CN110325886A - Cured film is formed with composition, orientation material and phase difference material - Google Patents

Abstract

The subject of the invention is to provide having excellent vertical orientation, the orientation material of polymerizable liquid crystal vertical orientation can be made with high sensitivity on resin film, and for providing the cured film formation composition of the phase difference material using such orientation material.Solution is cured film formation composition, orientation material, phase difference material, and above-mentioned cured film formation composition is characterized in that, contain: (A) has the polymer of vertical orientation group；(B) compound with 2 or more the polymerizable groups comprising C=C double bond；And (C) radical polymerization initiator, substantially only (B) ingredient has the polymerizable group comprising C=C double bond.

Description

Composition for forming cured film, orientation material and retardation material

technical field

The present invention relates to a cured film-forming composition suitable for a vertical alignment material that vertically aligns liquid crystal molecules. In particular, the present invention relates to a composition for forming a cured film, an orientation material, and a retardation material useful for producing a +C plate (positive C plate) for improving the filling of a compound having a positive Dielectrically anisotropic liquid crystal (△ε>0) IPS liquid crystal display (In-plane Switching LCD; in-plane orientation switching LCD) and other liquid crystal display (liquid crystal display; LCD) viewing angle characteristics, as an organic EL display The viewing angle characteristics of the circular polarizing plate used for the anti-reflection film are used.

Background technique

IPS-LCD is characterized in that since there is no inclination in the vertical direction of the liquid crystal molecules, there is little brightness change/color change due to the viewing angle, but the disadvantages include that it is difficult to increase contrast, brightness, and response speed. For example, as disclosed in Patent Document 1, the initial IPS-LCD does not use the compensation film of the viewing angle. Such IPS-LCD without the compensation film of the viewing angle has a relatively large light leakage in the dark state of the oblique angle, so it has a display Such disadvantages are low contrast values.

Patent Document 2 discloses an IPS-LCD compensation film using a +C plate and a +A plate (positive A plate). This document shows the following configurations about the liquid crystal display element described therein.

1) A liquid crystal layer having a horizontal alignment is interposed between two substrates supplied by electrodes capable of applying a parallel electric field to the liquid crystal layer.

2) More than one +A plate and +C plate are sandwiched by two polarizers.

3) The main optical axis of the +A plate is perpendicular to the main optical axis of the liquid crystal layer.

4) Determine the retardation value R _LC of the liquid crystal layer, the retardation value R ₊ C of the +C plate, and the retardation value R ₊ A of the +A plate in such a manner as to satisfy the following formula.

R _LC : R _{+ C} : R _{+ A} ≒ 1: 0.5: 0.25

5) The relationship (TAC, COP, PNB) of the retardation value in the thickness direction of the protective film of the polarizing plate with respect to the retardation value of the +A plate and the +C plate is not shown.

In addition, it is disclosed that an IPS-LCD having +A plate and IPS-LCD of +C plate (Patent Document 3). Furthermore, it has been proposed to use a +C plate in order to improve the viewing angle characteristics of a circularly polarizing plate used as an antireflection film of an organic EL display (Patent Document 5).

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 2-256023

Patent Document 2: Japanese Patent Application Laid-Open No. 11-133408

Patent Document 3: Japanese Patent Laid-Open No. 2009-122715

Patent Document 4: Japanese Patent Laid-Open No. 2001-281669

Patent Document 5: Japanese Patent Laid-Open No. 2015-79256

Contents of the invention

The problem to be solved by the invention

As previously proposed, the +C plate is very useful as an optical compensation film for circularly polarizing plates used as antireflection films for IPS-LCDs and organic EL displays because it can compensate for light leakage at places where the viewing angle of the polarizer is large. However, it is difficult to express vertical orientation (positive C-plate) property by conventionally generally known stretching treatment methods.

In addition, the conventionally proposed vertical alignment film using polyimide needs to use a polyimide solvent such as N-methyl-2-pyrrolidone during film production. Therefore, although there is no problem with the glass base material, when the base material is a film, there is a problem that the base material is damaged during formation of the alignment film. Furthermore, the vertical alignment film using polyimide requires firing at high temperature, and there is a problem that the film base material is not resistant to high temperature.

Furthermore, a method for forming a vertical alignment film by directly treating the substrate with a silane coupling agent having a long-chain alkyl group has been proposed, but it is difficult to handle when there is no hydroxyl group on the surface of the substrate. Such a problem is limited (Patent Document 4).

In recent years, in order to reduce the production cost, production by so-called roll-to-roll (roll to roll) on inexpensive resin films such as TAC (triacetate cellulose) films and COP (cycloolefin polymer) films has been demanded. However, it is difficult to produce a +C plate on a resin film for an alignment film formed of conventional materials as described above.

Therefore, an orientation material capable of forming a highly reliable +C plate even on a resin film such as a TAC film, and a cured film-forming composition for forming such an orientation material are required.

The present invention is based on the above knowledge and research results, and the problem to be solved is to provide the following cured film-forming composition for providing excellent vertical alignment and transparency required for optical compensation films. , Solvent resistance, even on a resin film, it is an alignment material that can stably align polymerizable liquid crystals vertically under low-temperature and short-time firing conditions.

Furthermore, another object of the present invention is to provide a cured film-forming composition obtained from the above-mentioned cured film-forming composition, which has excellent vertical orientation and solvent resistance, and can be stably baked on a resin film under low-temperature short-time firing conditions. An alignment material that vertically aligns a polymerizable liquid crystal, and a retardation material useful for a +C plate formed using the alignment material.

Other objects and advantages of the present invention will become clear from the following description.

method used to solve the problem

The inventors of the present invention conducted intensive studies to achieve the above object, and found that by selecting a polymer having a vertical alignment group and a compound having two or more polymerizable groups containing a C=C double bond as a basis for curing The present invention has been completed by providing a material for film formation so that a cured film having excellent vertical alignment can be formed.

That is, in the present invention, as a first viewpoint, it relates to a cured film forming composition characterized by containing:

(A) a polymer having a group represented by the following formula [1] as a vertical alignment group;

(B) a compound having two or more polymerizable groups containing a C=C double bond; and

(C) radical polymerization initiator,

Substantially, only (B) component has a polymeric group containing a C=C double bond.

(In formula [1],

Y ¹ represents a single bond, or represents a binding group, the above-mentioned binding group is selected from -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH- The group in CO-NH-,

^Y2 represents a single bond, linear or branched alkylene group having 1 to 15 carbon atoms (the alkylene group may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other.) Or -CH ₂ -CH(OH)-CH ₂ -, or Y ² represents a 2-valent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (on the cyclic group of the 2-valent cyclic group Any hydrogen atom can be replaced by a straight-chain or branched alkyl group with 1 to 3 carbon atoms, a straight-chain or branched alkoxy group with 1 to 3 carbon atoms, a straight-chain or branched chain A fluorine-containing alkyl group with 1 to 3 carbon atoms, a straight-chain or branched fluorine-containing alkoxy group with 1 to 3 carbon atoms or a fluorine atom substitution.),

Y represents a single bond or an alkylene group with ¹ to 15 carbon atoms (the alkylene group can be any one of linear, branched and cyclic or a combination thereof, and the alkylene group can be replaced by 1 ~3 binding groups A are interrupted, however, binding groups A do not bind to each other.),

Y Represents a single bond, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring ⁽ any hydrogen atom on the cyclic group of the divalent cyclic group can be replaced by a linear or Branched-chain alkyl group with 1-3 carbon atoms, straight-chain or branched-chain alkoxy group with 1-3 carbon atoms, straight-chain or branched chain 1-3 carbon atoms containing fluorine substituted with an alkyl group, a linear or branched fluorine-containing alkoxy group with 1 to 3 carbon atoms, or a fluorine atom.), or Y ⁴ represents a divalent organic compound with 17 to 30 carbon atoms having a steroid skeleton base,

Y represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring ⁽ any hydrogen atom on the cyclic group of the divalent cyclic group can be replaced by a straight-chain or branched carbon Alkyl group having 1 to 3 atoms, linear or branched alkoxy group having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl group having 1 to 3 carbon atoms, straight chain or branched carbon number of 1 to 3 fluorine-containing alkoxy or fluorine atom substitution.),

n represents an integer of 0 to 4, and when n is 2 or more, each Y ⁵ may be the same or different,

Y6 represents a hydrogen atom, an alkyl group with ¹ to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, or a fluorine-containing group with 1 to 18 carbon atoms. Alkoxy (the alkyl group with 1 to 18 carbon atoms, the fluorine-containing alkyl group with 1 to 18 carbon atoms, the alkoxy group with 1 to 18 carbon atoms and the fluorine-containing alkane group with 1 to 18 carbon atoms The oxygen group can be any one of linear, branched and cyclic, or a combination thereof, and can be interrupted by 1 to 3 binding groups A, but the binding groups A do not combine with each other.),

In the case where Y ² and Y ³ represent groups other than single bonds, the combination of Y ² and Y ³ may be a single bond, or may be combined via a bonding group A,

In the case where Y ³ and Y ⁴ represent groups other than single bonds, the combination of Y ³ and Y ⁴ may be a single bond, or may be combined via a bonding group A,

In the case where Y ⁴ and Y ⁵ represent groups other than single bonds, the combination of Y ⁴ and Y ⁵ may be a single bond, or may be combined via a binding group A,

^In the case where ^Y5 and ^Y6 represent a group other than a single bond, the combination of Y5 and Y6 may be a single bond, or may be combined via a bonding group ^A ,

When n is ² or more, the bond between one Y5 and its adjacent ^Y5 may be a single bond, or may be bonded via a bonding group A,

The bonding group A represents a group selected from -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-,

However, the total number of carbon atoms contained in the group represented by formula [1] is 6-30. ).

As a second viewpoint, it relates to the cured film-forming composition described in the first viewpoint, wherein the polymerizable group containing a C=C double bond of the component (B) is selected from acryloyl, methacryloyl, vinyl, olefin, At least one of a propyl group and a maleimide group.

As a 3rd viewpoint, it is related with the cured film formation composition as described in a 1st viewpoint or a 2nd viewpoint containing 10 mass parts - 2000 mass parts of (B) components based on 100 mass parts of (A) components.

As a fourth viewpoint, it relates to the cured film forming composition according to any one of the first viewpoint to the third viewpoint, which contains 0.1 to 50 parts by mass of (C) per 100 parts by mass of component (A) )Element.

As a 5th viewpoint, it is related with the orientation material obtained by hardening the composition for cured film formation in any one of a 1st viewpoint - a 4th viewpoint, It is related with the orientation material characterized by the above-mentioned.

As a 6th viewpoint, it is related with the retardation material characterized by being formed using the cured film obtained from the composition for cured film formation in any one of a 1st viewpoint - a 4th viewpoint.

The effect of the invention

According to the first aspect of the present invention, it is possible to provide a cured film-forming composition for providing a polymerizable liquid crystal that has excellent vertical alignment and can be stably formed on a resin film under low-temperature short-time firing conditions. Vertically oriented orientation materials are useful.

According to the second aspect of the present invention, it is possible to provide an alignment material capable of stably vertically aligning a polymerizable liquid crystal under low-temperature, short-time firing conditions having excellent vertical alignment.

According to the third aspect of the present invention, it is possible to provide a phase difference material which can be formed efficiently even on a resin film, has high transparency, and has high solvent resistance.

Detailed ways

<Cured film forming composition>

The cured film forming composition of the present invention is characterized in that it contains a polymer having a vertical alignment group as the component (A), and a polymerizable polymer having two or more C=C double bonds as the component (B). The radical polymerization initiator which is a radical compound and (C)component substantially only has a polymerizable group containing a C=C double bond in (B)component. Furthermore, other additives may be contained as long as the effects of the present invention are not impaired.

Hereinafter, details of each component will be described.

＜(A)Ingredient＞

(A) component contained in the cured film formation composition of this invention is a polymer which has a vertical alignment property group.

More specifically, the vertical alignment group is a group represented by the following formula [1].

In formula [1], represents a single bond, or represents a binding group, the above-mentioned binding group is selected from -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O Groups in - and -NH-CO-NH-.

In the formula [1], Y ² represents a single bond or a linear or branched alkylene group with 1 to 15 carbon atoms, and the alkylene group may be interrupted by 1 to 3 bonding groups A, but the bonding The groups A are not bonded to each other.

Y ² also includes -CH ₂ -CH(OH)-CH ₂ -.

In addition, as ^Y2 , a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring can be mentioned, and any hydrogen atom on these cyclic groups can be replaced by a straight-chain or branched carbon atom. Alkyl group of 1 to 3, linear or branched alkoxy group of 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl group of 1 to 3 carbon atoms, linear Substituted by a fluorine-containing alkoxy group or a fluorine atom having a carbon number of 1 to 3 in a shape or a branched chain.

Examples of the heterocyclic ring include pyrrole ring, imidazole ring, Azole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring , triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring , Oxadiazole ring, acridine ring, etc., more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, Pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring.

Examples of the alkyl group mentioned as the above-mentioned substituent include methyl, ethyl, n-propyl, isopropyl, and cyclopropyl, and examples of the above-mentioned alkoxy group include an oxygen atom -O- and the above-mentioned Specific examples of the alkyl group include groups obtained by combining the groups mentioned above. In addition, examples of the above-mentioned fluorine-containing alkyl group and fluorine-containing alkoxy group include groups in which any hydrogen atom in the above-mentioned alkyl group and alkoxy group is replaced by a fluorine atom.

Among them, in view of the ease of synthesis, ^Y2 is preferably a benzene ring or a cyclohexane ring.

In the above formula [1], ^Y3 represents a single bond or an alkylene group with 1 to 15 carbon atoms, and the alkylene group can be any one of linear, branched and cyclic or a combination thereof , can be interrupted by 1 to 3 binding groups A, but the binding groups A do not bind to each other.

In the above-mentioned formula [1], Y ⁴ represents a single bond, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups can be replaced by a linear Or a branched alkyl group with 1 to 3 carbon atoms, a straight chain or branched alkoxy group with 1 to 3 carbon atoms, a straight chain or branched chain with 1 to 3 carbon atoms containing A fluorine-containing alkyl group, a linear or branched fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom is substituted.

The alkyl group and the like mentioned as the above-mentioned heterocycle and substituents may be those mentioned above for ^Y2 .

Furthermore, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 30 carbon atoms having a steroid skeleton. Its preferred example is a compound selected from the group consisting of cholestene, androstene, β-cholestene, epiandrosterone, ergosterene, estrone, 11α-hydroxymethyl sterol, 11α-progesterone, wool Two hydrogen atoms have been removed from the structures of sterene, estradiol, methyltestosterone, norethindrone, pregnenolone, β-sitosterene, stigmasterene, testosterone, and cholesteryl acetate The divalent group of the obtained structure. More specifically, for example, it is as follows.

(In the formula, * indicates the binding position.)

Among them, Y ⁴ is preferably a divalent organic group having 17 to 30 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton, from the viewpoint of ease of synthesis.

In formula [ ¹ ], Y represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups can be replaced by a straight-chain or branched carbon Alkyl group having 1 to 3 atoms, linear or branched alkoxy group having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl group having 1 to 3 carbon atoms, straight Chain or branched C1-C3 fluorine-containing alkoxy group or fluorine atom substitution. The above-mentioned heterocycle and the alkyl group mentioned as substituents can be exemplified by the above ^- mentioned Y4.

Among them, ^Y5 is preferably a benzene ring or a cyclohexane ring.

In addition, in formula [1], n represents an integer of 0 to 4, and when n is 2 or more, Y ⁵ may be the same group or different groups. Among these, n is preferably 0-3 from the viewpoint of availability of raw materials and easiness of synthesis. More preferably, it is 0-2.

In formula [ ¹ ], Y6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms. 1 to 18 fluorine-containing alkoxy groups, the C1 to C18 alkyl groups, C1 to C18 fluorine-containing alkyl groups, C1 to C18 alkoxy groups and C1 The fluorine-containing alkoxy group of ~18 may be linear, branched, or cyclic, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other .

Among them, Y6 is preferably an alkyl group with ¹ to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, or a fluorine-containing group with 1 to 10 carbon atoms. alkoxy. More preferably, Y ⁶ is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In addition, when Y ⁴ is a divalent organic group having a steroid skeleton, Y ⁶ is preferably a hydrogen atom.

For example, the above-mentioned alkyl groups having 1 to 18 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1 -methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-Dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl , 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2- Dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl Base-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2- Dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl Base-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl Base-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl Butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-di Methyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl Base, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3 -Ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc.

Examples of the above-mentioned alkylene group having 1 to 15 carbon atoms include divalent groups obtained by removing one optional hydrogen atom from the above-mentioned alkyl group.

Examples of the above-mentioned alkoxy group having 1 to 18 carbon atoms include groups in which an oxygen atom -O- is bonded to the groups mentioned as specific examples of the above-mentioned alkyl group.

In addition, examples of the fluorine-containing alkyl group having 1 to 18 carbon atoms and the fluorine-containing alkoxy group having 1 to 18 carbon atoms include the above-mentioned alkyl group having 1 to 18 carbon atoms and the fluorine-containing alkyl group having 1 to 18 carbon atoms. A group in which any hydrogen atom in the alkoxy group of 18 is replaced by a fluorine atom.

Further, when ^Y2 and ^Y3 represent a group other than a single bond, the combination of ^Y2 and ^Y3 may be a single bond, or may be bonded via a bonding group A. When ^Y3 and ^Y4 represent a group other than a single bond In the case of a group, the combination of Y ³ and Y ⁴ may be a single bond, or may be combined via a bonding group A. In the case of Y ⁴ and Y ⁵ representing a group other than a single bond, Y ⁴ and Y ⁵ The combination of can be a single bond, or can be combined through the binding group A. ^In the case where ^Y5 and ^Y6 represent a group other than a single bond, the combination of Y5 and ^Y6 can be a single bond, or can be combined through a binding group A is bonded, and when n is 2 or more, the bond between one Y ⁵ and its adjacent Y ⁵ may be a single bond, or may be bonded via a bond A.

In addition, the above-mentioned bonding group A means selected from -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O- Groups in CO-NH- and -NH-CO-NH-.

Moreover, the total number of the carbon atoms contained in the group represented by formula [1] is 6-30, for example, it is 6-20.

Among them, in consideration of vertical alignment and coatability of polymerizable liquid crystals, the vertical alignment group represented by the formula [1] is preferably one containing an alkyl group having 7 to 18 carbon atoms, especially 8 to 15 carbon atoms. The group is more preferably an alkyl group having 7 to 18 carbon atoms, especially 8 to 15 carbon atoms.

The method to obtain the polymer of (A) component of this invention is not specifically limited. For example, the polymer of (A) component can be obtained by reacting the monomer which has a vertical alignment property group, and arbitrary monomers by polymerization methods, such as radical polymerization.

Specific examples of arbitrary monomers are given below. However, it is not limited to this.

As a monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacrylic acid) Acyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

Examples of monomers having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0] Heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

Examples of monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl acrylate. , 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, hexanol Esters 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl Ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6 -Lactone etc.

As a monomer which has an amino group, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned, for example.

Examples of monomers having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleyl imine etc.

As a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethylxylene isocyanate, etc. are mentioned, for example.

Examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, benzyl acrylate, and naphthyl acrylate. , anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl 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 acrylate Base-2-adamantyl ester, 8-methyl-8-tricyclodecanyl acrylate, and 8-ethyl-8-tricyclodecanyl acrylate, etc.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and ester, tert-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, methacrylic acid 2,2,2-Trifluoroethyl ester, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methacrylic acid 2-Ethoxyethyl ester, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, gamma-butyrolactone methacrylate ester, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, and 8-ethyl-8-tricyclodecanyl methacrylate, etc. .

Examples of vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] Heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide, etc.

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

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

(A) The weight average molecular weight of the polymer of component becomes like this. Preferably it is 1,000-200,000, More preferably, it is 2,000-150,000, More preferably, it is 3,000-100,000. When the weight-average molecular weight is too large, exceeding 200,000, the solubility in solvents may decrease and handleability may decrease, and when the weight-average molecular weight is too small, less than 1,000, solvent resistance and heat resistance may decrease.

In the polymer of the component (A), the ratio of the vertical alignment group is preferably 3 mol % to 90 mol %, more preferably 5 mol % to 100 mol of all repeating units of the polymer. 80 mol%. When it is less than 3 mol%, vertical alignment property may become insufficient, and when it is too large compared with 90 mol%, it may exert a bad influence on the applicability of a liquid crystal.

As the polymer having a vertical alignment group, a commercial item can be suitably used, and examples thereof include ARUFON UF-5041, UF-5080, and UF-5022 [the above are all manufactured by Toagosei Co., Ltd.] and the like.

＜Component (B)＞

The (B) component in the cured film forming composition of this invention is a compound which has 2 or more polymerizable groups containing a C=C double bond.

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

(B) The polymerizable group containing the C=C double bond of the component is preferably a polymerizable group having 3 to 16 carbon atoms and having an unsaturated bond at the end, and is particularly preferably a specific group represented by formula (b2). side chain.

In formula (b2), R ⁵¹ is an organic group with 1 to 14 carbon atoms selected from the group consisting of aliphatic groups, aliphatic groups containing ring structures, and aromatic groups, or an organic group selected from An organic group constituted by a combination of a plurality of organic groups in this group. R ⁵¹ may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.

In the formula (b2), R ⁵² is a hydrogen atom or a methyl group, preferably a specific side chain in which R ⁵² is a hydrogen atom, more preferably a specific side chain whose terminal is an acryloyl group, a methacryloyl group or a styryl group.

In addition, in this specification, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid means acrylic acid and methacrylic acid. In addition, the (meth)acryloyl group represents CH ₂ =CHCO-, and CH(CH ₃ )=CHCO-.

Although an example of a suitable compound is given below as a compound which has a polymeric group containing a C=C double bond, (B) component is not limited to these illustrations.

Examples of compounds having two (meth)acryloyl groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Propylene Glycol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Polyethylene Glycol Di(meth)acrylate, Polypropylene Glycol Di(meth)acrylate, 1,4-Butanediol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-Methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, tricyclo[5.2.1.02 ,6] Decanedimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy Propane, 2-hydroxy-1,3-di(meth)acryloxypropane, trihydroxyethylisocyanurate di(meth)acrylate, 9,9-bis[4-(2-( Meth)acryloyloxyethoxy)phenyl]fluorene, undecylenoyl glycol di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1, 3-Adamantanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and the like.

As a compound having two or more (meth)acryloyl groups, a commercially available product can be suitably used, and examples thereof include Light Acrylite 3EG-A, Light Acrylite 4EG-A, Light Acrylite 9EG-A, Light Acrylite 14EG-A, and Light Acrylite 14EG-A. PTMGA-250, Light Acrylet NP-A, Light Acrylet MPD-A, Light Acrylet 1.6HX-A, Light Acrylet 1.9ND-A, Light Acrylet MOD-A, Light Acrylet DCP-A, Light Acrylic BP-4EAL, Light Acrylet BP-4PA, Light Ester G-201P, Light Ester P-2M, Light Ester EG, Light Ester 2EG, Light Ester 3EG, Light Ester 4EG, Light Ester 9EG, Light Ester 14EG, Light Ester 1.4BG , Lightoster NP, Lightoster 1.6HX, Lightoster 1.9ND, Lightoster G-101P, Lightoster G-201P, Lightoster BP-2EMK [all of the above are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester 701A , NK Ester A-200, NK Ester A-400, NK Ester A-600, NK Ester A-1000, NK Ester A-B1206PE, NK Ester ABE-300, NK Ester A-BPE-10, NK Ester A-BPE -20, NK Ester A-BPE-30, NK Ester A-BPE-4, NK Ester A-BPEF, NK Ester A-BPP-3, NK Ester A-DCP, NK Ester A-DOD-N, NK Ester A -HD-N, NK Ester A-NOD-N, NK Ester APG-100, NK Ester APG-200, NK Ester APG-400, NK Ester APG-700, NK Ester A-PTMG-65, NK Ester 1G, NK Ester 2G, NK Ester 3G, NK Ester 4G, NK Ester 9G, NK Ester 14G, NK Ester 23G, NK Ester BPE-80N, NK Ester BPE-100, NK Ester BPE-200, NK Ester BPE-500, NK Ester BPE -900, NK Ester BPE-1300N, NK Ester DCP, NK Ester DCP-N, NK Ester HD-N, NK Ester NOD-N, NK Ester NPG, NK Ester 1206PE, NK Ester 701, NK Ester 9PG [above, all Yes Shin-Nakamura Chemical Industry Co., Ltd.]; FANCRYL FA-124AS, FANCRYL FA-129AS, FANCRYL FA-222A, FANCRYL FA-240A, FANCRYL FA-P240A, FANCRYL FA-P270A, FANCRYL FA-321A, FANCRYL FA-324A, FANCRYL FA-PTG9A, FANCRYL FA-121M, FANCRYL FA-124M, FANCRYL FA-125M, FANCRYL FA-220M, FANCRYL FA-240M, FANCRYL FA-320M, FANCRYL FA-321M, FANCRYL FA-3218M, FPTANCRYL [FA- All of the above are manufactured by Hitachi Chemical Co., Ltd.]; DPGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, EBECRYL 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [Daisel Ornex Co. ) system]; Bisucoat #195, Bisucoat #230, Bisucoat #260, Bisucoat #310HP, Bisucoat #335HP, Bisucoat #700HV, Bisucoat #540, Bisucoat #802, Bisucoat #295 ) system] and so on.

Examples of compounds having three (meth)acryloyl groups (trifunctional compounds) include ethylene oxide-modified 1,1,1-trimethylolethane tri(meth)acrylate [ethylene oxide plus 3~30 moles], ethylene oxide modified trimethylolpropane tri(meth)acrylate[3~30 ethylene oxide added moles], propylene oxide modified trimethylolpropane tri(methyl) Acrylate [3-30 moles of propylene oxide added], ethylene oxide modified glycerol tri(meth)acrylate [3-30 moles of ethylene oxide added], propylene oxide modified glycerol tri(meth)acrylate [The number of moles of propylene oxide added is 3~30], tris(2-(acryloyloxy)ethyl)isocyanurate, ε-caprolactone modified tris(2-(acryloyloxy)ethyl) ) isocyanurate [ε-caprolactone addition molar number 1 to 30], 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(methyl) ) acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, etc.

The above-mentioned trifunctional compound can be suitably used as a commercial product, for example, Bisucoat #360 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; NK Ester A-GLY-9E, NK Ester A-GLY-20E, NK Ester AT-20E [The above are all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [the above are all manufactured by Daisel Ornex Co., Ltd.], Bisucoat #295, Bisucoat #300 [the above are all manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylate TMP-A, Light Acrylate PE-3A, Light Ester TMP [the above are all manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9300, NK Ester A -9300-1CL, NK Ester A-TMM-3, NK Ester A-TMM-3L, NK Ester A-TMM-3LM-N, NK Ester A-TMPT, NK Ester TMPT Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [the above are all manufactured by Daicel Ornex Co., Ltd.], etc.

As a compound (tetrafunctional compound) having four (meth)acryloyl groups, for example, ethylene oxide-modified ditrimethylolpropane tetra(meth)acrylate [4 to 40 moles of ethylene oxide added ], ethylene oxide modified pentaerythritol tetra(meth)acrylate [4-40 moles of ethylene oxide added], ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.

Commercially available products can be suitably used for the above-mentioned tetrafunctional compound, and examples thereof include NK Ester ATM-4E, NK Ester ATM-35E [the above are all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 40 [Daisell. Ornex Co., Ltd.], etc., Biscott #300 [Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylette PE-4A [Kyoeisha Chemical Co., Ltd.]; NK Ester AD-TMP, NK Ester A-TMMT [ All of the above are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 140, EBECRYL 1142, and EBECRYL 180 [all of the above are manufactured by Daisel Ornex Co., Ltd.] and the like.

Examples of compounds having five or more (meth)acryloyl groups (compounds having five or more functions) include ethylene oxide-modified dipentaerythritol hexa(meth)acrylate [6 to 60 moles of ethylene oxide added] , Ethylene oxide modified tripentaerythritol octa(meth)acrylate [ethylene oxide added moles 6~60], dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa( Meth)acrylate, etc.

Commercially available compounds can be suitably used for the above-mentioned pentafunctional or higher functional compound, and examples thereof include NK Ester A-DPH-12E [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], Bisucoat #802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Acrylette DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, NK Ester A-DPH [all of the above are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; DPHA [manufactured by Daicel Ornex Co., Ltd.] ]Wait.

Examples of bifunctional urethane (meth)acrylates include (meth)acrylic acid adducts of phenyl glycidyl ether and urethanes of 1,6-hexamethylene diisocyanate, benzene (meth)acrylic adducts of glycidyl ether and carbamates of toluene diisocyanate, etc.

The above-mentioned bifunctional urethane (meth)acrylate can be suitably used as a commercially available product, and examples thereof include AH-600 and AT-600 [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Origo U- 2PPA, NK オリゴU-200PA, NK オリゴUA-160TM, NK オリゴUA-290TM, NK オリゴUA-4200, NK オリゴUA-4400, NK オリゴUA-122P, NK オリゴUA-W2A[The above are all new Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 210, EBECRYL 215, EBECRYL230, EBECRYL 244, EBECRYL 245, EBECRYL 270, EBECRYL 280/15IB, EBECRYL 284, EBECRYL285, EBECRYL 4858, EB20LECRYL 18308 EB, EB , EBECRYL 8804, EBECRYL8807, EBECRYL 9227EA, EBECRYL 9270, KRM (registered trademark) 7735 [the above are all manufactured by Daisel Ornex Co., Ltd.]; Ziguang (registered trademark) UV-6630B, Ziguang UV-7000B, Ziguang UV-7461TE , UV-2000B, UV-2750B, UV-3000, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B , Ziguang UV-6640B [the above are all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc.

Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having three (meth)acryloyl groups include NK Origo UA-7100 [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] ; EBECRYL (registered trademark) 204, EBECRYL 205, EBECRYL 264, EBECRYL 265, EBECRYL 294/25HD, EBECRYL 1259, EBECRYL4820, EBECRYL 8311, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, 8 (registered trademark) , are made by ダイセルオルネクス (Co., Ltd.)]; Ziguang (registered trademark) UV-7550B, Ziguang UV-7000B, Ziguang UV-7510B, Ziguang UV-7461TE, Ziguang UV-2750B [the above are Japan Synthetic Chemical Industry ( Co., Ltd.] and so on.

Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having four (meth)acryloyl groups include EBECRYL (registered trademark) 8210, EBECRYL 8405, and KRM (registered trademark) 8528. [All of the above are manufactured by Daisel Ornex Co., Ltd.]; Purple Light (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc.

As the polyfunctional urethane (meth)acrylate compound (pentafunctional or more functional urethane (meth)acrylate) having five or more (meth)acryloyl groups, for example, pentaerythritol tris( Urethane compound of meth)acrylate and 1,6-hexamethylene diisocyanate, carbamate compound of pentaerythritol tri(meth)acrylate and toluene diisocyanate, pentaerythritol tri(meth)acrylate and isofor Urethane compounds of ketone diisocyanate, carbamate compounds of dipentaerythritol penta(meth)acrylate and 1,6-hexamethylene diisocyanate, etc.

The above-mentioned urethane (meth)acrylate with more than five functions can be suitably used as a commercially available product, for example, UA-306H, UA-306T, UA-306I, UA-510H [the above are Kyoeisha Chemical (Co., Ltd.)]; NK Origo U-6LPA, NK Origo U-10HA, NK Origo U-10PA, NK Origo U-1100H, NK Origo U-15HA, NK Origo UA-53H, NK Origo UA-33H [above, All are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 220, EBECRYL 1290, EBECRYL5129, EBECRYL 8254, EBECRYL 8301R, KRM (registered trademark) 8200, KRM 8200AE, KRM 8904, KRM8452 · Made by Ornex Co., Ltd.]; Purple (registered trademark) UV-1700B, Purple UV-6300B, Purple UV-7600B, Purple UV-7605B, Purple UV-7610B, Purple UV-7620EA, Purple UV-7630B, Purple UV- 7640B, Ziguang UV-7650B [the above are all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc.

The component (B) of the present invention may be a polymer compound having one or more side chains whose terminals are polymerizable unsaturated bonds in the molecule. As such a polymer compound having a side chain whose terminal is a polymerizable unsaturated bond, a polymer compound having a (meth)acryloyl group in two or more side chains in the molecule is preferably mentioned.

Examples of the polymer compound include polymer compounds containing one or more (meth)acryloyl groups such as urethane acrylic, epoxy acrylic, and various (meth)acrylates.

(B) The weight average molecular weight of the high molecular compound of a component becomes like this. Preferably it is 1,000-200,000, More preferably, it is 5,000-50,000. If the molecular weight is less than 1,000, the effect of the present invention will not be exerted. On the other hand, when the molecular weight exceeds 100,000 and is too large, it may not dissolve in the composition.

Examples of compounds of such (B) components include Acryto 8BR-930M, Acryto 8UH-1006, Acryto 8KQ-2001, Acryto 8KX-078, Acryto 1SX-1055 [above, manufactured by Taisei Fine Chemical Co., Ltd.], SMP Polymers such as -250A, SMP-360A, and SMP-550A [above, manufactured by Kyoeisha Chemical Co., Ltd.].

Content in the case of containing (B) component is 10 mass parts - 2000 mass parts per 100 mass parts of (A) components, Preferably it is 15 mass parts - 500 mass parts.

＜(C)Ingredient＞

(C)component in the cured film formation composition of this invention is a radical polymerization initiator.

As the radical polymerization initiator, known radical polymerization initiators can be used, for example, alkyl phenones, benzophenones, acyl phosphine oxides, Micher's benzoylbenzoate, Oxime esters, tetramethylthiurams monosulfide, thioxanthones, etc.

As the radical polymerization initiator used in the present invention, for example, α-diketones such as diacetyl; azoin such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin Azoin ethers such as isopropyl ether; thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis(dimethyl benzophenone, 4,4'-bis(diethylamino)benzophenone and other benzophenones; acetophenone, p-dimethylaminoacetophenone, α,α-dimethyl Oxy-α-acetoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1-[2-methyl-4-methylthio Phenyl]-2-morpholino-1-propanone, α,α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butan-1-one and other acetophenones; anthraquinone, 1,4-naphthoquinone and other quinones; phenacyl chloride, tribromomethylphenyl Halogen compounds such as sulfone and tri(trichloromethyl)-s-triazine; [1,2'-biimidazole]-3,3',4,4'-tetraphenyl, [1,2'-biimidazole ]-1,2'-dichlorophenyl-3,3',4,4'-tetraphenyl and other biimidazoles, di-tert-butyl peroxide and other peroxides; 2,4,6- Acylphosphine oxides such as trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of commercially available products include Irugakyua 184, 369, 379EG, 651, 500, 907, CGI369, and CG24-61 (the above, manufactured by Chiba Special Chemicals Co., Ltd.), Lusirin LR8728, and Lussirin TPO (the above, manufactured by BASF (Co., Ltd.). )), Dorokinua 1116, 1173 (above, Ciba Special Chemicals Co., Ltd.), Yube Clear P36 (UCB Co., Ltd.) and other commercially available products.

Among the above, 1-[2-methyl-4-methylthiophenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenophenyl)-butan-1-one, α,α-dimethoxy-α-phenylacetophenone and other acetophenones, phenacyl chloride, tribromomethylphenyl sulfone, Combination of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2'-bidiimidazoles, 4,4'-diethylaminobenzophenone and mercaptobenzothiazole, Lucillin TPO (trade name), Irugacure 651 (trade name), and Irugacure 369 (trade name).

The above-mentioned radical polymerization initiators may be used alone or in combination of two or more. The said radical polymerization initiator is preferably 0.1-50 mass parts with respect to 100 mass parts of (A) components, More preferably, it is 1-30 mass parts, Especially preferably, it can use it in the quantity of 2-30 mass parts. If the amount of radical polymerization initiator used is less than the above range, it will be easily affected by the inactivation of free radicals caused by oxygen (reduction in sensitivity), and if it is more than the above range, there will be poor compatibility or storage Tendency to decrease stability.

<Solvent>

The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at this time should just be a solvent which can dissolve (A) component, (B) component, (C) component, and other additives mentioned later as needed, and its kind, structure, etc. are not specifically limited.

Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl Diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol , propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone , cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropionate ethyl ester, 2- Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, 3-methoxy ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate ester, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, etc.

When using the cured film-forming composition of the present invention to form a cured film on a resin film to produce an orientation material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1- Butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferable from the point of view that the resin film exhibits resistance.

These solvents may be used alone or in combination of two or more.

＜Other additives＞

Furthermore, the cured film-forming composition of the present invention may contain a sensitizer, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment as necessary, as long as the effect of the present invention is not impaired. , dyes, storage stabilizers, defoamers, antioxidants, etc.

<Preparation of cured film-forming composition>

The cured film forming composition of the present invention is: a polymer having a vertical alignment group containing (A) component, a compound having two or more polymerizable groups including a C=C double bond as component (B), (C) The polymerization initiator of a component can also contain other additives as long as the effect of this invention is not impaired further. And usually, these are used as the form of the solution which melt|dissolved in a solvent.

Preferred examples of the cured film-forming composition of the present invention are as follows.

[1]: A cured film forming composition comprising: (A) component; 10 to 2,000 parts by mass of (B) component based on 100 parts by mass of (A) component; (A) The polymer of a component is (C)component of 0.1 mass part - 50 mass parts.

[2]: A cured film forming composition comprising: component (A); 10 to 2000 parts by mass of component (B) based on 100 parts by mass of component (A); (A) The polymer of a component is (C) component of 0.1 mass part - 50 mass parts; and a solvent.

The compounding ratio, preparation method, etc. at the time of using the cured film forming composition of this invention as a solution are demonstrated in full detail below.

The ratio of the solid content 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 it is 1% by mass to 60% by mass, preferably 2% by mass to 50% by mass , and more preferably 2% by mass to 20% by mass. Here, the solid content refers to a component obtained by removing a solvent from all the components of the cured film forming composition.

The preparation method of the cured film forming composition of this invention is not specifically limited. As a preparation method, for example, in a solution of (A) component dissolved in a solvent, the method of mixing (B) component, (C) component, etc. in a predetermined ratio to obtain a homogeneous solution; or, in this A method in which other additives are further added and mixed as necessary at an appropriate stage of the preparation method.

In addition, it is preferable to use the prepared solution of the cured film-forming composition after filtration using a filter having a pore diameter of about 0.2 μm or the like.

＜Cured film, orientation material and retardation material＞

A solution of the composition for forming a cured film of the present invention is applied to a substrate (for example, a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc. substrates, etc.), film substrates (e.g., cellulose triacetate (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate Glycol ester (PET) film, resin film such as acrylic film, polyethylene film), etc., by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating after slit coating, inkjet coating Cloth, printing, etc. are applied to form a coating film, and then heated and dried with a hot plate or an oven to form a cured film. This cured film can be directly used as an orientation material.

As the conditions for heating and drying, as long as the components of the cured film (orientation material) are insoluble in the polymerizable liquid crystal solution coated thereon, the crosslinking reaction using the crosslinking agent can be carried out. The heating temperature and heating time are suitably selected in the range of °C to 200 °C and time of 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70° C. to 160° C. and 0.5 minutes to 10 minutes.

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

Since the orientation material formed by the cured film composition of the present invention has solvent resistance and heat resistance, it is possible to coat a phase difference material such as a polymerizable liquid crystal solution with vertical orientation on the orientation material, and to make it on the orientation material. orientation. Furthermore, the phase difference material can be formed as a layer which has an optical anisotropy by directly hardening the phase difference material in an aligned state. Furthermore, when the substrate on which the orientation material is formed is a film, it becomes useful as a retardation film.

In addition, it is also possible to use two substrates having the orientation material of the present invention formed as described above, and after bonding the orientation materials on the two substrates to face each other through a spacer, between these substrates Liquid crystal is injected to make a liquid crystal display element with liquid crystal aligned.

Thus, the composition for cured film formation of this invention can be used suitably for manufacture of various phase difference materials (retardation film), liquid crystal display elements, etc.

Example

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

[Abbreviated symbols used in Examples]

The meanings of the abbreviated symbols used in the following examples are as follows.

＜Materials of component (A)＞

LAA: lauryl acrylate

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-Hydroxyethyl methacrylate

MA1:

AIBN: α,α'-Azobisisobutyronitrile

ARU: ARUFON UF-5041 manufactured by Toagosei Co., Ltd.

＜Component (B)＞

DPHA: dipentaerythritol hexaacrylate

8KX: 8KX-078 manufactured by Taisei Fine Chemical Co., Ltd. (solid content concentration: 40% by mass)

8KQ: 8KQ-2001 manufactured by Taisei Fine Chemical Co., Ltd. (solid content concentration: 39% by mass)

8UH: 8UH-1006 manufactured by Taisei Fine Chemical Co., Ltd. (solid content concentration: 45% by mass)

＜(C)Ingredient＞

IRG: IRGACURE 907 manufactured by BASF

<Solvent>

Each resin composition of Examples and Comparative Examples contains a solvent, and as the solvent, propylene glycol monomethyl ether (PM), ethyl acetate (EA), and butyl acetate (BA) were used.

＜Measurement of molecular weight of polymer＞

The molecular weight of the acrylic copolymer in a polymerization example was measured as follows using GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by Shimadzu Corporation. In addition, the following number average molecular weight (hereinafter referred to as Mn) and number average molecular weight (hereinafter referred to as Mw) are represented by polystyrene conversion values.

Eluent: tetrahydrofuran

Flow rate: 1mL/min

Column temperature: 40°C

Standard samples for calibration curve creation: Showa Denko polystyrene (molecular weight approx. 197,000, 55,100, 12,800, 3,950, 1,260, 580)

<Synthesis Example 1> Synthesis of MA1

4-(trans-4-pentylcyclohexyl)benzoic acid 4.0g (14.6mmol), HEMA 1.0g (13.3mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodi 2.5 g (15.9 mmol) of imine, 0.1 g (0.7 mmol) of 4-dimethylaminopyridine, and 19.3 g of tetrahydrofuran were mixed and stirred at room temperature for 24 hours. After completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, dissolved in 150 mL of ethyl acetate, and washed three times by adding 100 mL of ammonium chloride aqueous solution. Ethyl acetate was distilled off under reduced pressure to obtain 4.3 g of the target substance MA1 (yield: 84%).

＜Polymerization Example 1＞

1.0 g of LAA, 3.2 g of MAA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 15.3 g of PM, and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 20% by mass) ( P1). Mn of the obtained acrylic copolymer was 5,500, and Mw was 7,100.

＜Polymerization example 2＞

1.0 g of LAA, 0.8 g of MAA, and 0.1 g of AIBN as a polymerization catalyst were dissolved in 7.8 g of PM, and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) ( P2). Mn of the obtained acrylic copolymer was 13,700, and Mw was 24,000.

＜Polymerization example 3＞

1.0 g of LAA, 3.7 g of MMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 15.3 g of PM, and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) ( P3). Mn of the obtained acrylic copolymer was 7,700, and Mw was 13,600.

＜Polymerization Example 4＞

3.0 g of MMA, 0.3 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 14.6 g of PM, and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 30% by mass) ( P4). Mn of the obtained acrylic copolymer was 18,000, and Mw was 32,800.

＜Polymerization example 5＞

1.0 g of MA1, 0.8 g of MAA, and 0.1 g of AIBN as a polymerization catalyst were dissolved in 7.7 g of PM, and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 20% by mass) ( P5). Mn of the obtained acrylic copolymer was 8,900, and Mw was 30,800.

<Examples 1-11, Comparative Examples 1-2>

Each cured film forming composition was prepared with the composition shown in Table 1.

[Table 1]

<Examples 12 to 28, Comparative Examples 3 to 5>

Next, a cured film was formed using each composition for phase difference material formation, and the evaluation of the vertical orientation property was performed about each obtained cured film.

[Evaluation of Vertical Orientability]

Each of the cured film-forming compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 2 was coated on each substrate with a wet (Wet) film thickness of 4 μm using a bar coater. After heating and drying in a heat circulation oven at a temperature of 110° C. for 60 seconds, the coating film was exposed to form a cured film on each base material.

A polymerizable liquid crystal solution RMS03-015 for vertical alignment manufactured by Merck Co., Ltd. was applied on the cured film with a wet film thickness of 6 μm using a bar coater. After heating and drying on a hot plate at a temperature of 60° C. for 60 seconds, the coating film was exposed at 500 mJ/cm ² to prepare a phase difference material.

The incident angle dependence of the in-plane retardation was measured using the retardation measurement apparatus RETS100 manufactured by Otsuka Electronics Co., Ltd. using these manufactured retardation materials. When the in-plane retardation value at an incident angle of 0° is 0 and the in-plane retardation at an incident angle of ±50° is in the range of 38±5 nm, it is judged to be vertically aligned. The evaluation results are summarized in Table 2 below.

[Table 2]

[Table 2]

Cured Film Composition Substrate film Cured film exposure vertical orientation Example 12 A-1 TAC 100mJ/cm² ○ Example 13 A-1 TAC 300mJ/cm² ○ Example 14 A-1 TAC 500mJ/cm² ○ Example 15 A-1 TAC 800mJ/cm² ○ Example 16 A-1 COP 500mJ/cm² ○ Example 17 A-1 PET 500mJ/cm² ○ Example 18 A-1 PC 500mJ/cm² ○ Example 19 A-2 TAC 500mJ/cm² ○ Example 20 A-3 TAC 500mJ/cm² ○ Example 21 A-4 TAC 500mJ/cm² ○ Example 22 A-5 TAC 500mJ/cm² ○ Example 23 A-6 TAC 500mJ/cm² ○ Example 24 A-7 TAC 500mJ/cm² ○ Example 25 A-8 TAC 500mJ/cm² ○ Example 26 A-9 TAC 500mJ/cm² ○ Example 27 A-10 TAC 800mJ/cm² ○ Example 28 A-11 TAC 500mJ/cm² ○ Comparative example 3 B-1 TAC 500mJ/cm² x Comparative example 4 B-1 TAC 800mJ/cm² x Comparative Example 5 B-2 TAC 500mJ/cm² x

As shown in Table 2, the orientation material obtained using the cured film-forming composition of the Example showed favorable vertical orientation. On the other hand, in the cured film obtained using the cured film-forming composition of the comparative example, it was difficult to obtain vertical alignment property.

industry availability

The cured film-forming composition according to the present invention is very useful as a material for forming a liquid crystal alignment film for forming a liquid crystal display element, an alignment material for an optically anisotropic film provided inside or outside a liquid crystal display element, and is particularly useful. Yes, it is suitable as a material for the optical compensation film of circularly polarizing plates used as anti-reflection films for IPS-LCD and organic EL displays.

Claims (6)

1. a kind of cured film, which is formed, uses composition, which is characterized in that contain:

(A) there is polymer of the group as vertical orientation group shown in following formula [1]；

(B) compound with 2 or more the polymerizable groups comprising C=C double bond；And

(C) radical polymerization initiator,

Substantially only (B) ingredient has the polymerizable group comprising C=C double bond,

In formula [1],

Y¹It indicates singly-bound or indicates to combine base, the combination base is selected from-O- ,-CH₂O-、-COO-、-OCO-、-NHCO-、-NH- Group in CO-O- and-NH-CO-NH-,

Y²Indicate the alkylidene or-CH of the carbon atom number 1~15 of singly-bound, straight-chain or branched₂-CH(OH)-CH₂, the alkylene Base can combine base A to interrupt by 1~3, still, not combine each other in conjunction with base A or Y²Indicate selected from phenyl ring, cyclohexane ring or Divalent cyclic group in heterocycle, any hydrogen atom in the cyclic group of the divalent cyclic group can be by the carbon of straight-chain or branched The carbon atom of the alkoxy of the carbon atom number 1~3 of the alkyl of atomicity 1~3, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom of the carbon atom number 1~3 of the alkyl containing fluorine of number 1~3, straight-chain or branched take Generation,

Y³Indicate that the alkylidene of singly-bound or carbon atom number 1~15, the alkylidene can be appointing in straight-chain, branched and ring-type One or their combination, the alkylidene can combine base A to interrupt, still, not combine each other in conjunction with base A by 1~3,

Y⁴It indicates singly-bound, or indicates the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, the ring-type of the divalent cyclic group Any hydrogen atom on base can be former by the carbon of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The alkyl containing fluorine of the carbon atom number 1~3 of the alkoxy of subnumber 1~3, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom of carbon atom number 1~3 replace or Y⁴Carbon atom number 17 of the expression with steroid skeleton~ 30 divalent organic group,

Y⁵Indicate the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, any hydrogen in the cyclic group of the divalent cyclic group Atom can be by the alkane of the carbon atom number 1~3 of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The carbon atom number 1~3 of the alkyl containing fluorine of the carbon atom number 1~3 of oxygroup, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom replace,

N indicates 0~4 integer, in the case where n is 2 or more, each Y⁵It can be the same or different,

Y⁶Indicate hydrogen atom, the alkyl of carbon atom number 1~18, the alkyl containing fluorine of carbon atom number 1~18, carbon atom number 1~18 Alkoxy or carbon atom number 1~18 the alkoxy containing fluorine, the alkyl of the carbon atom number 1~18, carbon atom number 1~18 The alkoxy containing fluorine of alkyl containing fluorine, the alkoxy of carbon atom number 1~18 and carbon atom number 1~18 can be straight chain Any one of shape, branched and ring-type or their combination, can by 1~3 combine base A interrupt, still, in conjunction with base A that This is not combined,

In Y²And Y³In the case where indicating the group other than singly-bound, Y²With Y³Combination can be singly-bound, can also via combine base A And combine,

In Y³And Y⁴In the case where indicating the group other than singly-bound, Y³With Y⁴Combination can be singly-bound, can also via combine base A And combine,

In Y⁴And Y⁵In the case where indicating the group other than singly-bound, Y⁴With Y⁵Combination can be singly-bound, can also via combine base A And combine,

In Y⁵And Y⁶In the case where indicating the group other than singly-bound, Y⁵With Y⁶Combination can be singly-bound, can also via combine base A And combine,

In the case where n is 2 or more, 1 Y⁵With the Y adjacent with its⁵Combination can be singly-bound, can also via in conjunction with base A and In conjunction with,

It indicates to be selected from-O- ,-CH in conjunction with base A₂Base in O- ,-COO- ,-OCO- ,-NHCO- ,-NH-CO-O- and-NH-CO-NH- Group,

Wherein, the number for the carbon atom for including in group shown in formula [1] adds up to 6~30.

2. cured film according to claim 1, which is formed, uses composition, the polymerizable group comprising C=C double bond of (B) ingredient For selected from least one of acryloyl group, methylacryloyl, vinyl, allyl and dimaleoyl imino.

3. cured film according to claim 1 or 2, which is formed, uses composition, 100 mass parts of (A) ingredient are based on, contain 10 matter Measure part~2000 mass parts (B) ingredient.

4. cured film described in any one of claim 1 to 3, which is formed, uses composition, (A) relative to every 100 mass parts Ingredient contains 0.1 mass parts~50 mass parts (C) ingredient.

5. a kind of orientation material, which is characterized in that be to make cured film formation composition according to any one of claims 1 to 4 Solidify and obtains.

6. a kind of phase difference material, which is characterized in that be to form use using by cured film according to any one of claims 1 to 4 Composition obtain cured film and formed.