 to 6 carbon atoms, a haloalkyl) carbonyl group having 1 to 6 carbon atoms, an alkoxy) carbonyl group having 1 to 6 carbon atoms, a haloalkoxy) carbonyl group having 1 to 6 carbon atoms, an alkylamino) carbonyl group having 1 to 6 carbon atoms, a haloalkyl) aminocarbonyl group having 1 to 6 carbon atoms, a di (alkyl) aminocarbonyl group having 1 to 6 carbon atoms, a cyano group, and a cyano groupSubstituent in nitro, R 2 Represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group, R 3 Represents a single bond, an oxygen atom, -COO-or-OCO-, R 4 ～R 7 Each independently represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, 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, and n is an integer of 0 to 3.
2. The cured film-forming composition according to claim 1, further comprising (C) a polymer having at least 1 group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.
3. The cured film-forming composition according to claim 1 or 2, further comprising (D) a crosslinking catalyst.
4. The cured film-forming composition according to claim 1 or 2, comprising (E) a compound having 1 or more polymerizable groups and at least 1 group A selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group or at least 1 group reactive with the group A.
5. The composition for forming a cured film according to claim 2, wherein the component (C) is contained in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).
6. The composition for forming a cured film according to claim 3, wherein the component (D) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).
7. The composition for forming a cured film according to claim 4, wherein the component (E) is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).
8. A cured film obtained by using the composition for forming a cured film according to any one of claims 1 to 7.
9. An alignment material formed by using the cured film-forming composition according to any one of claims 1 to 7.
10. A phase difference material comprising a cured film obtained by using the composition for forming a cured film according to any one of claims 1 to 7.
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