CN111164120A - Cured film forming composition, alignment material, and retardation material - Google Patents
Cured film forming composition, alignment material, and retardation material Download PDFInfo
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- CN111164120A CN111164120A CN201880064199.0A CN201880064199A CN111164120A CN 111164120 A CN111164120 A CN 111164120A CN 201880064199 A CN201880064199 A CN 201880064199A CN 111164120 A CN111164120 A CN 111164120A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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Abstract
本发明的课题是提供用于提供显示良好的液晶取向性，并且与液晶层的密合性优异的取向材的固化膜形成用组合物。解决手段是固化膜形成用组合物、以及由该固化膜形成用组合物获得的固化膜、取向材、和相位差材，上述固化膜形成用组合物含有：(A)具有环氧基的聚合物与具有包含聚合性双键的基团的肉桂酸衍生物的反应生成物；以及(B)交联剂。The subject of this invention is to provide the cured film formation composition for providing the orientation material which shows favorable liquid crystal orientation, and is excellent in adhesiveness with a liquid crystal layer. The solution is a cured film-forming composition, and a cured film, an orientation material, and a retardation material obtained from the cured film-forming composition, wherein the cured film-forming composition contains: (A) a polymer having an epoxy group A reaction product of a cinnamic acid derivative having a polymerizable double bond-containing group; and (B) a crosslinking agent.
Description
Technical Field
The present invention relates to a composition for forming a cured film for aligning liquid crystal molecules, an alignment material, and a retardation material. In particular, the present invention relates to a composition for forming a cured film, an alignment material, and a retardation material which are useful for a patterned retardation material used for producing a circularly polarized light glasses type 3D display and a retardation material used for a circularly polarized light plate used as an antireflection film of 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. The phase difference material is composed of a plurality of 2 phase difference regions having different phase difference characteristics, which are regularly arranged. 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 a polymerizable liquid crystal, as disclosed in patent document 1, for example. Optical patterning of a phase difference material formed of a polymerizable liquid crystal utilizes a photo-alignment technique known in the formation of an alignment material for 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. Further, a photo alignment film was obtained as an alignment material in which 2 liquid crystal alignment regions having different liquid crystal alignment control directions were formed. 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 aligned polymerizable liquid crystal is cured to form a patterned retardation material.
The antireflection film of the organic EL display is configured by a linear polarizer and an 1/4 wavelength phase difference plate, and converts external light directed to the panel surface of the image display panel into linearly polarized light by the linear polarizer and then into circularly polarized light by the 1/4 wavelength phase difference plate. Here, although the external light based on the circularly polarized light is reflected on the surface of the image display panel, 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, contrary to the arrival time, and then shielded by the linearly polarizing plate, and as a result, the emission to the outside is remarkably suppressed.
Patent document 2 proposes an 1/4 wavelength phase difference plate: a method of forming the optical film by inverse dispersion characteristics by forming a 1/4 wavelength phase difference plate by combining an 1/2 wavelength plate and a 1/4 wavelength plate. In the case of this method, an optical film can be formed by inverse dispersion characteristics using a liquid crystal material based on the forward dispersion characteristics in a wide wavelength band for display of a color image.
In recent years, liquid crystal materials having an inverse dispersion property 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 an inverse dispersion characteristic, instead of constituting a 1/4 wavelength retardation plate by a 2-layer retardation layer by combining an 1/2 wavelength plate and a 1/4 wavelength plate, an optical film capable of securing a desired retardation over a wide wavelength band can be realized by a simple configuration by constituting a retardation layer by a single layer to secure an inverse dispersion characteristic.
In order to align the liquid crystal, an alignment layer is used. 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 static electricity and dust, which are problems of the rubbing method, do not occur and quantitative alignment treatment can be controlled.
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 by polarized UV irradiation (hereinafter, also referred to as liquid crystal alignment property) (see patent documents 5 to 7).
In addition to liquid crystal alignment ability, the alignment layer is also required to have adhesion to the liquid crystal layer. For example, when the adhesion force between the alignment layer and the liquid crystal layer formed thereon is insufficient, the liquid crystal layer may be peeled off in a winding step or the like included in the production of the retardation film.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2005-49865
Patent document 2: japanese laid-open patent 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
Disclosure of Invention
Problems to be solved by the invention
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 for providing an alignment material which exhibits good liquid crystal alignment properties and has excellent adhesion to a liquid crystal layer.
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 exhibiting good liquid crystal alignment properties and excellent adhesion to a liquid crystal layer can be formed by selecting a composition for forming a cured film based on (a) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group having a polymerizable double bond, and (B) a crosslinking agent, and have completed the present invention.
That is, the present invention relates to, as a 1 st aspect, a cured film-forming composition containing: (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond; and (B) a crosslinking agent.
An aspect 2 relates to the cured film-forming composition according to aspect 1, wherein the group containing a polymerizable double bond is a (meth) acryloyl group.
A 3 rd aspect relates to the cured film-forming composition according to the 1 st or 2 nd aspect, wherein the cinnamic acid derivative having a polymerizable double bond-containing group is a compound represented by the following formula (1).
In the formula (1), A1And A2Each independently represents a hydrogen atom or a methyl group,
R1represents a group represented by the following formula (c-2),
(in the formula (c-2), the dotted line represents a bond, R101Represents an alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms of the alkylene group may be replaced by fluorine atoms or organic groups. Furthermore, R101In (C-CH)2CH2-may be substituted by-CH ═ CH-, and further, when any of the groups listed below are not adjacent to each other, R101In (C-CH)2CH2May be substituted by a group selected from-O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-and-CO-, M1Represents a hydrogen atom or a methyl group. )
R2Represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group,
R3represents a single bond, an oxygen atom, -COO-, -OCO-, -CH ═ CHCOO-or-OCOCH ═ CH-,
R4～R7each 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,
furthermore, R2、R3And R4May together form an aromatic radical, or R2、R3And R6It is possible to form the aromatic groups together,
n is an integer of 0 to 3. )
The cured film-forming composition according to claim 4 relates to any one of claims 1 to 3, wherein the crosslinking agent of component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
The 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, 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 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, further comprising: (D) a crosslinking catalyst.
The 7 th aspect of the present invention is the cured film-forming composition according to any one of the 1 st to 6 th aspects, which contains a compound (E) having:
1 or more polymerizable groups, and,
at least 1 group a selected from hydroxyl, carboxyl, amido, amino, and alkoxysilyl groups or at least 1 group reactive with the group a.
An 8 th aspect of the present invention relates to the cured film forming composition according to any one of the 1 st to 7 th aspects, which contains the component (B) in an amount of 1 to 500 parts by mass based on 100 parts by mass of the component (a).
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, which comprises 1 to 400 parts by mass of the component (C) per 100 parts by mass of the total amount of the crosslinking agents of the components (a) and (B).
A 10 th aspect of the present invention relates to the cured film forming composition according to any one of the 6 th to 9 th aspects, which comprises 0.01 to 20 parts by mass of the component (D) per 100 parts by mass of the total amount of the crosslinking agents of the components (a) and (B).
An11 th aspect of the present invention relates to the cured film forming composition according to any one of the 7 th to 10 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 crosslinking agents of the components (a) and (B).
The 12 th aspect of the present invention relates to a cured film obtained from the composition for forming a cured film according to any one of the 1 st to 11 th aspects.
An alignment material according to claim 13 is obtained from the cured film-forming composition according to any one of claims 1 to 11.
The 14 th aspect of the present invention relates to a phase difference material produced using the cured film obtained from the cured film-forming composition according to any one of the 1 st to 11 th aspects.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a cured film exhibiting good liquid crystal alignment properties and excellent adhesion to a liquid crystal layer, and a composition for forming a cured film suitable for forming the same can be provided. According to the present invention, an alignment material having excellent liquid crystal alignment properties and light transmittance can be provided. Further, according to the present invention, a phase difference material capable of performing optical patterning with high accuracy can be provided.
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 cinnamic acid derivative having a group containing a polymerizable double bond; 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). A crosslinking catalyst may be further 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 having a group containing a polymerizable double bond.
< 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, α -glycidyl ethacrylate, α -n-propyl glycidyl acrylate, α -n-butyl glycidyl acrylate, 3, 4-epoxybutyl methacrylate, 6, 7-epoxyheptyl acrylate, 6, 7-epoxyheptyl methacrylate, α -6, 7-epoxyheptyl 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 methacrylate such as hydroxymethyl methacrylate, 2-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, and methacrylic acid2-ethylhexyl acid, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like; 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 ]2,6]Decan-8-yl methacrylate, tricyclo [5.2.1.02,6]Decane-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc.; examples of the cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, and tricyclo [5.2.1.0 ]2,6]Decane-8-yl acrylate, tricyclo [5.2.1.02,6]Decane-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl 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; examples of the bicyclic unsaturated compounds 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-diethoxydicyclo [2.2.1]Hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1]Hept-2-ene, 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-maleimidohexanoate, and N-succinimidylAmino-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like, as the unsaturated aromatic compound, for example, styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like, as the conjugated diene compound, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like, as the unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid and the like, as the unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like, as the unsaturated dicarboxylic anhydride, for example, each anhydride of the above unsaturated dicarboxylic acid, and as the other polymerizable unsaturated compound, for example, acrylonitrile, methacrylonitrile, vinyl chloride, 1-dichloroethylene, acrylamide, methacrylamide, vinyl acetate and the like.
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 EHPE3150, EHPE3150CE (manufactured by NIGHT ダイセル (old ダイセル CHEMICAL INDUSTRIAL CO., LTD)), UG-4010, UG-4035, UG-4040, UG-4070 (manufactured by NIGHMA SYNTHESIS (LTD.), ECN-1299 (manufactured by Asahi Kasei corporation), DEN431, DEN438 (manufactured by NIGHT ダウケミカル (LTD.), JeR-152 (manufactured by TRITON ケミカル (JER ジャパンエポキシレジン (LTD)), old エピクロン N-660, n-665, N-670, N-673, N-695, N-740, N-770, N-775(DIC (manufactured by NIDAIZHON インキ CHEMICAL WORKS )), EOCN-1020, and EOCN-102S, EOCN-104S (manufactured by NITRIC CHEMICAL KOKAI Co., Ltd.), and the like.
< cinnamic acid derivative having a polymerizable double bond-containing group >
The polymerizable double bond is preferably a carbon-carbon double bond. Examples of the group containing such a carbon-carbon double bond include a vinyl group, a (meth) acryloyl group, and an acrylamide group, but a (meth) acryloyl group is preferable.
The cinnamic acid derivative having a group containing a polymerizable double bond is preferably a compound represented by the following formula (1).
In the formula (1), A1And A2Each independently represents a hydrogen atom or a methyl group,
R1represents a group represented by the following formula (c-2),
(in the formula (c-2), the dotted line represents a bond, R101Represents an alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms of the alkylene group may be replaced by fluorine atoms or organic groups. Furthermore, R101In (C-CH)2CH2-may be substituted by-CH ═ CH-, and further, in the case where any of the groups listed below are not adjacent to each other, may be substituted by a group selected from the group consisting of-O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-and-CO-, M1Represents a hydrogen atom or a methyl group. )
R2Represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group,
R3represents a single bond, an oxygen atom, -COO-, -OCO-, -CH ═ CHCOO-or-OCOCH ═ CH-,
R4～R7each 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,
furthermore, R2、R3And R4May together form an aromatic radical, or R2、R3And R6It is possible to form the aromatic groups together,
n is an integer of 0 to 3. )
As R2Examples of the 2-valent aromatic group in (b) include a 1, 4-phenylene group, a 2-fluoro-1, 4-phenylene group, a 3-fluoro-1, 4-phenylene group, a 2,3,5, 6-tetrafluoro-1, 4-phenylene group, and the like; as R2Examples of the 2-valent alicyclic group of (a) include a 1, 2-cyclopropylene group, a 1, 3-cyclobutylene group, a 1, 4-cyclohexylene group and the like; as R2Examples 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 R2Examples of the 2-valent condensed ring group include a 2, 6-naphthylene group and the like. As R2Preferably 1, 4-phenylene.
Preferable examples of the compound represented by the above formula (1) include, for example, the following formulae M1-1 to M1-5.
(in the formula, M1Is a hydrogen atom or a methyl group, and s1 represents the number of methylene groups and is a natural number of 2 to 9. )
The compound represented by the above formula (1) can be synthesized by appropriately combining the compounds according to a general method 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 liquid crystal aligning agent 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 cinnamic acid derivative is used in the reaction in a proportion of preferably 0.01 to 1.5 mol, more preferably 0.05 to 1.3 mol, and even more preferably 0.1 to 1.1 mol, based on 1 mol of the epoxy group contained in the polymer having an epoxy group.
As the organic catalyst that can be used here, a compound known as an organic base or 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; such as 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
Trimellitic acid salt, 1- (2-cyanoethyl) -2-phenylimidazole
Trimellitic acid salt, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole
Trimellitate, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- (2 ' -n-undecylimidazolyl) ethylImidazole compounds such as sym-triazine, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-sym-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-sym-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite; such as benzyltriphenylphosphonium chloride
Tetra-n-butylbromide
Methyl triphenyl phosphonium bromide
Ethyltriphenylphosphonium bromide
N-butyl triphenyl phosphonium bromide
Tetraphenyl bromides
Ethyl triphenyl iodide
Ethyl triphenyl acetic acid
Tetra-n-butyl
o, o-diethyldithiophosphate tetra-n-butyl
Benzotriazole salts tetra-n-butyl
Tetrafluoroborate, tetra-n-butyl
Tetraphenylborate, tetraphenyl
Quaternary phosphonium salts such as tetraphenylborate
Salt; such as 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 complex; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; halogenated metal compounds such as zinc chloride and tin tetrachloride; 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, organic phosphorus compound and quaternary phosphonium compound
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, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.
The catalyst is used in a proportion of 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.
Thus, a solution containing a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative was obtained. The solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be supplied to the preparation of the liquid crystal aligning agent after the polymer contained in the solution is separated, or may be supplied to the preparation of the liquid crystal aligning agent after the separated polymer is purified.
< ingredient (B) >
The component (B) in the composition for forming a cured film of the present invention is a crosslinking agent.
The crosslinking agent as the component (B) is preferably a crosslinking agent having a group which forms a crosslink with the thermally crosslinkable functional group of the component (A), for example, a methylol group or an alkoxymethyl group.
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, 3-tetrakis (butoxymethyl) urea, 1,3, 3-tetrakis (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Commercially available products include glycoluril compounds (trade names: サイメル (registered trademark) 1170 and パウダーリンク (registered trademark) 1174) manufactured by Nippon サイテック & インダストリーズ (old Mitsui サイテック), urea/formaldehyde resins (highly condensed type, trade names: ベッカミン (registered trademark) J-300S, ベッカミン P-955 and ベッカミン N) manufactured by Nippon Kagaku (old Mitsui サイテック), methylated urea resins (trade name: UFR (registered trademark) 65), butylated urea resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R and U-VAN11HV), DIC (old Nippon インキ chemical industry ) (old Japan ベッカミン).
Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzguanamine and the like. Commercially available products include those manufactured by Nippon Kogyo No. サイテック & インダストリーズ (old Mitsui No. サイテック) (trade name: サイメル (registered trademark) 1123), and those manufactured by Nippon Kogyo No. ケミカル (trade name: ニカラック (registered trademark) BX-4000, ニカラック BX-37, ニカラック BL-60, ニカラック BX-55H).
Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl-type melamine compounds (trade names: サイメル (registered trademark) 300, サイメル 301, サイメル 303, サイメル 350) prepared by Nippon サイテック - インダストリーズ (old Mitsui サイテック (Co.)), butoxymethyl-type melamine compounds (trade names: マイコート (registered trademark) 506, マイコート 508), (Nippon und ケミカル -prepared methoxymethyl-type melamine compounds (trade names: ニカラック (registered trademark) 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), butoxymethyl-type melamine compounds (trade name: ニカラック (registered trademark) MX-45, 5636 MX-035), ニカラック MX-410, ニカラック MX-302), and the like.
Further, the compound may be one obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is replaced with a hydroxymethyl group or an alkoxymethyl group. Examples thereof include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds as described in U.S. Pat. No. 6323310. Examples of commercially available products of the melamine compound include trade names: サイメル (registered trademark) 303, and the trade names of the benzoguanamine compounds include: サイメル (registered trademark) 1123 (manufactured by サイテック, インダストリーズ, japan, inc., サイテック, ltd.), and the like.
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 can be used.
Examples of the polymerizable group having 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 1 is produced in advance by a polymerization method such as radical polymerization. Next, the specific functional group 1 is reacted with a compound having an unsaturated bond at the end (hereinafter referred to as a specific compound), whereby a polymerizable group containing a C ═ C double bond can be introduced into the polymer as the component (B).
Here, the specific functional group 1 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, the specific functional group 1, and the functional group of the specific compound and the group participating in the reaction are preferably combined with 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, or the like. Further, a more preferred combination is carboxyl group and glycidyl methacrylate, or hydroxyl group and isocyanate ethyl 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 polymer as 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, if the content is too large, the liquid crystal alignment property and storage stability may be deteriorated.
< ingredient (C) >
The cured film-forming composition of the present invention may contain, as the component (C), a polymer having at least 1 group (hereinafter, also referred to as a specific functional group 2) selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.
Examples of the polymer of 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 of component (C) include acrylic polymers, hydroxyalkyl 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 long as it is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or a vinyl compound, and a polymer obtained by polymerizing a monomer containing a monomer having the specific functional group 2 or a mixture thereof.
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, and a monomer having an alkoxysilyl group and a group represented by the above formula 2.
Examples of the monomer having a polyethylene glycol ester group include H- (OCH)2CH2) Monoacrylates or monomethacrylates of n-OH. The value of n is 2 to 50, preferably 2 to 10.
Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 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 in a side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
Examples of the monomer having an alkoxysilyl group in a side chain thereof include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
In the present embodiment, when an acrylic polymer as an example of the component (C) is synthesized, a monomer having no group represented by a hydroxyl group, a carboxyl group, an amide group, an amino group, or an alkoxysilyl group 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, anthracenyl methyl acrylate, phenyl acrylate, 2,2, 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, 2,2, 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 mixtures thereof, And 8-ethyl-8-tricyclodecyl methacrylate and the like.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, 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). In the case where the monomer having the specific functional group 2 is too small as compared with 2 mol%, the solvent resistance of the resulting cured film tends to become 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, a polymerization initiator, and the like, which are used as needed. Specific examples thereof are described in the section of [ solvent ] mentioned below.
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 acrylic polymer solution as an example of the component (C) obtained by the above-mentioned method may be put into diethyl ether, water or the like under stirring to reprecipitate, and the formed precipitate may be filtered and washed, and then dried at normal temperature or under reduced pressure or dried by heating to obtain an acrylic polymer powder 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. When 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 acrylic polymer as a preferable example of the component (C) has a weight average molecular weight of 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. In addition, 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, preferable examples of the polyether polyol as the component (C) include polyether polyols 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. Specific examples of the polyether polyol include アデカポリエーテル P series, G series, EDP series, BPX series, FC series, CM series, Japanese oil ユニオックス (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, ユニオール (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, ノニオン (registered trademark) LT-221, ST-221, and OT-221 manufactured by ADEKA.
As a preferable example of the polyester polyol as 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 or polypropylene glycol with a polycarboxylic acid such as adipic acid, sebacic acid or isophthalic acid. Specific examples of the polyester polyol include ポリライト (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560, クラレ polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-510, F-1010, F-6012010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.
As a preferred example of the polycaprolactone polyol as the component (C), there can be mentioned a polycaprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone using a polyol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include DIC ポリライト (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, ダイセル プ ラ ク セ ル (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, and 320.
Preferable examples of the polycarbonate polyol as the component (C) include polycarbonate polyols obtained by reacting a polyol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, or the like. Specific examples of the polycarbonate polyol include CD205, CD205PL (registered trademark) made by ダイセル プ ラ ク セ ル (registered trademark), CD210, C-590, C-1050, C-2050, C-2090 and C-3090 made by CD220 and クラレ.
Examples of preferable celluloses as 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 preferred examples are hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.
Preferred examples of the cyclodextrin as the component (C) include α -cyclodextrin, β -cyclodextrin, gamma-cyclodextrin and other cyclodextrins, methyl- β 0-cyclodextrin, methyl- β 1-cyclodextrin, methyl-gamma-cyclodextrin and other methylated cyclodextrins, hydroxymethyl- β 2-cyclodextrin, hydroxymethyl- β 3-cyclodextrin, hydroxymethyl-gamma-cyclodextrin, 2-hydroxyethyl- α -cyclodextrin, 2-hydroxyethyl- β -cyclodextrin, 2-hydroxyethyl-gamma-cyclodextrin, 2-hydroxypropyl- α -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, 2-hydroxypropyl-gamma-cyclodextrin, 3-hydroxypropyl- α -cyclodextrin, 3-hydroxypropyl- β -cyclodextrin, 3-hydroxypropyl-gamma-cyclodextrin, 2, 3-dihydroxypropyl- α -cyclodextrin, 2, 3-dihydroxypropyl- β -cyclodextrin, 2, 3-dihydroxypropyl-gamma-cyclodextrin and other alkyl cyclodextrins.
A melamine-formaldehyde resin, which is a preferred example of the component (C), is a resin obtained by polycondensation of melamine and formaldehyde.
From the viewpoint of storage stability, the melamine-formaldehyde resin as the component (C) is preferably one in which a methylol group formed at the time of polycondensation of melamine and formaldehyde is alkylated. Examples of the melamine formaldehyde resin as the component (C) include resins having a unit structure represented by the following formula.
In the above formula, R21Represents 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 the component (C) is not particularly limited, but generally, the melamine resin is synthesized by mixing melamine with formaldehyde, making the mixture weakly alkaline with sodium carbonate, ammonia, or the like, and then heating the mixture at 60 to 100 ℃. The methylol group may be alkoxylated by further reacting it with an alcohol.
(C) The melamine formaldehyde resin of component (A) 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 dissolving a purified liquid in a solvent to be described later.
As a preferable example of the phenol novolac resin as the component (C), for example, a phenol-formaldehyde condensation polymer and the like can be given.
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 to be 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).
When the component (C) is contained in the cured film-forming composition of the present invention, the content is preferably 400 parts by mass or less, 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 polymer 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 accelerating 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. Further, 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
Salt, morpholine p-toluenesulfonate
Salts, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2, 2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and compounds represented by the following formulae.
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 polymer 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) >
The present invention may contain, 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. This acts as a component for improving the adhesiveness of the formed cured film (hereinafter, also referred to as adhesion improving component).
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 may be linked by a covalent bond in order to improve 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.
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 multifunctional acrylate (hereinafter, also referred to as a hydroxyl group-containing multifunctional acrylate).
Examples of the hydroxyl group-containing multifunctional acrylate as the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
An example of the component (E) is a compound having 1 acryloyl group and 1 or more hydroxyl groups. Preferred examples of such compounds having 1 acryloyl group and 1 or more hydroxyl groups are mentioned. The compound of component (E) is not limited to the following compound examples.
(in the above formula, R11Represents 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 at least 1 polymerizable group containing a C ═ C double bond and at least 1N-alkoxymethyl group in1 molecule can be cited.
Examples of the polymerizable group having 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, the N-alkoxymethyl group includes 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 heterocycle, and the like.
The component (E) may have the above-mentioned group, and preferable examples thereof include compounds represented by the following formula (X1).
(in the formula, R31Represents a hydrogen atom or a methyl group, R32Represents a hydrogen atom or a linear or branched carbon atom having 1 to 10 carbon atomsAlkyl of (2)
Examples of the alkyl group include a methyl group, 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 1, 2-dimethyl-n-propyl group, a 2, 2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 1, 1-dimethyl-n-butyl group, a 1, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1-dimethyl-n-pentyl, 1, 2-dimethyl-n-pentyl, 1, 3-dimethyl-n-pentyl, 2, 2-dimethyl-n-pentyl, 2, 3-dimethyl-n-pentyl, 1, 2-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-, 3, 3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 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, 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-3-ethyl-n-pentyl, n-nonyl, n-decyl, and the like.
Specific examples of the compound represented by the formula (X1) include acrylamide compounds or methacrylamide compounds 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 in the component (E), a compound represented by the following formula (X2) is preferably exemplified.
In the formula, R51Represents a hydrogen atom or a methyl group.
R52The aliphatic ring may be 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 the structure.
R53The aliphatic ring is 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.
R54Represents a linear or branched aliphatic group having 2 to 9 valences and having 1 to 20 carbon atoms, an aliphatic ring group having 2 to 9 valences and having 5 to 6 carbon atoms, or an aliphatic ring having 2 to 9 valences and having 5 to 6 carbon atoms, wherein one methylene group or a plurality of non-adjacent methylene groups in these groups may be substituted with an ether bond.
Z represents > NCOO-, OR-OCON < (where "-" represents 1 bonding bond. furthermore, ">" < "represents 2 bonding bonds, and represents that an alkoxymethyl group (i.e., -OR52 group) is bonded to any 1 bonding bond).
r is a natural number of 2 to 9.
As R53Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of (1) include a 2-valent group obtained by further removing 1 hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
Furthermore as R54Specific examples of the C1-20 2-to 9-valent aliphatic group in the definition of (1) include those obtained by further removing 1 to 8 carbon atoms from an alkyl group having 1 to 20 carbon atomsA 2-to 9-valent radical of a hydrogen atom.
Examples of the alkyl group having 1 carbon atom are methyl groups, and examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1-dimethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1, 2-trimethyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n, Examples thereof include n-nonadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, a group in which one or more of these groups are bonded in the range up to 20 carbon atoms, and a group in which one methylene group or a plurality of methylene groups which are not adjacent to each other are replaced with an ether bond.
Among them, preferred is an alkylene group having 2 to 10 carbon atoms, R53Is ethylene, R54The hexamethylene group is particularly preferable in view of availability of the raw material.
As R52Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of (1) include R53Specific 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 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 polymer 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 used mainly in the form of a solution 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.
Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-heptanone, γ -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, Ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.
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 preferred as solvents that exhibit resistance to the resin film.
These solvents may be used alone in1 kind or in a combination of 2 or more kinds.
< other additives >
The composition for forming a cured film of the present invention may further 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 polymer 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), an adhesion promoter of the component (E), and further other additives as long as the effects of the present invention are not impaired, if necessary. Further, they are usually used in the form of a solution in which they are 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 (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 component (C) in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of a polymer as the component (A) and a crosslinking agent as the component (B).
[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 (A), a component (B) in an amount of 1 to 500 parts by mass based on 100 parts by mass of the component (A), a component (C) in an amount of 1 to 400 parts by mass based on 100 parts by mass of the total amount of a polymer as the component (A) and a crosslinking agent as the component (B), 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 the polymer as (A) component and the crosslinking agent as (B) component, 0.01 to 20 parts by mass of (D) component based on 100 parts by mass of the total amount of the polymer as (A) component and the crosslinking agent as (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 the polymer as (A) component and the crosslinking agent as (B) component, 0.01 to 20 parts by mass of (D) component based on 100 parts by mass of the total amount of the polymer as (A) component and the crosslinking agent as (B) component, 1 to 100 parts by mass of (E) component based on 100 parts by mass of the total amount of the polymer as (A) component and the crosslinking agent as (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 the solvent from all the components of the composition for forming a cured film.
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 of mixing the component (B) and the components (C), (D), and (E) in a solution of the component (a) dissolved in a solvent at a predetermined ratio to prepare a uniform solution, and a method of further adding other additives as necessary at an appropriate stage of the preparation method and mixing.
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 in the concentration adjustment of the cured film-forming composition.
The solution of the cured film-forming composition thus prepared is preferably filtered using a filter having a pore size of about 0.2 μm and the like.
< cured film, alignment material and retardation material >
A solution of the composition for forming a cured film of the present invention is applied by bar coating, spin coating, flow coating, roll coating, slit-coating-followed spin coating, inkjet coating, printing, or the like onto a substrate (for example, a silicon/silica-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, or the like, a glass substrate, a quartz substrate, an ITO substrate, or the like), a film substrate (for example, 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, or the like) to form a coating film, and then, is heated and dried by an electric heating plate, an oven, or the like, thereby forming a cured film. The cured film can be directly applied as an alignment material.
The conditions for the heat drying may be such that the component of the cured film (alignment material) does not dissolve in the polymerizable liquid crystal solution applied thereon, and the crosslinking reaction is carried out by the crosslinking agent, and for example, a heating temperature and a heating time appropriately selected from the range of 60 ℃ to 200 ℃ and the range of 0.4 to 60 minutes are used. The heating temperature and the heating time are preferably 70 ℃ to 160 ℃ for 0.5 minutes 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 μm to 5 μm, and can be appropriately selected in consideration of the difference in height of the substrate to be used, optical properties, and electrical properties.
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 also 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 with a spacer interposed therebetween, 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 specifically explained below by referring 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
AIBN α' -azobisisobutyronitrile
BMAA: n-butoxymethylacrylamide
MMA: methacrylic acid methyl ester
HEMA: 2-Hydroxyethyl methacrylate
< cinnamic acid Compound having polymerizable group >
CIN 1: 4- (6-methacryloyloxyhexyl-1-oxy) cinnamic acid
CIN 2: 4- (3-methacryloxypropyl-1-oxy) cinnamic acid
CIN 3: 4- (6-Acryloyloxyhexyl-1-oxy) cinnamic acid
< cinnamic acid Compound having no polymerizable group >
CIN 4: 4-methoxy cinnamic acid
< ingredient B >
HMM: a melamine crosslinking agent represented by the following structural formula [ サイメル (CYMEL) (registered trademark) 303 (manufactured by Mitsui サイテック Co., Ltd.) ]
< ingredient D >
PTSA: p-toluenesulfonic acid monohydrate
< ingredient E >
E-1: a compound having an N-alkoxymethyl group and an acryloyl group represented by the following structural formula
< 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 columns (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) shown 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 reacted under heating and reflux for 20 hours to obtain an acrylic polymer solution. The resulting acrylic copolymer solution was slowly added dropwise to 500.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an epoxy group-containing acrylic polymer (P1). The obtained acrylic polymer had Mn of 25,000 and Mw of 10,000.
< Synthesis example 1 >
5.2g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 112.0 g of CIN, and ethyltriphenylphosphonium bromide as a reaction catalyst
0.1g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g, was dissolved in PM70.0g, and reacted at 100 ℃ for 20 hours. This solution was slowly added dropwise to 1000g 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 disappearance of the epoxy group was confirmed.
< Synthesis example 2 >
5.2g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, CINN211.0 g, and ethyltriphenylphosphonium bromide as a reaction catalyst
0.1g of dibutyl group as a polymerization inhibitor0.2g of hydroxytoluene was dissolved in 70.0g of PMs, and the mixture was reacted at 100 ℃ for 20 hours. This solution was slowly added dropwise to 1000g 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 >
5.2g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 312.0 g of CIN, and ethyltriphenylphosphonium bromide as a reaction catalyst
0.1g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g, was dissolved in PM70.0g, and reacted at 100 ℃ for 20 hours. This solution was slowly added dropwise to 1000g 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 >
5.7g of phenol novolak type epoxy resin N-775 (EPICLON series, manufactured by DIC Co., Ltd.), 111.0 g of CIN, and ethyltriphenylphosphonium bromide as a reaction catalyst
0.2g of dibutylhydroxytoluene as a polymerization inhibitor was dissolved in 40.0g of PMs, and reacted at 100 ℃ 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-4). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
< Synthesis example 5 >
5.2g of the epoxy group-containing acrylic polymer (P1) obtained in polymerization example 1, 110.0 g of CIN, 42.0g of CIN, and ethyltriphenylphosphonium bromide as a reaction catalyst
0.1g of dibutylhydroxytoluene as a polymerization inhibitor was dissolved in 70.0g of PM, and reacted at 100 ℃ for 20 hours. The solution was slowly added dropwise to IIA solid was precipitated from 1000g of ethyl ether, and the precipitate was filtered and dried under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
< Synthesis example 6 >
5.2g of the acrylic polymer having an epoxy group (P1) obtained in polymerization example 1, 46.5 g of CIN, and Ethyl triphenyl phosphonium Bromide as a reaction catalyst
0.1g of this was dissolved in 48.0g of PM, and the mixture was reacted at 100 ℃ 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-6). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
< Synthesis example 7 >
5.3g of phenol novolak type epoxy resin N-775 (EPICLON series, manufactured by DIC Co., Ltd.), 45.0 g of CIN, and ethyltriphenylphosphonium bromide as a reaction catalyst
0.2g of this was dissolved in 25.0g of PM, and the mixture was reacted at 100 ℃ 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-7). The epoxy value of the obtained polymer was measured, and disappearance of the epoxy group was confirmed.
< Synthesis of component B >
< polymerization example 2 >
100.0g of BMAA and 4.2g of AIBN as a polymerization catalyst were dissolved in 193.5g of PM, and reacted at 90 ℃ for 20 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had Mn of 2,700 and Mw of 3,900. The acrylic polymer solution was slowly added dropwise to 2000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PB-1).
Synthesis of < C component >
< polymerization example 3 >
MMA 30.0g, HEMA 3.0g, and AIBN 0.3g as a polymerization catalyst were dissolved in PM146.0g, and reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly added dropwise to 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 Mn of 18,000 and Mw of 32,800.
< 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, cured films were formed using the respective compositions for forming a retardation material, and the obtained cured films were evaluated for orientation and adhesion.
[ evaluation of orientation ]
Each of the cured film-forming compositions of examples and comparative examples was coated on an ozone-treated COP film with a wet film thickness of 4 μm using a bar coater. The cured films were formed on the COP films by heating and drying at 110 ℃ for 60 seconds in a thermal cycle oven, respectively. To each cured film, 313nm linearly polarized light was applied at a wavelength of 10mJ/cm2The alignment material is formed by irradiating the substrate perpendicularly with the exposure. A polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by メルク K.K. was coated on the alignment material on the COP film with a Wet film thickness of 6 μm using a bar coater. The coating film was coated at 300mJ/cm2The retardation material on the prepared substrate was sandwiched between a pair of polarizing plates, the state of the retardation property in the retardation material was observed, the case where the retardation was expressed without being defective was ○, and the case where the retardation was not expressed was x, and the evaluation results are listed in the column of "orientation".
[ evaluation of adhesion ]
Each of the cured film-forming compositions of examples and comparative examples was coated on an ozone-treated COP film with a wet film thickness of 4 μm using a bar coater. Respectively at a temperature of 110 DEG CThe cured films were formed on the COP films by heating and drying in a thermal cycle oven for 60 seconds. To each cured film, 313nm linearly polarized light was applied at a wavelength of 10mJ/cm2The alignment material is formed by irradiating the substrate perpendicularly with the exposure. A polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by メルク K was applied to the alignment material on the COP film in a wet film thickness of 6 μm using a bar coater. The coating film was coated at 300mJ/cm2The retardation material was exposed to light to prepare a retardation material, cuts were made into the retardation material at intervals of 1mm in length and width by a cutter knife to form 10 × 10 meshes, a cellophane tape peeling test was performed on the cuts using a transparent tape, the evaluation results were "adhesiveness", the case where 100 meshes were left without peeling off was ○, and the evaluation results were x for 1 piece of peeling off as well, and are shown in table 2 below.
TABLE 2
| Liquid crystal orientation | Adhesion Property | |
| Example 1 | ○ | ○ |
| Example 2 | ○ | ○ |
| Example 3 | ○ | ○ |
| Example 4 | ○ | ○ |
| Example 5 | ○ | ○ |
| Example 6 | ○ | ○ |
| Example 7 | ○ | ○ |
| Example 8 | ○ | ○ |
| Example 9 | ○ | ○ |
| Comparative example 1 | ○ | × |
| Comparative example 2 | ○ | × |
As shown in table 2, the alignment material obtained using the cured film-forming composition of the example exhibited good alignment properties and adhesion.
In contrast, the alignment material obtained using the cured film-forming composition of the comparative example exhibited good alignment properties, but adhesion was not obtained.
Industrial applicability
The composition for forming a cured film according to the present invention is very useful as a material for forming a liquid crystal alignment film of a liquid crystal display device and an alignment material for 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 (14)
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| CN202310790480.5A CN116789871A (en) | 2017-08-03 | 2018-08-03 | Composition for forming cured film, alignment material, and retardation material |
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| JP2017151140 | 2017-08-03 | ||
| JP2017-151140 | 2017-08-03 | ||
| PCT/JP2018/029248 WO2019027045A1 (en) | 2017-08-03 | 2018-08-03 | Cured film forming composition, orienting material, and phase contrast material |
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| CN201880064199.0A Pending CN111164120A (en) | 2017-08-03 | 2018-08-03 | Cured film forming composition, alignment material, and retardation material |
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| JP (1) | JP7365003B2 (en) |
| KR (1) | KR102662084B1 (en) |
| CN (2) | CN116789871A (en) |
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| WO2025173781A1 (en) * | 2024-02-14 | 2025-08-21 | 日産化学株式会社 | Resin composition for thermosetting photo-alignment film |
| WO2025173783A1 (en) * | 2024-02-14 | 2025-08-21 | 日産化学株式会社 | Resin composition for thermosetting optical alignment film |
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| JP5373293B2 (en) | 2008-01-29 | 2013-12-18 | 富士フイルム株式会社 | Compound, liquid crystal composition and anisotropic material |
| JP6146100B2 (en) | 2012-06-21 | 2017-06-14 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, retardation film, liquid crystal display element and method for producing retardation film |
| JP6658213B2 (en) | 2015-06-30 | 2020-03-04 | Jsr株式会社 | Viewing angle compensation film, manufacturing method of viewing angle compensation film, polarizing plate, liquid crystal display device, and organic EL device |
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2018
- 2018-08-03 CN CN202310790480.5A patent/CN116789871A/en active Pending
- 2018-08-03 KR KR1020207004627A patent/KR102662084B1/en active Active
- 2018-08-03 TW TW107127065A patent/TWI794261B/en active
- 2018-08-03 CN CN201880064199.0A patent/CN111164120A/en active Pending
- 2018-08-03 JP JP2019534604A patent/JP7365003B2/en active Active
- 2018-08-03 WO PCT/JP2018/029248 patent/WO2019027045A1/en not_active Ceased
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| WO2009069724A1 (en) * | 2007-11-27 | 2009-06-04 | Jsr Corporation | Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device |
| CN102337140A (en) * | 2010-07-15 | 2012-02-01 | Jsr株式会社 | Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof |
| CN103214620A (en) * | 2012-01-23 | 2013-07-24 | 住友化学株式会社 | Composition for producing optical film and optical film |
| CN105659120A (en) * | 2013-10-17 | 2016-06-08 | 日产化学工业株式会社 | Composition for forming cured film, alignment material, and retardation material |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019027045A1 (en) | 2020-09-24 |
| JP7365003B2 (en) | 2023-10-19 |
| CN116789871A (en) | 2023-09-22 |
| WO2019027045A1 (en) | 2019-02-07 |
| TW201920320A (en) | 2019-06-01 |
| TWI794261B (en) | 2023-03-01 |
| KR20200037278A (en) | 2020-04-08 |
| KR102662084B1 (en) | 2024-05-02 |
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