CN116789871A - Composition for forming cured film, alignment material, and retardation material - Google Patents

Composition for forming cured film, alignment material, and retardation material Download PDF

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Publication number
CN116789871A
CN116789871A CN202310790480.5A CN202310790480A CN116789871A CN 116789871 A CN116789871 A CN 116789871A CN 202310790480 A CN202310790480 A CN 202310790480A CN 116789871 A CN116789871 A CN 116789871A
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cured film
composition
forming
component
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伊藤润
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—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

Abstract

The present application addresses the problem of providing a composition for forming a cured film for an alignment material which exhibits good liquid crystal alignment properties and has excellent adhesion to a liquid crystal layer. The solution is that a composition for forming a cured film, a cured film obtained from the composition for forming a cured film, an orientation material, and a phase difference material are provided, wherein the composition for forming a cured film comprises: (A) A reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond; and (B) a crosslinking agent.

Description

Composition for forming cured film, alignment material, and retardation material
The present application is a divisional application with application number 201880064199.0, title of the application being cured film forming composition, orientation material, and retardation material, and application date being 2018, 8, and 3.
Technical Field
The present application relates to a composition for forming a cured film, an alignment material, and a retardation material for aligning liquid crystal molecules. In particular, the present application relates to a composition for forming a cured film, an alignment material, and a retardation material useful for a patterned retardation material used for a 3D display of a circularly polarized light glasses system, and a retardation material used for a circularly polarized light plate used as an antireflection film for an organic EL display.
Background
In the case of a 3D display of a circularly polarized glasses type, a phase difference material is generally disposed on a display element such as a liquid crystal panel for forming an image. The phase difference material is structured by regularly disposing a plurality of 2 kinds of phase difference regions having different phase difference characteristics. In the following description, a phase difference material patterned so as to arrange a plurality of phase difference regions having different phase difference characteristics is referred to as a patterned phase difference material.
The patterned retardation material can be produced by optically patterning a retardation material made of a polymerizable liquid crystal, as disclosed in patent document 1, for example. The optical patterning of the phase difference material formed of the polymerizable liquid crystal uses a photo-alignment technique known in the formation of alignment materials for liquid crystal panels. That is, a coating film made of a material having a light-directing property is provided on a substrate, and 2 kinds of polarized light having different polarization directions are irradiated thereto. Further, as an alignment material in which 2 kinds of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed, a photo-alignment film was obtained. A phase difference material in the form of a solution containing a polymerizable liquid crystal is applied to the photo-alignment film to orient the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.
The antireflection film of the organic EL display is constituted by a linear polarizing plate and a 1/4 wavelength retardation plate, and external light directed to the panel surface of the image display panel is converted into linear polarized light by the linear polarizing plate, and then into circular polarized light by the 1/4 wavelength retardation plate. Here, the external light based on the circularly polarized light is reflected on the surface of the image display panel or the like, but the rotation direction of the polarized light 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 polarized light plate by the 1/4 wavelength phase difference plate, and then shielded by the linearly polarized light plate, and as a result, emission to the outside is significantly suppressed.
Regarding this 1/4 wavelength retardation plate, patent document 2 proposes: a method of forming the optical film by combining a 1/2 wavelength plate and a 1/4 wavelength plate to form a 1/4 wavelength phase difference plate and thereby forming the optical film by the inverse dispersion characteristic. In the case of this method, in a wide wavelength band for display of a color image, an optical film can be configured by a reverse dispersion characteristic using a liquid crystal material based on a forward dispersion characteristic.
In recent years, as a liquid crystal material applicable to the retardation layer, a liquid crystal material having an inverse dispersion characteristic has been proposed (patent documents 3 and 4). According to the liquid crystal material having such an inverse dispersion characteristic, the 1/4 wavelength retardation plate can be constituted by a single layer of the retardation layer instead of the combination of the 1/2 wavelength plate and the 1/4 wavelength plate, and the inverse dispersion characteristic can be ensured by the 2 layer retardation layer, whereby an optical film capable of ensuring a desired phase difference in a wide wavelength band can be realized by a simple constitution.
In order to orient the liquid crystal, an orientation 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, are not generated and control of the alignment treatment can be performed quantitatively.
As a material having a photo-alignment property which can be used for forming 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 are reported to exhibit properties of controlling the orientation of liquid crystals by UV irradiation with polarized light (hereinafter also referred to as liquid crystal orientation property ") (see patent documents 5 to 7).
In addition, the alignment layer is required to have adhesion to the liquid crystal layer in addition to liquid crystal alignment ability. For example, when the adhesion 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.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2005-49865
Patent document 2: japanese patent laid-open No. 10-68816
Patent document 3: U.S. Pat. No. 8119026 Specification
Patent document 4: japanese patent laid-open No. 2009-179563
Patent document 5: japanese patent No. 3611342
Patent document 6: japanese patent laid-open No. 2009-058584
Patent document 7: japanese patent application laid-open No. 2001-517719
Disclosure of Invention
Problems to be solved by the invention
The invention is based on the above knowledge and research results. 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 conducted intensive studies to achieve the above object, and as a result, have found that a cured film having excellent adhesion to a liquid crystal layer and good liquid crystal orientation 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 containing a polymerizable double bond and (B) a crosslinking agent, and have completed the present invention.
That is, in the present invention, as the 1 st aspect, there is provided a composition for forming a cured film, comprising: (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 according to the aspect 2 is the composition for forming a cured film according to the aspect 1, wherein the group containing a polymerizable double bond is a (meth) acryloyl group.
The composition for forming a cured film according to any one of the aspects 1 and 2, wherein the cinnamic acid derivative having a group containing a polymerizable double bond is a compound represented by the following formula (1).
In formula (1), A 1 And A is a 2 Each independently represents a hydrogen atom or a methyl group,
R 1 a group represented by the following formula (c-2),
(in the formula (c-2), the dotted line represents a bond, R 101 An alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms of the alkylene group may be replaced with a fluorine atom or an organic group. In addition, R 101 In (C) is-CH 2 CH 2 Can be replaced by-CH=CH-, and R is further defined as being not adjacent to any of the groups listed below 101 In (C) is-CH 2 CH 2 -OCO- -NH- -OCO-, -NH-, groups in NHCONH-and-CO-, M is M 1 Represents a hydrogen atom or a methyl group. )
R 2 Represents a 2-valent aromatic group, a 2-valent alicyclic group, and a 2A valence heterocyclic group or a 2-valence condensed ring group,
R 3 represents a single bond, an oxygen atom, -COO-, -OCO-, -CH=CHCOO-, or-OCOCH=CH-,
R 4 ～R 7 each independently represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group,
In addition, R 2 、R 3 And R is 4 Can together form an aromatic group, or R 2 、R 3 And R is 6 May be taken together to form an aromatic group,
n is an integer of 0 to 3. )
The composition for forming a cured film according to any one of the aspects 1 to 3, wherein the crosslinking agent of the component (B) is a crosslinking agent having a hydroxymethyl group or an alkoxymethyl group.
As the 5 th aspect, the composition for forming a cured film according to any one of the 1 st to 4 th aspects, further comprising: (C) A polymer having at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.
The composition for forming a cured film according to any one of the aspects 1 to 5, as the 6 th aspect, further comprising: (D) a crosslinking catalyst.
As a 7 th aspect, the composition for forming a cured film according to any one of the 1 st to 6 th aspects comprises a compound (E) having:
more than 1 polymerizable group,
at least 1 group a selected from hydroxyl, carboxyl, amide, amino, and alkoxysilyl groups or at least 1 group reactive with the group a.
The composition for forming a cured film according to any one of the aspects 1 to 7 contains 1 to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A).
The composition for forming a cured film according to any one of the aspects 5 to 8 contains 1 to 400 parts by mass of the component (C) based on 100 parts by mass of the total amount of the crosslinking agents of the component (A) and the component (B).
The composition for forming a cured film according to any one of the aspects 6 to 9 contains 0.01 to 20 parts by mass of the component (D) based on 100 parts by mass of the total amount of the crosslinking agents of the component (A) and the component (B).
The 11 th aspect relates to the cured film forming composition according to any one of the 7 th to 10 th aspects, wherein the composition contains 1 to 100 parts by mass of the component (E) based on 100 parts by mass of the total amount of the crosslinking agents of the component (a) and the component (B).
As a 12 th aspect, 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.
As a 13 th aspect, there is provided an alignment material obtained from the cured film-forming composition according to any one of the 1 st to 11 th aspects.
As a 14 th aspect, the present invention relates to a retardation material produced by using a cured film obtained from the composition for forming a cured film 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 the formation thereof 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 high-precision optical patterning 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 cured film-forming composition of the present invention may further contain, as the component (C), a polymer having at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, in addition to the component (A) and the component (B). The composition may further contain a crosslinking catalyst as the component (D). The compound may further contain, as the component (E), a compound having 1 or more polymerizable groups, at least 1 group A selected from the group consisting of 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 the components are described below.
Component (A)
The component (A) contained in the composition for forming a cured film 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.
< Polymer having epoxy group >
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 -ethyl glycidyl acrylate, α -n-propyl glycidyl acrylate, α -n-butyl glycidyl acrylate, 3, 4-epoxybutyl methacrylate, 6, 7-epoxyheptyl acrylate, 6, 7-epoxyheptyl methacrylate, 6, 7-epoxyheptyl α -ethyl acrylate, 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.
Specific examples of the alkyl methacrylates include 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, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like; examples of the alkyl acrylate include methyl acrylate and isopropyl acrylate; examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo [5.2.1.0 ] 2,6 ]Decane-8-yl methacrylate, tricyclo [5.2.1.0 2,6 ]Decane-8-yloxy ethyl methacrylate, isobornyl methacrylate, cholesteryl methacrylate, and the like; 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 [5.2.1.0 2,6 ]Decane-8-yloxy ethyl acrylate, isobornyl acrylate, cholesteryl acrylate, and the like; examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate; examples of the aryl acrylate include phenyl acrylate and benzyl acrylate; 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-ene5-ethoxybicyclo [2.2.1]Hept-2-ene, 5, 6-dimethoxy bicyclo [2.2.1]Hept-2-ene, 5, 6-diethoxybicyclo [2.2.1]Hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1]Hept-2-ene, 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-maleimidocaprooate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like; examples of the unsaturated aromatic compound include styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; examples of the conjugated diene compound include 1, 3-butadiene, isoprene, and 2, 3-dimethyl-1, 3-butadiene; examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid; examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; examples of the unsaturated dicarboxylic acid anhydride include anhydrides of the above unsaturated dicarboxylic acids; examples of the polymerizable unsaturated compound other than the above include acrylonitrile, methacrylonitrile, vinyl chloride, 1-dichloroethylene, acrylamide, methacrylamide, and vinyl acetate.
The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, more preferably 50% by mass or more.
The synthesis of the polymer having an epoxy group can be preferably performed by a known radical polymerization method in a solvent in the presence of an appropriate polymerization initiator.
As the polymer having an epoxy group, commercially available ones can be used. As such a commercially available product, there is a commercially available product, examples thereof include EHPE3150, EHPE3150CE (manufactured by Wakugaku Koku Co., ltd.), UG-4010, UG-4035, UG-4040, UG-4070 (manufactured by Toyama Co., ltd.), ECN-1299 (manufactured by Asahi Kagaku Co., ltd.), DEN431, DEN438 (manufactured by Waku Koku Co., ltd.), and the like jER-152 (Mitsubishi, inc.), d-660, N-665, N-670, N-673, N-695, N-740, d-65, d-67, d-3, d-3, and the like; N-770, N-775 (DIC, manufactured by Shimadzu chemical Co., ltd.), EOCN-1020, EOCN-102S, EOCN-104S (manufactured by Japanese chemical Co., ltd.), and the like.
Cinnamic acid derivative having a group containing a polymerizable double bond
The polymerizable double bond is preferably a carbon-carbon double bond. Examples of the group containing the double bond between carbon and carbon include vinyl, (meth) acryl, and acrylamide, but (meth) acryl 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 formula (1), A 1 And A is a 2 Each independently represents a hydrogen atom or a methyl group,
R 1 a group represented by the following formula (c-2),
(in the formula (c-2), the dotted line represents a bond, R 101 An alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms of the alkylene group may be replaced with a fluorine atom or an organic group. In addition, R 101 In (C) is-CH 2 CH 2 Can be replaced by-CH=CH-and, in the case where any of the groups mentioned below are not adjacent to one another, can be replaced by a compound selected from the group consisting of-O-, -NHCO--CONH-, -COO-, -OCO-, -NH-; groups in NHCONH-and-CO-, M is M 1 Represents a hydrogen atom or a methyl group. )
R 2 Represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group,
R 3 represents a single bond, an oxygen atom, -COO-, -OCO-, -CH=CHCOO-, or-OCOCH=CH-,
R 4 ～R 7 each independently represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group,
in addition, R 2 、R 3 And R is 4 Can together form an aromatic group, or R 2 、R 3 And R is 6 May be taken together to form an aromatic group,
n is an integer of 0 to 3. )
As R 2 Examples of the 2-valent aromatic group include 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, 2,3,5, 6-tetrafluoro-1, 4-phenylene and the like; as R 2 Examples of the 2-valent alicyclic group include 1, 2-cyclopropylene, 1, 3-cyclobutylene, and 1, 4-cyclohexylene; as R 2 Examples of the 2-valent heterocyclic group include a 1, 4-pyridylene group, a 2, 5-pyridylene group, and a 1, 4-furanylene group; as R 2 Examples of the condensed ring type group having a valence of 2 include 2, 6-naphthylene group and the like. As R 2 Preferably 1, 4-phenylene.
Preferable examples of the compound represented by the above formula (1) include, for example, the following formulas M1-1 to M1-5.
(wherein M 1 S1 represents a methylene group and is a natural number of 2 to 9. )
The compound represented by the above formula (1) can be synthesized by appropriately combining general methods of organic chemistry.
Reaction of epoxy group-containing Polymer 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, preferably in the presence of a catalyst, and preferably in an appropriate organic solvent.
The proportion of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1.3 mol, and 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, diazabicycloundecene; quaternary organic amines such as tetramethyl ammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine are preferable; quaternary organic amines such as tetramethyl ammonium hydroxide.
Examples of the curing accelerator include tertiary amines such as benzyl dimethylamine, 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-undecylimidazoleTrimellitate, 1- (2-cyanoethyl) -2-phenylimidazole +.>Trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole +.>Imidazole compounds such as trimellitates, 2, 4-diamino-6- [ 2 '-methylimidazolyl- (1')) ethyl s-triazine, 2, 4-diamino-6- (2 '-n-undecylimidazolyl) ethyl s-triazine, 2, 4-diamino-6- [ 2' -ethyl-4 '-methylimidazolyl- (1')) ethyl s-triazine, isocyanuric acid adducts of 2-methylimidazole, isocyanuric acid adducts of 2-phenylimidazole, and isocyanuric acid adducts of 2, 4-diamino-6- [ 2 '-methylimidazolyl- (1')ethyls-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; such as benzyl triphenylchloride->Tetra-n-butyl bromide->Methyltriphenylbromide->Ethyltriphenyl bromide->N-butyltriphenyl bromide->Tetraphenylbromide->Ethyltriphenyl iodination->Ethyltriphenylacetic acid->Tetra-n-butyl->o, o-diethyl dithiophosphate, tetra-n-butyl +. >Benzotriazole salts, tetra-n-butylTetrafluoroborate, tetra-n-butyl +.>Tetraphenylborate, tetraphenyl->Quaternary ∈4 as tetraphenylborates>A salt; such as 1, 8-diazabicyclo [5.4.0]Diazabicycloolefins such as undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octoate, tin octoate, aluminum acetylacetonate complex compounds; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, 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 dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide and adducts of amine and epoxy resin; mixing the above imidazole compound, organic phosphorus compound, and quaternary onium compound>A microcapsule-type latent curing accelerator in which the surface of the curing accelerator such as a salt is coated with a polymer; amine salt type latent curing agent accelerators; and latent curing accelerators such as Lewis acid salts and thermal cationic polymerization type latent curing accelerators which are dissociated at high temperature such as Bronsted acid salts.
Among them, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride are preferable.
The catalyst is used in an amount 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 viewpoints of the solubility of raw materials and products and the ease of purification of the products. The solvent is used in an amount of preferably 0.1% by mass or more, more preferably 5 to 50% by mass, based on the total mass of the solution, of the solid content concentration (the ratio of the mass of the components other than the solvent in the reaction solution).
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.
This operation gives a solution containing the reaction product of the polymer having an epoxy group and the specific cinnamic acid derivative. The solution may be directly supplied to the preparation of the liquid crystal aligning agent, may be supplied to the preparation of the liquid crystal aligning agent after separating the polymer contained in the solution, or may be supplied to the preparation of the liquid crystal aligning agent after purifying the separated polymer.
Component (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 hydroxymethyl group or an alkoxymethyl group.
Examples of the compound having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine and alkoxymethylated melamine.
Specific examples of alkoxymethylated glycolurils include, for example, 1,3,4, 6-tetra (methoxymethyl) glycoluril, 1,3,4, 6-tetra (butoxymethyl) glycoluril, 1,3,4, 6-tetra (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetra (butoxymethyl) urea, 1, 3-tetra (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Examples of the commercial products include compounds such as a sweet-urea compound (trade name: brand 1170, a sweet-urea resin (trade name: UFR (registered trademark) 65), a butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11 HV), a DIC urea/formaldehyde resin (high condensation type, trade name: brand J-300S, and brand horsetail) produced by san-device, and so on.
Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine and the like. Examples of the commercial products include the doctor rail of japan (old three-well joint brand) brand, manufactured (trade name: doctor rail 1123), (plant) three and the doctor rail of the world (trade name: the registered trademark) brand, brand name BX-4000, brand name of the red tongue, brand red tongue BX-37, brand red tongue BL-60, and red tongue BX-55H).
Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethyl melamine. As a commercial product, there is exemplified a methoxymethyl melamine compound (trade name: reference numerals "b" 300, b "301, b" 303, b "350", and "n" methyl melamine compounds (trade name: the "matri コ" 506, the "matri コ" 508, the "tri-and-chemical compound" are methoxymethyl melamine compounds (trade name: the parts include, for example, modern parts such as, but not limited to, modern parts such as, modern parts of the modern, sear, etc., sear, etc., which are known by sear, etc., which are the sear, which is known the sear, which is a technology which is made of the technology which the technology the technology the.
Further, the compound may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound, in which a hydrogen atom of such an 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. The melamine compound is commercially available under the trade name: the "ct" (registered trademark) 303 and the like, and trade names are given as commercial products of the benzoguanamine compound: and ct 1123 (manufactured by the above, japan, ct) and the like.
Further, as the crosslinking agent of the component (B), it is also possible to use: polymers produced by using an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group (i.e., hydroxymethyl group) or an alkoxymethyl group, such as N-methylolacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylacrylamide, are used.
Examples of such polymers include poly (N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethacrylamide 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 also be used.
Examples of the polymerizable group containing a c=c double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.
The method for obtaining the polymer is not particularly limited. In an example, an acrylic polymer having a specific functional group 1 is produced by a polymerization method such as radical polymerization. Then, the specific functional group 1 is reacted with a compound having an unsaturated bond at the terminal (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).
The specific functional group 1 is a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amino group having active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a plurality of functional groups selected from these groups.
In the above reaction, preferable combinations of the specific functional group 1 and the functional group possessed by the specific compound and involved in the reaction are a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxyl group and an acyl chloride, and the like. Further, a more preferred combination is carboxyl with glycidyl methacrylate, or hydroxyl with isocyanate ethyl methacrylate.
The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 ～ 500,000, preferably 2,000 ～ 200,000, more preferably 3,000 ～ 150,000, and even 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 the 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 the component (a). When the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition decreases, and the liquid crystal alignment property decreases. On the other hand, when the content is too large, the liquid crystal alignment property and the storage stability may be lowered.
Component (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 the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.
Examples of the polymer as the component (C) include acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkyleneimines, polyallylamines, celluloses (celluloses or derivatives thereof), phenol novolac resins, melamine formaldehyde resins and other polymers having a linear or branched structure, cyclodextrin and other cyclic polymers.
The polymer of component (C) is preferably an acrylic polymer, a hydroxyalkyl cyclodextrin, a cellulose, a polyether polyol, a polyester polyol, a polycarbonate polyol, or a polycaprolactone polyol.
The acrylic polymer as 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, vinyl compound, and the like, and a polymer obtained by polymerizing a monomer including a monomer having a specific functional group 2 or a mixture thereof, and the kind of a backbone and a side chain of a main chain of a polymer constituting the acrylic polymer is not particularly limited.
Examples of the monomer having a specific functional group 2 include a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxyl group, a monomer having a carboxyl group, a monomer having an amino group, a monomer having an alkoxysilyl group and a group represented by the above formula 2.
As the toolExamples of the monomer having a polyethylene glycol ester group include H- (OCH) 2 CH 2 ) n-OH monoacrylate or monomethacrylate. 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 the side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
Examples of the monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
In the present embodiment, in the synthesis of the acrylic polymer as an example of the component (C), 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, naphthalene acrylate, anthracene methyl acrylate, phenyl acrylate, 2-trifluoroethyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.
Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, 2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
Examples of the styrene compound include styrene, methyl styrene, chlorostyrene, and bromostyrene.
Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
The amount of the monomer having a specific functional group 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 excessively small compared to 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 it is obtained by, for example, polymerizing a monomer containing a monomer having a specific functional group 2, a monomer not having a specific functional group 2 if necessary, and a polymerization initiator or the like in a solvent in which the monomer and the polymerization initiator coexist 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 not having the specific functional group 2, and the polymerization initiator, etc., which are used as needed. Specific examples thereof are described in the following [ solvent ].
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.
The acrylic polymer powder as an example of the component (C) can be produced by adding the acrylic polymer solution as an example of the component (C) obtained by the above method to diethyl ether, water or the like under stirring to reprecipitate, filtering and washing the resulting precipitate, and then drying at normal temperature or heating under normal pressure or reduced pressure. By the above-described operation, the polymerization initiator and unreacted monomer which coexist with the acrylic polymer as an example of the component (C) can be removed, and as a result, a purified powder of the acrylic polymer as an example of the component (C) can be obtained. In the case where the purification cannot be performed sufficiently by one operation, the obtained powder is dissolved in a solvent again, and the above-described operation may be repeated.
The weight average molecular weight of the acrylic polymer as a preferable example of the component (C) is preferably 3000 to 200000, more preferably 4000 to 150000, and still more preferably 5000 to 100000. If the weight average molecular weight exceeds 200000, the solubility in a solvent may be lowered, and if the weight average molecular weight is less than 3000, the solvent resistance may be lowered due to insufficient curing at the time of heat curing. The weight average molecular weight is a value obtained by Gel Permeation Chromatography (GPC) using polystyrene as a standard sample. Hereinafter, the same applies to the present specification.
Next, as a preferred example of the polyether polyol of the component (C), there may be mentioned a polyether polyol obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol and the like to a polyol such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol a, triethylene glycol, sorbitol and the like. As a specific example of the polyether polyol, examples of the materials include ADEKA's slow P series, G series, EDP series, BPX series, FC series, CM series, and solar oil system slow (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, super-hard (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, super (registered trademark) LT-221, ST-221, OT-221, and the like.
As a preferred example of the polyester polyol as the component (C), a polyester polyol obtained by reacting a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. with a polycarboxylic acid such as adipic acid, sebacic acid, isophthalic acid, etc. can be mentioned. Specific examples of the polyester polyol include DIC-made polyethylene (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, and a gamma-made polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016.
As a preferred example of the polycaprolactone polyol of the component (C), there may 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 (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, smart clay 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.
The polycarbonate polyol as a preferred example of the component (C) may be a polycarbonate polyol 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 a dame (registered trademark) CD205, CD205PL, CD210, CD220, and C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by rawale.
Preferable examples of the cellulose in the component (C) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and celluloses, and preferable examples thereof include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.
Preferred examples of the cyclodextrin of component (C) include cyclodextrin such as α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin, methylated cyclodextrin such as methyl- α -cyclodextrin, methyl- β -cyclodextrin and methyl- γ -cyclodextrin, hydroxyalkyl cyclodextrin such as hydroxymethyl- α -cyclodextrin, hydroxymethyl- β -cyclodextrin, hydroxymethyl- γ -cyclodextrin, 2-hydroxyethyl- α -cyclodextrin, 2-hydroxyethyl- β -cyclodextrin, 2-hydroxyethyl- γ -cyclodextrin, 2-hydroxypropyl- α -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, 2-hydroxypropyl- γ -cyclodextrin, 3-hydroxypropyl- α -cyclodextrin, 3-hydroxypropyl- β -cyclodextrin, 3-hydroxypropyl- γ -cyclodextrin, 2, 3-dihydroxypropyl- α -cyclodextrin, 2, 3-dihydroxypropyl- β -cyclodextrin, 2, 3-dihydroxypropyl- γ -cyclodextrin and the like hydroxyalkyl cyclodextrin.
The melamine formaldehyde resin as a preferred example of the component (C) is a resin obtained by polycondensing melamine with formaldehyde.
From the viewpoint of storage stability, the melamine formaldehyde resin of the component (C) is preferably alkylated with methylol groups generated during polycondensation of melamine and formaldehyde. The melamine formaldehyde resin as the component (C) may be, for example, a resin having a unit structure represented by the following formula.
In the above formula, R 21 The number of the repeating units is a natural number, and n represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The method for obtaining the melamine-formaldehyde resin of the component (C) is not particularly limited, but generally, the melamine-formaldehyde resin is synthesized by mixing melamine with formaldehyde, forming a weak alkali with sodium carbonate, ammonia or the like, and then heating at 60 to 100 ℃. The hydroxymethyl group may be alkoxylated by further reacting it with an alcohol.
(C) The melamine formaldehyde resin as the 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 exceeds 5000 and is excessively large, solubility in a solvent may be lowered, and workability may be lowered, and if the weight average molecular weight is less than 250 and is excessively small, curing may become insufficient at the time of heat curing, and the effect of improving solvent resistance may not be sufficiently exhibited.
In the embodiment of the present invention, the melamine formaldehyde resin as the component (C) may be used in a liquid form or in a solution form in which the purified liquid is redissolved in a solvent described later.
The phenol novolac resin as a preferable example of the component (C) includes, for example, phenol-formaldehyde polycondensate and the like.
In the cured film-forming composition of the present embodiment, the polymer of component (C) may be used in the form of a powder or in the form of a solution obtained by redissolving the purified powder in a solvent described later.
In the cured film-forming composition of the present embodiment, the component (C) may be a mixture of a plurality of polymers exemplified as the component (C).
The content of the component (C) in the cured film-forming composition of the present invention is preferably 400 parts by mass or less, more preferably 10 parts by mass to 380 parts by mass, and even more preferably 40 parts by mass 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 tends to be lowered.
Component (D)
The cured film-forming composition of the present invention may further contain a crosslinking catalyst as the component (D) in addition to the components (a) and (B).
As the crosslinking catalyst of the component (D), for example, an acid or a thermal acid generator can be suitably used. The component (D) is effective in promoting the heat curing reaction of the cured film-forming composition of the present invention.
The component (D) is specifically a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof. The thermal acid generator is not particularly limited as long as it is a compound that generates an acid by thermal decomposition at the time of heat treatment, that is, a compound that generates an acid by thermal decomposition at a temperature of 80 to 250 ℃.
Specific examples of the acid include hydrochloric acid and salts 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, mesitylene sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethanesulfonic acid), pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and hydrates and salts thereof.
Examples of the compound that 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-toluenesulfonateSalt, p-toluenesulfonic acid morpholine->Salt, ethyl p-toluenesulfonatePropyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and compounds represented by the following formula. / >
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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 even 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). When the content of the component (D) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, in the case of more than 20 parts by mass, the storage stability of the composition may be lowered.
Component (E)
The present invention may contain a compound having 1 or more polymerizable groups and at least 1 group a selected from the group consisting of 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 as the component (E). It functions as a component for improving the adhesiveness of the formed cured film (hereinafter, also referred to as an 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 adhesion between the alignment material and the layer of the polymerizable liquid crystal. As a result, the retardation material of the present embodiment, which is 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 the group consisting of 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.
Examples of the component (E) include hydroxy group-containing multifunctional acrylates (hereinafter, also referred to as hydroxy group-containing multifunctional acrylates).
Examples of the hydroxyl group-containing polyfunctional acrylate as the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
As an example of the component (E), a compound having 1 acryl group and 1 or more hydroxyl groups may be mentioned. Preferable examples of the compound having 1 acryl group and 1 or more hydroxyl groups are given. The compound of component (E) is not limited to the following examples.
(in the above formula, R 11 Represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10. )
Further, as the compound of the component (E), there may be mentioned a compound having at least 1 polymerizable group containing a c=c double bond in 1 molecule and at least 1N-alkoxymethyl group.
Examples of the polymerizable group containing a c=c double bond include an acryl group, a methacryl 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 a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of a carbamate, a nitrogen atom bonded to a position adjacent to a nitrogen atom of a nitrogen-containing heterocycle, and the like. Thus, the N-alkoxymethyl group may be a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from the group consisting of a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of a urethane, a nitrogen atom bonded to a position adjacent to a nitrogen atom of a nitrogen-containing heterocycle, and the like.
The component (E) may have any of the above groups, and examples thereof include compounds represented by the following formula (X1).
(wherein R is 31 Represents a hydrogen atom or a methyl group, R 32 Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)
Examples of the alkyl group include, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 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-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-dimethyl-n-pentyl, 2, 3-dimethyl-n-pentyl, 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-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-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-n-pentyl, n-decyl, n-decyl, etc.
Specific examples of the compound represented by the above formula (X1) include an acrylamide compound or a methacrylamide compound in which N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide or the like is substituted with hydroxymethyl or alkoxymethyl. The term "meth" acrylamide means both of methacrylamide and acrylamide.
As another embodiment of the compound having a polymerizable group having a c=c double bond and an N-alkoxymethyl group as the component (E), a compound represented by the following formula (X2) is preferable.
Wherein R is 51 Represents a hydrogen atom or a methyl group.
R 52 An alkyl group having 2 to 20 carbon atoms, a 1-valent aliphatic cyclic group having 5 to 6 carbon atoms, or a 1-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms may contain an ether bond in the structure.
R 53 Represents a linear or branched alkylene group having 2 to 20 carbon atoms, a 2-valent aliphatic ring group having 5 to 6 carbon atoms, or a 2-valent lipid containing an aliphatic ring having 5 to 6 carbon atomsThe aliphatic group may contain an ether bond in the structure.
R 54 The aliphatic group having 1 to 20 carbon atoms, the aliphatic ring having 5 to 6 carbon atoms, or the aliphatic group having 5 to 6 carbon atoms and 2 to 9 carbon atoms, which are linear or branched, may be substituted with an ether bond by one methylene group or a plurality of non-adjacent methylene groups.
Z represents > NCOO-, OR-OCON < (where "-" represents 1 bond; furthermore, ">" < "represents 2 bonds and represents an alkoxymethyl group (i.e., -OR52 group) bonded to any 1 bond).
r is a natural number of 2 to 9 inclusive.
As R 53 Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of (a) include a 2-valent group in which 1 hydrogen atom is further removed from an alkyl group having 2 to 20 carbon atoms.
In addition as R 54 Specific examples of the aliphatic group having 2 to 9 carbon atoms in the definition of (a) include a group having 2 to 9 carbon atoms in which 1 to 8 hydrogen atoms are further removed from the alkyl group having 1 to 20 carbon atoms.
Specific examples of the alkyl group having 1 carbon atom is a methyl group, and further 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-octadecyl group, n-nonadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, and one or more of them bonded within a range of 20 carbon atoms, and a group having one or not adjacent methylene group of these groups are replaced with an ether bond.
Among them, the group of the organic compounds is,preferably an alkylene group having 2 to 10 carbon atoms, R 53 Is ethylene, R 54 The use of the hexamethylene group is particularly preferable from the viewpoint of availability of the raw material and the like.
As R 52 Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of (a) include R 53 Specific examples of the alkyl group having 2 to 20 carbon atoms and the methyl group in the definition of (a). Among them, an alkyl group having 1 to 6 carbon atoms is preferable, and methyl, ethyl, n-propyl or n-butyl is particularly preferable.
The natural number r is preferably 2 to 6, and is preferably 2 to 9.
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, 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). By setting the content of the component (E) to 1 part by mass or more, sufficient adhesion can be imparted to the formed cured film. However, in the case of more than 100 parts by mass, the liquid crystal alignment tends to be lowered.
In the cured film-forming composition of the present embodiment, the component (E) may be a mixture of a plurality of compounds of the component (E).
< solvent >
The composition for forming a cured film of the present invention is mainly used in a solution state dissolved in a solvent. The solvent to be used in this case is not particularly limited 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, for example, 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, methyl ethyl ketone, ethyl alcohol, methyl alcohol propyl ether, propyl alcohol propyl ether propyl alcohol propyl methyl propyl cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutanoate, 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, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.
In the case of producing an alignment material by forming a cured film on a resin film using the composition for forming a cured film of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate and the like are preferable from the viewpoint of the solvent exhibiting resistance to the resin film.
These solvents may be used singly or in combination of 2 or more.
< other additives >)
Further, the composition for forming a cured film of the present invention may contain an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, a defoaming agent, an antioxidant, and the like as required as long as the effect of the present invention is not impaired.
Preparation of composition for Forming cured film
The cured film-forming composition of the present invention is a composition containing a polymer of component (A) and a crosslinking agent of component (B), optionally containing a polymer of component (C), a crosslinking catalyst of component (D) and an adhesion promoter of component (E), and further containing other additives as long as the effects of the present invention are not impaired. Further, they are generally 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 contains a component (A) and 1 to 500 parts by mass of a component (B) based on 100 parts by mass of the component (A).
[2]: the composition for forming a cured film contains (A) 1 to 500 parts by mass of (B) based on 100 parts by mass of (A) and (C) 1 to 400 parts by mass of (C) based on 100 parts by mass of the total amount of the polymer as (A) and the crosslinking agent as (B).
[3]: a composition for forming a cured film, which contains a component (A), 1 to 500 parts by mass of a component (B) based on 100 parts by mass of the component (A), and a solvent.
[4]: a composition for forming a cured film, which comprises (A) 1 to 500 parts by mass of (B) based on 100 parts by mass of (A), 1 to 400 parts by mass of (C) based on 100 parts by mass of the total amount of a polymer as (A) and a crosslinking agent as (B), and a solvent.
[5]: the composition for forming a cured film contains 1 to 500 parts by mass of component (B) based on 100 parts by mass of component (A), 1 to 400 parts by mass of component (C) based on 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent for component (B), and 0.01 to 20 parts by mass of component (D) based on 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent for component (B).
[6]: the composition for forming a cured film contains 1 to 500 parts by mass of component (B) based on 100 parts by mass of component (A), 1 to 400 parts by mass of component (C) based on 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent of component (B), 0.01 to 20 parts by mass of component (D) based on 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent of component (B), and 1 to 100 parts by mass of component (E) based on 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent of component (B), and a solvent.
The blending ratio, the preparation method, and the like in the case of using the composition for forming a cured film of the present invention in a solution are 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% by mass, preferably 2 to 50% by mass, and more preferably 2 to 20% by mass. The solid component herein refers to a component obtained by removing the solvent from all the components of the cured film-forming composition.
The method for preparing the composition for forming a cured film of the present invention is not particularly limited. Examples of the preparation method include a method of preparing a uniform solution by mixing the component (B), the component (C), the component (D), the component (E) and the like in a predetermined ratio in a solution of the component (a) dissolved in a solvent, and a method of further adding other additives as needed at an appropriate stage of the preparation method and mixing them.
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 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, the solvent may be further added for the purpose of concentration adjustment. In this case, the solvent used in the production process of the component (a) and the solvent used in the concentration adjustment of the cured film-forming composition may be the same or different.
The solution of the cured film-forming composition thus prepared is preferably filtered using a filter or the like having a pore diameter of about 0.2 μm.
Curing film, alignment material and retardation material >
The solution of the composition for forming a cured film of the present invention is applied 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 triacetyl cellulose (TAC) film, a Polycarbonate (PC) film, a Cyclic Olefin Polymer (COP) film, a Cyclic Olefin Copolymer (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, a polyethylene film, or the like) by bar coating, spin coating, roll coating, slot coating, spin coating, inkjet coating, printing, or the like, and then heat-dried with a hot 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 heat drying may be such that the components of the cured film (alignment material) are not dissolved in the polymerizable liquid crystal solution applied thereto, and the crosslinking reaction is carried out by a crosslinking agent, and for example, a heating temperature and a heating time appropriately selected from the range of 60 to 200 ℃ and a time of 0.4 to 60 minutes are used. The heating temperature and heating time are preferably 70 to 160 ℃ and 0.5 to 10 minutes.
The film thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 to 5. Mu.m, and may be appropriately selected in consideration of the level difference, optical properties, and electrical properties of the substrate used.
Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having vertical alignment properties can be applied to the alignment material, and the alignment material can be aligned. Further, by directly curing the retardation material in an oriented 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 film is useful as a retardation film.
Further, 2 substrates having the alignment material of the present invention formed as described above may be used, and after bonding the alignment materials on both substrates to face each other via a spacer, liquid crystal may be injected between these substrates to produce a liquid crystal display element in which the liquid crystal is aligned.
The composition for forming a cured film of the present invention can be suitably used for the production of various retardation materials (retardation films), liquid crystal display elements, and the like.
Examples
The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.
Abbreviations used in the examples ]
The shorthand notation used in the following examples is as follows.
< raw materials >
GMA: glycidyl methacrylate
AIBN: alpha, alpha' -azobisisobutyronitrile
BMAA: N-Butoxymethacrylamide
MMA: methyl methacrylate
HEMA: methacrylic acid 2-hydroxy ethyl ester
< cinnamic acid Compound having polymerizable group >
CIN1:4- (6-methacryloyloxyhexyl-1-oxy) cinnamic acid
CIN2:4- (3-methacryloxypropyl-1-oxy) cinnamic acid
CIN3:4- (6-Acryloyloxyhexyl-1-oxy) cinnamic acid
Cinnamic acid Compound having no polymerizable group
CIN4: 4-Methoxycinnamic acid
< component B >
HMM: melamine crosslinking agent 303 (Sanjingyi brand) shown by the following structural formula
< D component >)
PTSA: para-toluenesulfonic acid monohydrate
< E component >)
E-1: compounds having N-alkoxymethyl and acryl groups represented by the following structural formula
< solvent >
The resin compositions of examples and comparative examples each contained a solvent, and propylene glycol monomethyl ether (PM) was used as the solvent.
< determination of molecular weight of Polymer >)
The molecular weight of the acrylic copolymer in the polymerization example was measured by using a normal temperature Gel Permeation Chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., ltd., and columns (KD-803, KD-805) manufactured by Shodex Co., ltd.) in the following manner.
The number average molecular weight (hereinafter, mn.) and the weight average molecular weight (hereinafter, mw.) are expressed by polystyrene conversion values.
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Standard sample for standard curve preparation: standard polystyrene (molecular weight of about 197,000, 55,100, 12,800, 3,950, 1,260, 580) manufactured by Showa electric company.
< Synthesis of component A >
Polymerization example 1 >
15.0g of GMA and 0.5g of AIBN as a polymerization catalyst were dissolved in 46.4g of tetrahydrofuran and reacted under reflux for 20 hours to obtain an acrylic polymer solution. The obtained acrylic copolymer solution was slowly dropped into 500.0g of hexane to precipitate a solid, which was filtered and dried under reduced pressure, thereby obtaining an acrylic polymer (P1) having an epoxy group. The Mn of the resulting acrylic polymer was 25,000 and the Mw was 10,000.
Synthesis example 1 >
5.2g of the acrylic polymer (P1) having an epoxy group obtained in Polymer 1, CIN112.0g, ethyl triphenyl bromide as a reaction catalyst0.1g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g of which was dissolved in 70.0g of PM, was reacted at 100℃for 20 hours. The solution was slowly dropped into 1000g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure, whereby a polymer (PA-1) was obtained. The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
Synthesis example 2
5.2g of the acrylic polymer (P1) having an epoxy group obtained in Polymer 1, CIN211.0g, ethyl triphenyl bromide as a reaction catalyst0.1g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g of which was dissolved in 70.0g of PM, was reacted at 100℃for 20 hours. The solution was slowly dropped into 1000g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure, whereby a polymer (PA-2) was obtained. The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
Synthesis example 3 >
5.2g of the acrylic polymer (P1) having an epoxy group obtained in Polymer 1, CIN312.0g, ethyl triphenyl bromide as a reaction catalyst 0.1g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g of which was dissolved in 70.0g of PM, was reacted at 100℃for 20 hours. Slowly dropping the solution into 1000g diethyl ether to precipitate solid, filtering and drying under reduced pressure to obtainPolymer (PA-3). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
Synthesis example 4 >
5.7g of phenol novolac type epoxy resin N-775 (EPICLON series manufactured by DIC Co., ltd.) and 11.0g of CIN1 were brominated with ethyl triphenyl as a reaction catalyst0.2g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g of which was dissolved in 40.0g of PM, was reacted at 100℃for 20 hours. The solution was slowly dropped into 500g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure, whereby a polymer (PA-4) was obtained. The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
Synthesis example 5 >
5.2g of the acrylic polymer (P1) having an epoxy group obtained in Polymer 1, 110.0g of CIN, 2.0g of CIN4, and ethyl triphenyl bromide as a reaction catalyst were reacted0.1g of dibutylhydroxytoluene as a polymerization inhibitor, 0.2g of which was dissolved in 70.0g of PM, was reacted at 100℃for 20 hours. The solution was slowly dropped into 1000g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure, whereby a polymer (PA-5) was obtained. The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
Synthesis example 6 >
5.2g of the acrylic polymer (P1) having an epoxy group obtained in Polymer 1, CIN46.5g, ethyl triphenyl bromide as a reaction catalyst0.1g of PM 48.0g was dissolved and reacted at 100℃for 20 hours. The solution was slowly dropped into 500g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure, whereby a polymer (PA-6) was obtained. The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
Synthesis example 7 >
5.3g of phenol novolac type epoxy resin N-775 (EPICLON series manufactured by DIC Co., ltd.) and 5.0g of CIN4 were brominated with ethyl triphenyl as a reaction catalyst0.2g of PM 25.0g was dissolved and reacted at 100℃for 20 hours. The solution was slowly dropped into 500g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure, whereby a polymer (PA-7) was obtained. The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.
< 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, thereby obtaining an acrylic polymer solution. The Mn of the resulting acrylic polymer was 2,700 and the Mw was 3,900. The acrylic polymer solution was slowly dropped into 2000.0g of hexane to precipitate a solid, which was filtered and dried under reduced pressure, thereby obtaining a 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 dropped into 1000.0g of hexane to precipitate a solid, which was filtered and dried under reduced pressure, thereby obtaining an acrylic copolymer (PC-1). The Mn of the resulting acrylic copolymer was 18,000 and the Mw was 32,800.
< examples, comparative examples >
The compositions for forming cured films of examples and comparative examples were prepared with the compositions shown in Table 1. Next, cured films were formed using the respective phase difference material-forming compositions, and the obtained cured films were evaluated for orientation and adhesion.
[ evaluation of orientation ]
The cured film-forming compositions of examples and comparative examples were applied to the ozone-treated COP film at a wet film thickness of 4 μm using a bar coater. The cured films were formed on the COP films by heat-drying at a temperature of 110 ℃ in a heat-circulating oven for 60 seconds, respectively. Linearly polarized light of 313nm was applied to each of the cured films at 10mJ/cm 2 Is irradiated perpendicularly to the exposure amount to form an alignment material. The alignment material on the COP film was coated with a polymerizable liquid crystal solution RMS03-013C for horizontal alignment, manufactured by trunk corporation, at a Wet film thickness of 6 μm using a bar coater. The film was coated at 300mJ/cm 2 Exposing to prepare the phase difference material. The phase difference material on the fabricated substrate was sandwiched between a pair of polarizing plates, and the appearance of the phase difference characteristics in the phase difference material was observed, and the appearance of the phase difference without defects was indicated as "o", and the appearance of the phase difference without appearance was indicated as "x" and described in the "orientation" column. The evaluation results are summarized in table 2 below.
[ evaluation of adhesion ]
The cured film-forming compositions of examples and comparative examples were applied to the ozone-treated COP film at a wet film thickness of 4 μm using a bar coater. The cured films were formed on the COP films by heat-drying at a temperature of 110 ℃ in a heat-circulating oven for 60 seconds, respectively. Linearly polarized light of 313nm was applied to each of the cured films at 10mJ/cm 2 Is irradiated perpendicularly to the exposure amount to form an alignment material. The polymerizable liquid crystal solution RMS03-013C for horizontal alignment, manufactured by the company corporation, was applied to the alignment material on the COP film with a wet film thickness of 6 μm using a bar coater. The film was coated at 300mJ/cm 2 Exposing to prepare the phase difference material. The retardation material was cut into a 10×10 lattice with a cutter at 1mm intervals. A cellophane tape peel test was performed on the incision using a transparent adhesive tape. The evaluation result was "adhesion", and the case where all the 100 meshes were left without peeling was defined as "o", and even 1 peeling was defined as "x". The evaluation results are summarized in table 2 below.
TABLE 2
Orientation of liquid crystal Adhesion of
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 materials obtained using the cured film-forming composition of examples exhibited good alignment properties and adhesion.
On the other hand, the alignment material obtained using the cured film-forming composition of the comparative example showed good alignment properties, but no adhesion was 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 element or an alignment material of an optically anisotropic film provided inside or outside the liquid crystal display element, and is particularly suitable as a material for a retardation material for a circularly polarizing plate used as an antireflection film for IPS-LCDs or organic EL displays.

Claims (14)

1. A composition for forming a cured film, which 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.
2. The composition for forming a cured film according to claim 1, wherein the group containing a polymerizable double bond is a (meth) acryloyl group.
3. The composition for forming a cured film according to claim 1 or 2, wherein the cinnamic acid derivative having a group containing a polymerizable double bond is a compound represented by the following formula (1),
in formula (1), A 1 And A is a 2 Each independently represents a hydrogen atom or a methyl group,
R 1 a group represented by the following formula (c-2),
in formula (c-2), the dotted line represents a bond, R 101 An alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms of the alkylene group may be replaced with a fluorine atom or an organic group; in addition, R 101 In (C) is-CH 2 CH 2 Can be replaced by-CH=CH-, and R is further defined as being not adjacent to any of the groups listed below 101 In (C) is-CH 2 CH 2 -OCO- -NH- -OCO-, -NH-, groups in NHCONH-and-CO-, M is M 1 Represents a hydrogen atom or a methyl group;
R 2 represents a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group or a 2-valent condensed ring group,
R 3 represents a single bond, an oxygen atom, -COO-, -OCO-, -CH=CHCOO-, or-OCOCH=CH-,
R 4 ～R 7 each independently represents an alkoxy group having 1 to 6 carbon atoms 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 atomsSubstituents in the group, the halogenated alkoxy group with 1 to 6 carbon atoms, the cyano group and the nitro group,
In addition, R 2 、R 3 And R is 4 May together form an aromatic group, or R 2 、R 3 And R is 6 May be taken together to form an aromatic group,
n is an integer of 0 to 3.
4. The composition for forming a cured film according to any one of claims 1 to 3, wherein the crosslinking agent of component (B) is a crosslinking agent having a hydroxymethyl group or an alkoxymethyl group.
5. The composition for forming a cured film according to any one of claims 1 to 4, further comprising: (C) A polymer having at least 1 group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.
6. The composition for forming a cured film according to any one of claims 1 to 5, further comprising: (D) a crosslinking catalyst.
7. The composition for forming a cured film according to any one of claims 1 to 6, which contains a compound (E) having:
more than 1 polymerizable group,
at least 1 group a selected from hydroxyl, carboxyl, amide, amino, and alkoxysilyl groups or at least 1 group reactive with the group a.
8. The composition for forming a cured film according to any one of claims 1 to 7, which contains 1 to 500 parts by mass of the component (B) based on 100 parts by mass of the component (a).
9. The composition for forming a cured film according to any one of claims 5 to 8, which contains 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).
10. The composition for forming a cured film according to any one of claims 6 to 9, which contains 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).
11. The composition for forming a cured film according to any one of claims 7 to 10, which contains 1 to 100 parts by mass of the component (E) per 100 parts by mass of the total amount of the crosslinking agents of the components (a) and (B).
12. A cured film obtained from the composition for forming a cured film according to any one of claims 1 to 11.
13. An alignment material obtained from the composition for forming a cured film according to any one of claims 1 to 11.
14. A retardation material comprising a cured film obtained from the composition for forming a cured film according to any one of claims 1 to 11.
CN202310790480.5A 2017-08-03 2018-08-03 Composition for forming cured film, alignment material, and retardation material Pending CN116789871A (en)

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