KR20220108097A - Cured film forming composition, orientation material and retardation material - Google Patents

Abstract

[Problem] To provide a cured film-forming composition having excellent orientation sensitivity, excellent orientation, and providing an orientation material having excellent adhesion to a TAC film, and improved storage stability.
[Solutions] The cured film forming composition is (A) a compound having any one substituent selected from a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group, (B) a hydroxyl group, a carboxyl group, and an amino group. A hydrophilic polymer having two or more substituents, (C) a polymer obtained by polymerizing a monomer containing a N-hydroxymethyl compound or an N-alkoxymethyl (meth)acrylamide compound, (D) a crosslinking catalyst, and a C1 to C5 The solvent containing both the alcohol of and the C1-C4 alkylester of a C1-C4 fatty acid is contained. A cured film is formed using this cured film formation composition, and an orientation material is formed using the photo-alignment technique. A polymeric liquid crystal is apply|coated on the orientation material, it is made to harden|cure, and retardation material is obtained.

Description

Cured film forming composition, orientation material and retardation material

The present invention relates to a cured film forming composition, an orientation material, and a retardation material.

In the case of a circularly polarized glasses type 3D display, a phase difference material is usually disposed on a display element that forms an image such as a liquid crystal panel. In this phase difference material, two types of phase difference areas from which phase difference characteristics differ are respectively arrange|positioned regularly and plural, respectively, and comprise the patterned phase difference material. On the other hand, hereinafter, in the present specification, the 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.

A patterned retardation material can be produced by optically patterning the retardation material which consists of a polymeric liquid crystal, as disclosed by patent document 1, for example. The optical patterning of the retardation material made of polymerizable liquid crystal uses a photo-alignment technique known in the formation of an alignment material of a liquid crystal panel. That is, a coating film made of a material having a photo-alignment property is provided on a substrate, and two types of polarized light having different polarization directions are irradiated thereon. And a photo-alignment film is obtained as an orientation material in which two types of liquid-crystal orientation regions from which the orientation control direction of a liquid crystal differ are formed. A solution phase difference material containing a polymerizable liquid crystal is applied on the photo-alignment film to achieve alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

The antireflection film of the organic EL display is composed of a linear polarizer and a quarter-wave retardation plate, and the extraneous light directed toward the panel surface of the image display panel is converted into linearly polarized light by the linear polarizer, followed by a quarter-wave retardation plate converted to circular polarization by Here, the extraneous light by the circularly polarized light is reflected on the surface of the image display panel or the like, but the rotational direction of the polarization plane is reversed at the time of this reflection. As a result, the reflected light is converted from the quarter-wave retardation plate to the linearly polarized light in the direction blocked by the linear polarizing plate, and is then blocked by the subsequent linear polarizing plate, as a result of which, as a result, emission is significantly suppressed.

Regarding this 1/4 wavelength retardation plate, in Patent Document 2, a 1/2 wave plate and a 1/4 wave plate are combined to form a 1/4 wave retardation plate, so that this optical film is constructed by inverse dispersion characteristics. A method is proposed. In the case of this method, in a wide wavelength band provided for the display of a color image, an optical film can be constructed according to the inverse dispersion characteristic by using a liquid crystal material according to the positive dispersion characteristic.

Furthermore, in recent years, as a liquid crystal material applicable to this retardation layer, the thing provided with the reverse dispersion characteristic is proposed (patent document 3, 4). According to the liquid crystal material of such reverse dispersion characteristics, the phase difference layer is composed of a single layer, instead of forming a quarter-wave retardation plate by two layers of retardation layers by combining a half-wave plate and a quarter-wave plate. An optical film capable of securing the reverse dispersion characteristics and thereby securing a desired retardation in a wide wavelength band can be realized with a simple configuration.

An alignment layer is used to orient the liquid crystal. As a method of forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is useful in that it does not generate static electricity or dust, which is a problem of the rubbing method, and allows quantitative control of the alignment treatment. .

In the formation of an orientation material using the photo-alignment method, as a usable photo-alignment material, an acrylic resin or polyimide resin having a photodimerization site such as a cinnamoyl group and a chalcone group in a side chain is known. It has been reported that these resins exhibit the performance (hereinafter, also referred to as liquid crystal orientation) for controlling the orientation of the liquid crystal by polarized UV irradiation (refer to Patent Documents 5 to 7).

In addition, in a photo-alignment agent using a cinnamoyl moiety, there is an example in which a thermal crosslinking system is introduced to improve orientation sensitivity and impart solvent resistance (see Patent Documents 8 and 9).

Japanese Patent Laid-Open No. 2005-49865 Japanese Patent Laid-Open No. H10-68816 Specification of US Patent No. 8119026 Japanese Patent Laid-Open No. 2009-179563 Japanese Patent No. 3611342 publication Japanese Patent Laid-Open No. 2009-058584 Japanese Patent Publication No. 2001-517719 International Patent Application Publication No. WO2011/126022 International Patent Application Publication No. WO2014/010688

On the other hand, when a thermal crosslinking system is introduced into a cured film, particularly in a state in which a crosslinking agent and a crosslinking catalyst are coexisted, if the cured film forming composition can be stably stored, there is a great advantage in handling properties. Therefore, there is a demand for a simple method capable of improving the storage stability. Here, in Patent Document 8 and the like, there is a description that an alcohol solvent is preferable when a TAC substrate is used, and as this reason, it is described that the TAC film exhibits resistance. On the other hand, in those patent documents, it is not described that an alcohol solvent is added to stabilize the varnish, and in order to ensure adhesion between the TAC film and the orientation material, a fatty acid that dissolves TAC together with the alcohol solvent The mixing of the ester solvent is not described.

The present invention has been made based on the above knowledge and examination results. That is, the objective is to provide the cured film formation composition which has the outstanding orientation sensitivity, is excellent also in orientation, and is excellent also in adhesiveness with a TAC film, and is improved storage stability while providing the orientation material.

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

A first aspect of the present invention is

(A) a compound having any one substituent selected from a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group;

(B) a hydrophilic polymer having one or more substituents selected from a hydroxyl group, a carboxyl group and an amino group;

(C) a polymer obtained by polymerizing a monomer containing an N-hydroxymethyl compound or an N-alkoxymethyl (meth)acrylamide compound;

(D) a crosslinking catalyst, and

It is related with the cured film formation composition characterized by containing the solvent containing both C1-C5 alcohol and C1-C4 alkylester of a C1-C4 fatty acid.

1st aspect of this invention WHEREIN: It is preferable that the photo-alignment group of (A) component is a functional group of the structure which photodimerizes or photoisomerizes.

1st aspect of this invention WHEREIN: It is preferable that the photo-alignment group of (A) component is a cinnamoyl group.

1st aspect of this invention WHEREIN: It is preferable that the photo-alignment group of (A) component is group of an azobenzene structure.

1st aspect of this invention WHEREIN: It is preferable that (B) component is at least 1 sort(s) of polymer selected from the group which consists of polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.

1st aspect of this invention WHEREIN: It is preferable that (B) component is a cellulose or its derivative(s).

1st aspect of this invention WHEREIN: The (B) component has at least one of a polyethyleneglycol ester group and a C2-C5 hydroxyalkyl ester group, and at least one of a carboxyl group and a phenolic hydroxyl group. It is preferably a polymer.

1st aspect of this invention WHEREIN: (B) component has at least one of the monomer which has a polyethyleneglycol ester group, and the monomer which has a C2-C5 hydroxyalkyl ester group, The monomer which has a carboxyl group, and phenolic hydroxy It is preferable that it is an acrylic copolymer obtained by the polymerization reaction of the monomer containing at least one of the monomers which have a group.

Moreover, in the 1st aspect of this invention, it is preferable that (B) component is an acrylic polymer which has a hydroxyalkyl group in a side chain.

Moreover, in the 1st aspect of this invention, as (E) component, it is preferable to contain an adhesion|adherence improving component further.

1st aspect of this invention WHEREIN: It is preferable that the ratio of (A) component and (B) component is 5:95-60:40 by mass ratio.

1st aspect of this invention WHEREIN: Based on 100 mass parts which is the total amount of the compound of (A) component, and the polymer of (B) component, it is preferable to contain 10 mass parts - 150 mass parts (C)component. .

1st aspect of this invention WHEREIN: It is preferable to contain 0.01 mass parts - 10 mass parts (D)component with respect to 100 mass parts which is the total amount of the compound of (A) component, and the polymer of (B) component.

A 2nd aspect of this invention is obtained using the cured film formation composition of a 1st aspect of this invention, It relates to the orientation material characterized by the above-mentioned.

A 3rd aspect of this invention is formed using the cured film obtained from the cured film formation composition of the 1st aspect of this invention, It relates to the retardation material characterized by the above-mentioned.

According to the first aspect of the present invention, it is possible to provide an orientation material having excellent orientation sensitivity, excellent orientation, and excellent adhesion to a TAC film, and a cured film forming composition having improved storage stability.

According to the second aspect of the present invention, it is possible to provide an orientation material having excellent orientation sensitivity, pattern formability and transparency, and also excellent in orientation uniformity.

According to the third aspect of the present invention, it is possible to provide a retardation material that can be formed with high efficiency even on alkali glass and can be optically patterned.

<Cured film forming composition>

The cured film formation composition of this embodiment is the low molecular photo-alignment component which is (A) component, the hydrophilic polymer which is (B) component, and the N-hydroxymethyl compound or N-alkoxymethyl (meth) which is (C)component It contains the polymer which superposed|polymerized the monomer containing an acrylamide compound, and the crosslinking catalyst which is (D)component. In addition to (A) component, (B) component, (C) component, and (D), the cured film formation composition of this embodiment can also contain the component which improves the adhesiveness of the cured film as (E) component further. have. In addition, other additives may be contained as long as the effects of the present invention are not impaired.

Hereinafter, the detail of each component is demonstrated.

<(A) component>

(A) component contained in the cured film formation composition of this embodiment is the above-mentioned low molecular photo-alignment component.

And the low-molecular photo-alignment component which is (A) component can be made into the compound which has any one substituent chosen from a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group. In the compound having any one substituent selected from a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group, as described above, the photoreactive group constitutes a hydrophobic photoreactive moiety in the photoreactive component, a hydroxyl group, etc. This hydrophilic thermal reaction part is constituted.

On the other hand, in the present invention, the photo-alignment group refers to a functional group of a structural site to be photodimerized or photoisomerized.

The structural site for photodimerization is a site for forming a dimer by light irradiation, and specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Among them, a cinnamoyl group having high transparency and photodimerization reactivity in the visible region is preferable. In addition, the structural moiety to be photoisomerized refers to a structural moiety that changes into a cis-form and a trans-form upon irradiation with light, and specific examples thereof include a moiety composed of an azobenzene structure, a stilbene structure, and the like. Among these, the azobenzene structure is preferable at a point with high reactivity. The compound which has a photo-alignment group and a hydroxyl group is represented by a following formula, for example.

[Formula 1]

In the above formula, A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and X ¹ is one selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, or a combination thereof; A structure formed by bonding 1 to 3 units selected from alkylene having 1 to 18 carbon atoms, phenylene, biphenylene, or a combination thereof via two or more bonds is shown. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In that case, the alkyl group, phenyl group, biphenyl group and cyclohexyl group having 1 to 18 carbon atoms may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond or a urea bond. X ⁵ represents a hydroxyl group, a carboxyl group, an amino group, or an alkoxysilyl group. X represents a single bond, an oxygen atom or a sulfur atom. X ⁶ represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or a phenyl group. X ⁷ each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group, or an aliphatic ring group. Here, the C1-C20 alkylene group may be branched or linear may be sufficient as it.

On the other hand, in these substituents, phenylene, phenyl group, biphenylene and biphenyl group are selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group and a cyano group. It may be substituted by the same or different 1 or several substituents.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms. group, a halogen atom, a trifluoromethyl group or a cyano group.

(A) As a specific example of the compound which has the photo-alignment group which is a component and a hydroxyl group, For example, 4-(8-hydroxyoctyloxy) cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy) methyl cinnamate Ester, 4-(4-hydroxybutyloxy) cinnamic acid methyl ester, 4-(3-hydroxypropyloxy) cinnamic acid methyl ester, 4-(2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy Cinnamon methyl ester, 4-hydroxycinnamic acid methyl ester, 4-(8-hydroxyoctyloxy) cinnamic acid ethyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid ethyl ester, 4-(4-hydroxybutyloxy) ) Cinnamon ethyl ester, 4-(3-hydroxypropyloxy) cinnamic acid ethyl ester, 4-(2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxycinnamic acid ethyl ester , 4- (8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid phenyl ester, 4- (3-hydroxy) Roxypropyloxy) cinnamic acid phenyl ester, 4-(2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy) Cinnamon acid biphenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4-(4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4-(3-hydroxypropyloxy) cinnamic acid biphenyl ester , 4-(2-hydroxyethyloxy)cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl Ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4-(8-hydroxyoctyloxy) azobenzene, 4-(6-hydro hydroxyhexyloxy) azobenzene, 4-(4-hydroxybutyloxy) azobenzene, 4-(3-hydroxypropyloxy) azobenzene, 4-(2-hydroxyethyloxy) azobenzene, 4-hydroxymethyloxyazobenzene , 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy) chalcone, 4- ( 6-hydroxyhexyloxy) chalcone, 4-(4-hydroxybutyloxy) chalcone, 4-(3-hydroxypropyloxy) chalcone, 4-(2-hydroxyethyloxy) chalcone, 4-hydroxy Methyloxychalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyloxy)chalcone, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutyloxy)chalcone, 4'-(3-hydroxypropyloxy)chalcone, 4'-(2-hydroxyethyloxy)chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyl) Oxy)coumarin, 7-(6-hydroxyhexyloxy)coumarin, 7-(4-hydroxybutyloxy)coumarin, 7-(3-hydroxypropyloxy)coumarin, 7-(2-hydroxyethyloxy) ) Coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6-(4-hydroxybutyloxy)coumarin, 6-(3- Hydroxypropyloxy) coumarin, 6-(2-hydroxyethyloxy) coumarin, 6-hydroxymethyloxy coumarin, and 6-hydroxycoumarin are mentioned.

Specific examples of the compound having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxycinnamic acid, 3,4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4-(N,N- dimethylamino) cinnamic acid and the like.

Specific examples of the compound having a photo-alignment group and an amino group include methyl-4-aminocinnamic acid, ethyl-4-aminocinnamic acid, methyl-3-aminocinnamic acid, and ethyl-3-aminocinnamic acid.

(A) Although the above specific example is given as for the low molecular photo-alignment component which is a component, it is not limited to these.

In addition, when the photo-alignment component as component (A) is a compound having a photo-alignment group and a hydroxyl group, as the component (A), a compound having two or more photo-alignment groups and/or two or more hydroxyl groups in the molecule is used. it is possible Specifically, as component (A), a compound having two or more photo-alignment groups together with one hydroxyl group in a molecule, a compound having two or more hydroxyl groups together with one photo-alignment group in a molecule, and photo-alignment property in a molecule It is possible to use compounds each having two or more groups and hydroxyl groups. For example, about the compound which has each two or more of photo-alignment group and a hydroxyl group in a molecule|numerator, the compound represented by the following formula can be shown as the example.

[Formula 2]

By selecting such a compound suitably, control which raises the molecular weight of the photo-alignment component which is (A) component becomes possible. As a result, as described later, when the photo-alignment component as component (A) and the polymer as component (B) and the cross-linking agent as component (C) thermally react, the sublimation of the photo-alignment component as component (A) can be suppressed. have. And the cured film formation composition of this embodiment can form the orientation material with high photoreaction efficiency as a cured film.

Moreover, as a compound of (A) component in the cured film formation composition of this embodiment, it has a photo-alignment group, a hydroxyl group, a carboxyl group, and any one substituent selected from an amino group, It is a mixture of multiple types of compounds may be

<(B) component>

(B) component contained in the cured film formation composition of this embodiment is a hydrophilic polymer.

And the polymer which is (B) component can be set as the polymer (henceforth a specific polymer) which has 1 type(s) or 2 or more types of substituents chosen from a hydroxyl group, a carboxyl group, and an amino group.

Cured film formation composition of this embodiment WHEREIN: As a specific polymer which is (B) component, selection of the high hydrophilic polymer with high hydrophilicity is preferable so that it may become more hydrophilic than (A) component. The specific polymer is preferably a polymer having a hydrophilic group such as a hydroxyl group, a carboxyl group, or an amino group, and specifically, a polymer having one or two or more substituents selected from a hydroxyl group, a carboxyl group, and an amino group. do.

(B) As a polymer which is a component, For example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone Polyols, polyalkyleneimines, polyallylamines, celluloses (cellulose or derivatives thereof), phenol novolac resins, polymers having a linear or branched structure such as melamine-formaldehyde resins, cyclic polymers such as cyclodextrins, etc. can

Among them, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, or styrene may be applied.

(B) As a specific polymer which is a component, Preferably, at least one of hydroxyalkylcyclodextrins, celluloses, a polyethyleneglycol ester group, and a C2-C5 hydroxyalkyl ester group, a carboxyl group, and a phenolic hydroxy Acrylic polymers having at least one of hydroxy groups, acrylic polymers having an aminoalkyl group in a side chain, acrylic polymers having a hydroxyalkyl group in a side chain such as polyhydroxyethyl methacrylate, polyether polyols, polyester polyols, polycarbonate polyols and It is polycaprolactone polyol.

(B) An acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxyl group, which is a preferable example of the specific polymer of the component, As long as it is an acrylic polymer having a structure, it is not particularly limited with respect to the backbone of the main chain of the polymer constituting the acrylic polymer and the kind of side chains.

As the structural unit having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, a preferable structural unit is represented by the following formula [B1].

As the structural unit having at least one of a carboxyl group and a phenolic hydroxyl group, a preferable structural unit is represented by the following formula [B2].

[Formula 3]

In Formulas [B1] and [B2], X ³ and X ⁴ each independently represents a hydrogen atom or a methyl group, Y ¹ is H-(OCH ₂ CH ₂ ) _n -group, where the value of n is 2 to 50, preferably 2 to 10) or a hydroxyalkyl group having 2 to 5 carbon atoms, and Y ² represents a carboxyl group or a phenolic hydroxyl group.

(B) It is preferable that weight average molecular weights are 3,000-200,000, as for the acrylic polymer which is an example of a component, it is more preferable that it is 4,000-150,000, It is more preferable that it is 5,000-100,000. If the weight average molecular weight exceeds 200,000, the solubility in solvents may decrease and handleability may decrease. Heat resistance may fall. Meanwhile, the weight average molecular weight is a value obtained using polystyrene as standard data by gel permeation chromatography (GPC). Hereinafter, it is set similarly also in this specification.

(B) As a method for synthesizing an acrylic polymer as an example of component, a monomer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms (hereinafter also referred to as a b1 monomer), a carboxyl group and a phenol A method of copolymerizing a monomer having at least one of the sex hydroxyl groups (hereinafter also referred to as b2 monomer) is simple.

As a monomer which has the above-mentioned polyethyleneglycol ester group, the monoacrylate or monomethacrylate _of H-(OCH2CH2) _{n -} OH is mentioned. The value of n is 2 to 50, preferably 2 to 10.

As a monomer which has the above-mentioned C2-C5 hydroxyalkyl ester group, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate are mentioned.

As a monomer which has the above-mentioned carboxyl group, acrylic acid, methacrylic acid, and vinylbenzoic acid are mentioned, for example.

As a monomer which has the above-mentioned phenolic hydroxyl group, p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene are mentioned, for example.

In addition, in this embodiment, when synthesize|combining the acrylic polymer which is an example of (B) component, unless the effect of this invention is impaired, monomers other than b1 monomer and b2 monomer, specifically, a hydroxyl group and a carboxyl group A monomer which does not have all of them can be used together.

Examples of such monomers include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl methacrylate, butyl acrylate, isobutyl acrylate, and t-butyl acrylate. , methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, methacrylic acid ester compounds such as t-butyl methacrylate, maleimide, N-methyl maleimide , N-phenylmaleimide, and maleimide compounds such as N-cyclohexylmaleimide, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

The amount of the b1 monomer and b2 monomer used to obtain the acrylic polymer serving as an example of the component (B) is 2 mol% to 95 mol% of the b1 monomer based on the total amount of all monomers used to obtain the acrylic polymer serving as the component (B). , b2 It is preferable that the monomer is 5 mol% to 98 mol%.

When a monomer having only a carboxyl group is used as the b2 monomer, based on the total amount of all monomers used to obtain the acrylic polymer as component (B), the b1 monomer is 60 mol% to 95 mol%, and the b2 monomer is 5 mol% to 40 mol%. % is preferred.

On the other hand, when a monomer having only a phenolic hydroxyl group is used as the b2 monomer, it is preferable that the content of the b1 monomer is 2 mol% to 80 mol% and the content of the b2 monomer is 20 mol% to 98 mol%. When there is too little b2 monomer, liquid-crystal orientation tends to become inadequate, and when excessive, compatibility with (A) component falls easily.

The method for obtaining the acrylic polymer as an example of component (B) is not particularly limited, but for example, in a solvent in which the b1 monomer, the b2 monomer, and a monomer other than the b1 monomer and b2 monomer, and a polymerization initiator, etc. coexist in a solvent, 50 It is obtained by polymerization under a temperature of ℃ to 110 ℃. In that case, the solvent used will not be specifically limited if it dissolves monomers other than the b1 monomer and b2 monomer, and the b1 monomer and b2 monomer used as needed, a polymerization initiator, etc. in that case. As a specific example, it describes in the term of the <solvent> mentioned later.

(B) The acrylic polymer which has an aminoalkyl group in a side chain which is a preferable example of the specific polymer of component, For example, aminoalkyl, such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate Selected from the group consisting of polymerized ester monomers, or the aminoalkyl ester monomer, the b1 monomer, the b2 monomer, and a monomer other than these monomers, for example, a monomer having neither a hydroxyl group nor a carboxyl group. What copolymerized the 1 type, or 2 or more types of monomers used is mentioned.

(B) As an acrylic polymer which has a hydroxyalkyl group in a side chain which is a preferable example of the specific polymer of component, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl meth A product obtained by polymerizing hydroxyalkyl ester monomers such as acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate and hydroxypentyl methacrylate, or the hydroxyalkyl ester monomer; The above-mentioned b1 monomer, the above-mentioned b2 monomer, and monomers other than these monomers, for example, one or two or more types of monomers selected from the group consisting of monomers having neither a hydroxy group nor a carboxy group are copolymerized.

The acrylic polymer which is an example of (B) component obtained by the said method is the state of the solution melt|dissolved in the solvent normally.

In addition, the solution of the acrylic polymer, which is an example of component (B) obtained by the above method, is added to diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, then dried at room temperature under normal pressure or reduced pressure, or It can be heat-dried and it can be set as the powder of the acrylic polymer which is an example of (B) component. By the said operation, the polymerization initiator and unreacted monomer which coexist with the acrylic polymer which are an example of (B) component can be removed, As a result, the powder of the acrylic polymer which is an example of the refined (B) component is obtained. What is necessary is just to make the obtained powder re-dissolve in a solvent again, and just to perform said operation repeatedly, when refinement|purification cannot fully be carried out by one operation.

(B) Polyether polyol which is a preferable example of the specific polymer of component includes polyethylene glycol, polypropylene glycol and propylene glycol, Furthermore, polyhydric alcohol, such as bisphenol A, triethylene glycol, sorbitol, propylene oxide and polyethylene glycol , polypropylene glycol, etc. may be added or condensed. Specific examples of the polyether polyol include ADEKA Adeka polyether P series, G series, EDP series, BPX series, FC series, CM series, Nichiyu Uniox (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB- 400, Nonion (trademark) LT-221, ST-221, OT-221, etc. are mentioned.

(B) As a polyester polyol which is a preferable example of the specific polymer of a component, polyhydric carboxylic acids, such as adipic acid, sebacic acid, isophthalic acid, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. What made diol react is mentioned. Specific examples of the polyester polyol include DIC polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X- 668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560, Kurarayje 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, etc. are mentioned.

(B) As a polycaprolactone polyol which is a preferable example of the specific polymer of component, what carried out ring-opening polymerization of epsilon caprolactam using polyhydric alcohols, such as trimethylol propane and ethylene glycol, as an initiator is mentioned. Specific examples of polycaprolactone polyol include DIC's Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical's Fraxel (registered trademark) 205, L205AL , 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

(B) As a polycarbonate polyol which is a preferable example of the specific polymer of component, what made diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. react with polyhydric alcohols, such as trimethylol propane and ethylene glycol, is mentioned. Specific examples of the polycarbonate polyol include Fraxel (registered trademark) CD205, CD205PL, CD210, CD220, C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Daicel Chemicals.

(B) As a cellulose which is a preferable example of the specific polymer of component, hydroxyalkyl celluloses, such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, etc. of hydroxyalkylalkyl celluloses and cellulose, and for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

(B) As a cyclodextrin which is a preferable example of the specific polymer of component, Cyclodextrin, such as alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin, methyl-alpha-cyclodextrin, methyl- beta-cyclodextrin, and methyl Methylated cyclodextrin such as -γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2 -Hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ -Cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin and hydroxyalkyl cyclodextrins such as 2,3-dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin.

As a melamine-formaldehyde resin which is a preferable example of the specific polymer of (B) component, it is resin obtained by polycondensing melamine and formaldehyde, and is represented by a following formula.

[Formula 4]

In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

As for the melamine formaldehyde resin of (B) component, it is preferable that the methylol group produced|generated at the time of polycondensation of melamine and formaldehyde from a viewpoint of storage stability is alkylated.

The method for obtaining the melamine formaldehyde resin of component (B) is not particularly limited, but generally it is synthesized by mixing melamine and formaldehyde, making it slightly alkaline using sodium carbonate or ammonia, and then heating at 60-100 ° C. . The methylol group can be alkoxylated by reacting again with an alcohol.

(B) It is preferable that weight average molecular weights are 250-5,000, As for the melamine formaldehyde resin of a component, it is more preferable that it is 300-4,000, It is more preferable that it is 350-3,500. If the weight average molecular weight exceeds 5,000 and is excessive, the solubility in solvents may decrease and handleability may decrease. If the weight average molecular weight is too small, the weight average molecular weight is less than 250. Heat resistance may fall.

In this invention, the melamine formaldehyde resin of (B) component can also be used with the liquid form or the solution form which re-dissolved the refined liquid in the solvent mentioned later.

Moreover, in this invention, the mixture of the melamine formaldehyde resin of multiple types (B) component may be sufficient as the melamine formaldehyde resin of (B) component.

(B) As a phenol novolak resin which is a preferable example of the specific polymer of component, a phenol- formaldehyde polycondensate etc. are mentioned, for example.

Cured film formation composition of this embodiment WHEREIN: The polymer of (B) component can also be used in the form of a solution which melt|dissolved again in the solvent mentioned later in the form of powder or refined powder.

In addition, the cured film formation composition of this embodiment WHEREIN: The mixture of multiple types of the polymer of (B) component may be sufficient as the polymer of (B) component.

<(C)component>

(C)component contained in the cured film formation composition of this embodiment is the polymer which superposed|polymerized the monomer containing an N-hydroxymethyl compound or N-alkoxymethyl (meth)acrylamide compound.

Examples of such a polymer include a polymer obtained by copolymerizing a monomer such as N-alkoxymethylacrylamide or N-hydroxymethylacrylamide alone or with a copolymerizable monomer. Examples of such polymers include poly(N-butoxymethylacrylamide), poly(N-ethoxymethylacrylamide), poly(N-methoxymethylacrylamide), poly(N-hydroxymethylacrylamide), and poly(N-hydroxymethylacrylamide). amide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-butoxymethylacrylamide and methyl methacrylate, and a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate Copolymers and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like are mentioned. The polymer has a weight average molecular weight of 1,000 to 500,000, preferably, 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

The polymer of these (C)component can be used individually or in combination of 2 or more type.

Content of the polymer which superposed|polymerized the monomer containing the N-hydroxymethyl compound or N-alkoxymethyl (meth)acrylamide compound of (C)component in the cured film formation composition of this embodiment is (A) component Based on 100 mass parts which is the total amount of the polymer of a phosphorus compound and (B) component, it is preferable that they are 10 mass parts - 150 mass parts, More preferably, they are 20 mass parts - 100 mass parts. (C) When content of the polymer which superposed|polymerized the monomer containing N-hydroxymethyl compound or N-alkoxymethyl (meth)acrylamide compound of component is too little, solvent resistance and heat resistance of the cured film obtained from a cured film formation composition This falls, and the sensitivity at the time of optical alignment falls. On the other hand, when the content is excessive, the optical orientation and storage stability may decrease.

<(D)component>

In addition to (A) component, (B) component, and (C)component, the cured film formation composition of this embodiment contains a crosslinking catalyst as (D)component further.

(D) As a crosslinking catalyst which is a component, it can be set as an acid or a thermal acid generator, for example. When this (D)component accelerates|stimulates the thermosetting reaction of the cured film formation composition of this embodiment, it is effective.

(D) As the component, a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, and a compound that thermally decomposes to generate an acid during pre-baking or post-baking, that is, a compound that generates an acid by thermal decomposition at a temperature of 80°C to 250°C. It is not limited. Such compounds include, for example, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, tri Fluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-Perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid Sulfonic acids, such as sulfonic acids, its hydrate, salt, etc. are mentioned. As a compound which generates an acid by heat, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, 1 ,2,3-phenylentris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonate Butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p- Toluenesulfonate, 2-hydroxybutylp-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and the compound represented by the following formula, etc. are mentioned.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

With respect to 100 mass parts which content of (D)component in the cured film formation composition of this embodiment is the total amount of the compound of (A) component, and the polymer of (B)component, Preferably 0.01 mass part - 10 It is a mass part, More preferably, it is 0.1 mass part - 6 mass parts, More preferably, it is 0.5 mass part - 5 mass parts. (D) By making content of component into 0.01 mass part or more, sufficient thermosetting and solvent tolerance can be provided, and the high sensitivity with respect to light irradiation can also be provided.

<(E) component>

The cured film formation composition of this invention may contain the component (henceforth a close_contact|adherence improving component.) which improves the adhesiveness of the cured film formed as (E) component.

(E) The adhesion-improving component is a covalent bond between the polymerizable functional group of the polymerizable liquid crystal and the cross-linking reaction site of the alignment material so that the adhesion between the layer of the polymerizable liquid crystal and the alignment material obtained from the cured film forming composition of the present invention is improved. can be linked by As a result, the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesiveness even under conditions of high temperature and high humidity, and can exhibit high durability against peeling etc. .

(E) As a component, the monomer and polymer which have group chosen from a hydroxyl group and N-alkoxy methyl group, and a polymeric group are preferable.

As such component (E), the compound which has a hydroxyl group and a (meth)acryl group, the compound which has an N-alkoxymethyl group and a (meth)acryl group, the polymer etc. which have an N-alkoxymethyl group and a (meth)acryl group are mentioned. Hereinafter, each specific example is shown.

(E) As an example of a component, the polyfunctional acrylate containing a hydroxyl group (henceforth, it is also mentioned hydroxyl-group containing polyfunctional acrylate.) is mentioned.

(E) As a hydroxyl-group containing polyfunctional acrylate which is an example of a component, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. are mentioned, for example.

(E) As an example of a component, the compound which has one acryl group and one or more hydroxyl groups is also mentioned.

Moreover, as a compound of (E)component, the compound which has at least 1 polymerizable group containing a C=C double bond in 1 molecule, and at least 1 N-alkoxymethyl group is mentioned.

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.

As the compound having at least one polymerizable group containing a C=C double bond and at least one N-alkoxymethyl group in one molecule, preferably, for example, a compound represented by the following formula (X1) is exemplified can

[Formula 11]

(Wherein, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)

Specific examples of the compound represented by the formula (X1) include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N- and acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as butoxymethyl (meth)acrylamide. On the other hand, (meth)acrylamide means both methacrylamide and acrylamide.

(E) As another aspect of the compound which has a polymeric group containing C=C double bond of component and N-alkoxymethyl group, Preferably, the following compound is mentioned, for example.

[Formula 12]

To 100 mass parts of the orientation component which is (A) component, content of (E) component in the liquid crystal aligning agent of embodiment of this invention becomes like this. Preferably it is 1 mass part - 100 mass parts, More preferably It is 5 mass parts - 70 mass parts.

<solvent>

The cured film formation composition of this embodiment is mainly used in the solution state melt|dissolved in the solvent. The solvent used in that case contains a C1-C4 alkylester of a C1-C4 fatty acid, (A) component, (B) component, and (C)component, as needed (D)component, and/ Alternatively, other additives described later may be dissolved therein, and other compositions, types, and the like are not particularly limited.

As a C1-C4 alkylester of a C1-C4 fatty acid, Formula: R ¹ COOR ² (provided that R ¹ is a hydrogen atom or an alkyl group having preferably 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, , R ² is an alkyl group having 1 to 4 carbon atoms). Preferred examples include methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, i-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -butyl, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, or i-butyl propionate. In particular, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, or i-propyl propionate are preferable. One type or two or more types of these can be used.

Examples of the alcohol having 1 to 5 carbon atoms include methanol, ethanol, n-propanol, i-propanol, n-butanol, s-butanol, t-butanol, and n-pentanol. Among these, primary and secondary alcohols are preferable from the viewpoint of easy capping.

Moreover, the cured film formation composition of this invention may contain other solvent other than C1-C5 alcohol and C1-C4 alkylester of a C1-C4 fatty acid.

Specific examples of other solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2- Pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionate ethyl, ethoxyethyl acetate, ethyl hydroxyacetate, 2-hydroxyl Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, butyl lactate, N and N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

<Other additives>

Furthermore, the cured film formation composition of this embodiment is a sensitizer, a silane coupling agent, surfactant, a rheology modifier, a pigment, dye, a storage stabilizer, and an antifoamer as needed unless the effect of this invention is impaired. , antioxidants and the like.

For example, a sensitizer is effective in promoting a photoreaction, after forming a thermosetting film using the cured film formation composition of this embodiment.

As a sensitizer which is an example of another additive, benzophenone, anthracene, anthraquinone, thioxanthone, etc. and its derivative(s), a nitrophenyl compound, etc. are mentioned. Among these, benzophenone derivatives and nitrophenyl compounds are preferable. Specific examples of preferred compounds include N,N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, 5-nitroindole, etc. are mentioned. In particular, N,N-diethylaminobenzophenone which is a derivative of benzophenone is preferable.

These sensitizers are not limited to said thing. In addition, a sensitizer can be used individually or in combination of 2 or more types of compounds.

The use ratio of the sensitizer in the cured film formation composition of this embodiment is 0.1 mass part - 20 mass with respect to 100 mass parts which is the total mass of the specific copolymer of (A) component, and the acrylic polymer of (B) component It is preferable that it is negative, More preferably, it is 0.2 mass part - 10 mass parts. When this ratio is too little, the effect as a sensitizer may not fully be acquired, and when excessive, the fall of the transmittance|permeability and the roughening of a coating film may generate|occur|produce.

<Preparation of a cured film forming composition>

The cured film formation composition of this embodiment is (A) the compound which has any one substituent chosen from a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group, (B) 1 type chosen from a hydroxyl group, a carboxyl group, and an amino group or a hydrophilic polymer having two or more substituents, (C) a polymer obtained by polymerizing a monomer containing a N-hydroxymethyl compound or an N-alkoxymethyl (meth)acrylamide compound, (D) a crosslinking catalyst, and a carbon number of 1 to The solvent containing both the alcohol of 5 and the C1-C4 alkylester of a C1-C4 fatty acid is contained. In addition, other additives may be contained as long as the effects of the present invention are not impaired.

(A) As for the compounding ratio of component and (B) component, 5:95-60:40 are preferable at the point of liquid-crystal orientation and solvent tolerance by mass ratio.

It is preferable that the content ratio of a C1-C5 alcohol solvent and a C1-C4 fatty acid C1-C4 alkylester solvent is 10:90-90:10 by mass ratio. In addition, in the case of containing the above other solvents, it is preferable that the total amount of the alcohol solvent having 1 to 5 carbon atoms and the solvent having 1 to 4 carbon atoms of the fatty acid having 1 to 4 carbon atoms in the entire solvent is 30% by mass to 99% by mass. do.

The compounding ratio in the case of using the cured film formation composition of this embodiment as a solution, a preparation method, etc. are demonstrated in full detail below.

Although the ratio of solid content in the cured film formation composition of this embodiment is not specifically limited as long as each component is melt|dissolving in the solvent uniformly, It is 1 mass % - 80 mass %, Preferably it is 3 mass % thru|or 60 mass %, More preferably, it is 5 mass % - 40 mass %. Here, solid content means what removed the solvent from all the components of a cured film formation composition.

The preparation method of the cured film formation composition of this embodiment is not specifically limited. As a preparation method, (A) component, (E)component etc. are put into the solvent derived from (B) component or (C)component as needed, for example, and C1-C4 of a C1-C4 fatty acid After adding an alkyl ester, then adding an alcohol solvent having 1 to 5 carbon atoms, and then adding component (D) to make a uniform solution, or at an appropriate step of this preparation method, if necessary, component (E) or , and a method of mixing by additionally adding other additives.

Moreover, it is preferable to use, after filtering the solution of the prepared cured film formation composition using the filter etc. whose hole diameter is about 0.2 micrometer.

<Cured film, alignment material and phase difference material>

The solution of the cured film forming composition of this embodiment is applied to a substrate (for example, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a substrate, a glass substrate, Quartz substrate, ITO substrate, etc.) or film (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc. A cured film can be formed by coating, roll application, slit application, rotational application following the slit, inkjet application, printing, etc. to form a coating film, and then drying by heating on a hot plate or oven or the like.

As the conditions for drying by heat, the crosslinking reaction by the crosslinking agent may proceed to such an extent that the component of the alignment material formed into the cured film does not elute to the polymerizable liquid crystal solution applied thereon, for example, at a temperature of 60°C to 200°C. A heating temperature and a heating time appropriately selected within the range of from 0.4 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 70°C to 160°C, 0.5 minutes to 10 minutes.

The film thickness of the cured film formed using the curable composition of this embodiment is, for example, 0.05 micrometer - 5 micrometers, Considering the level|step difference of the board|substrate to be used, and an optical and electrical property, it can select suitably.

The cured film formed in this way can function as an orientation material, ie, a member which orientates the compound which has liquid crystals, such as a liquid crystal, by performing polarization|polarized-light UV irradiation.

As a method of irradiating polarized UV, usually, ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is used, and it is carried out by irradiating linearly polarized light from the perpendicular or oblique direction at room temperature or in a heated state.

Since the orientation material formed from the cured film composition of this embodiment has solvent resistance and heat resistance, on this orientation material, after apply|coating the retardation material which consists of a polymeric liquid crystal solution, by heating to the phase transition temperature of a liquid crystal, the retardation material is liquid-crystal state and oriented on the orientation material. And the retardation material which became an orientation state can be hardened as it is, and the retardation material can be formed as a layer which has optical anisotropy.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the board|substrate which forms an orientation material is a film, the film which has the retardation material of this embodiment is useful as retardation film. The retardation material forming such a retardation material is in a liquid crystal state, and there are some that take an orientation state such as horizontal orientation, cholesteric orientation, vertical orientation, hybrid orientation, etc. on the orientation material. Can be used.

In addition, when manufacturing the patterned retardation material used for 3D display, to the cured film formed by the above-mentioned method from the cured film composition of this embodiment from a predetermined reference|standard through the mask of a line and space pattern, for example, , +45 degrees of polarized UV exposure, and then, after removing the mask, polarized UV exposure is carried out in a -45 degree direction to obtain an alignment material in which two types of liquid crystal alignment regions having different orientation control directions of liquid crystals are formed. Then, after apply|coating the retardation material which consists of a polymeric liquid crystal solution, by heating to the phase transition temperature of a liquid crystal, the retardation material is made into a liquid crystal state, and it is oriented on an alignment material. And by hardening the phase difference material which became an orientation state as it is, the patterned phase difference material in which two types of phase difference areas from which phase difference characteristics differ were arrange|positioned regularly, respectively in multiple numbers can be obtained.

Further, using two substrates having the alignment material of the present embodiment formed as described above, and pasting the alignment materials on both substrates so that they face each other through a spacer, liquid crystal is injected between the substrates, and liquid crystal It can also be set as this aligned liquid crystal display element.

Thereby, the cured film formation composition of this embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

Example

Hereinafter, the present invention will be specifically described by way of examples of the present invention, but the present invention is not limited to these and interpreted.

[Abbreviations used in the examples]

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

<Raw material>

BMAA: N-butoxymethylacrylamide

AIBN: α,α′-azobisisobutyronitrile

<Component A>

MCA: 4-methoxycinnamic acid

[Formula 13]

<Component B>

PB-1

[Formula 14]

<C component>

HPC-SSL: Hydroxypropyl Cellulose

<Component D>

PTSA: p-toluenesulfonic acid monohydrate

<E component>

KAYARAD PET-30

<solvent>

Each resin composition of Examples and Comparative Examples contains a solvent, and as the solvent, propylene glycol monomethyl ether (PM), butyl acetate (BA), ethyl acetate (EA), 2-propanol (IPA), denatured ethanol (IPM) : ethanol/methanol/IPA=85.5/1.1/13.4) was used.

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example is as follows using a gel permeation chromatography (GPC) apparatus (HLC-8320) manufactured by Tosoh Corporation, a column manufactured by Tosoh Corporation (TSKgel ALPHA4000, TSKgel ALPHA3000). It was measured in the same way.

In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

Column temperature: 40℃

Eluent: tetrahydrofuran

Flow rate: 1.0 mL/min

Standard sample for calibration curve: standard polystyrene manufactured by Toso Corporation (molecular weights 427,000, 190,000, 37,900, 18,100, 5,970, 2,420, 1,010)

<Measurement of viscosity of liquid crystal alignment material>

Apparatus: EMS-1000 made by Kyoto Electronics Industry Co., Ltd.

Measuring temperature: 25℃

Probe size: 2.0mmΦ

RPM: 700rpm

Measurement time: 1 second

<Synthesis of B component>

<Polymerization Example-1>

An acrylic polymer solution was obtained by dissolving 100.0 g of BMAA and 1.0 g of AIBN as a polymerization catalyst in 193.5 g of PM, and reacting at 80° C. for 20 hours. Mn of the obtained acrylic polymer was 10,000, and Mw was 23,000. The acrylic polymer solution was gradually added dropwise to 2000.0 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PB-1).

<Preparation Example 1>

(A) 0.054 g of MCA as component, 0.378 g of PB-1 obtained in Polymerization Example-1 as (B) component, 0.144 g of HPC-SSL as (C) component, 0.144 g of PET-30 as (E) component (Nippon Chemicals) Co., Ltd.) was mixed, PM 2.484 g, BA 4.968 g, and IPA 0.828 g as solvents were added thereto, stirred for 1 hour, and dissolved visually to obtain a solution. Next, the liquid crystal aligning agent (A-1) was prepared by filtering this obtained solution with the filter with a hole diameter of 0.2 micrometer.

<Preparation Examples 2-6>

Except having used each component of the kind and compounding quantity shown in following Table 1, it operated similarly to Preparation Example 1, and (A-2)-(A-5), (B-1) was prepared.

[Table 1]

<Preparation of catalyst solution>

<Preparation Example 7>

(D) As a component, PM 18.0g was added as 2.0 g of PTSA, and a solvent, it stirred for 1 hour, and it confirmed that it melt|dissolved visually. A catalyst solution (D-1) was prepared by filtering the solution through a filter having a hole diameter of 0.2 µm.

<Preparation of cured film forming composition (liquid crystal aligning agent)>

<Example 1>

Liquid-crystal aligning agent AL-1 was obtained by adding EA 0.60g for 2.00 g of A-1 obtained in Preparation Example 1, 0.06 g for C-1 obtained by Preparation Example 7, and a dilution solvent, and stirring for 1 minute.

<Example 2>

Except having used A-2 obtained in Preparation Example 2, it prepared similarly to Example 1, and obtained liquid-crystal aligning agent AL-2.

<Example 3>

Except having used A-3 obtained by the preparation example 3, it prepared similarly to Example 1, and obtained liquid-crystal aligning agent AL-3.

<Example 4>

Except having used A-4 obtained by the preparation example 4, it prepared similarly to Example 1, and obtained liquid-crystal aligning agent AL-4.

<Example 5>

Except having used A-5 obtained in Preparation Example 5, it prepared similarly to Example 1, and obtained liquid-crystal aligning agent AL-5.

<Comparative Example 1>

Except having used B-1 obtained by the preparation example 6, it prepared similarly to Example 1, and obtained liquid-crystal aligning agent BL-1.

<Preparation of polymerizable liquid crystal solution for horizontal alignment>

<Preparation Example 9>

1.57 g of LC-242, a polymerizable liquid crystal for horizontal alignment (manufactured by BASF), 0.047 g of Irgacure907 (manufactured by BASF), a photo-radical initiator, and 0.008 g of BYK-361N, a leveling material, are added, and further as a solvent, NMP 6.55 g, cyclopentane 9.83 g of hot water was added, stirred for 2 hours, it was confirmed that it was melt|dissolving visually, and 9 mass % of polymerizable liquid crystal solution LC-1 was obtained.

<Formation of liquid crystal alignment film and production of retardation film>

<Example 7>

The liquid crystal aligning agent (AL-1) obtained in Example 1 was applied to a wet film thickness of 10 μm using a bar coater on a TAC film as a substrate. Heat-drying was performed for 1 minute at 120 degreeC in the heat circulation type oven, and the cured film was formed on the film. Next, 313 nm linearly polarized light was vertically irradiated to the surface of this cured film with the exposure amount of 10 mJ/cm< ² >, and the liquid crystal aligning film was formed. A polymerizable liquid crystal solution LC-1 for horizontal alignment was applied to the liquid crystal alignment layer with a wet film thickness of 34 μm using a bar coater. Then, after heating and drying at 120 ° C. for 2 minutes in an oven, the polymerizable liquid crystal was cured by vertically irradiating 365 nm of unpolarized light with an exposure amount of 500 mJ/cm ² under nitrogen to prepare a retardation film.

<Examples 8-11, Comparative Examples 3-4>

(AL-2) to (AL-5) and (BL-1) were used as liquid crystal aligning agents, and a retardation film was prepared in the same manner as in Example 7.

Each of the retardation films produced above was evaluated by the following method. Table 2 shows the evaluation results.

<Evaluation of orientation>

The retardation film on the produced substrate was sandwiched between a pair of polarizing plates, and the state of expression of the retardation characteristics under cross nicol was observed visually. It described in the column of "orientation property" by making into (circle) the thing in which the phase difference was expressed without a defect, and making x the thing in which the phase difference was not expressed.

<Adhesiveness evaluation>

Using a cutter knife, 100 cuts were made on the base wood at intervals of 1 mm on the retardation film on the produced substrate, and the adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd., 24mm width) was strongly pressed. By peeling at a time, it was evaluated by the number of grids remaining. If all remained, ○, if some were peeled off, △, if all peeled off, as ×, and described in the "Adhesiveness" column.

[Table 2]

<Evaluation of viscosity of liquid crystal aligning agent>

The viscosity was measured about liquid crystal aligning agent AL-1 - AL-6 prepared in Examples 1-6, and BL-1 and BL-2 prepared in Comparative Examples 1-2. The liquid crystal aligning agent obtained in Examples 1-6 and Comparative Examples 1-2 was stored at room temperature for a predetermined time, the viscosity was measured similarly, and it is described in Table 3.

[Table 3]

Although it turns out that it is a liquid crystal aligning agent composition from which orientation and adhesiveness can be obtained from the result of Table 2, from the result of Table 3, it becomes possible to stabilize the viscosity after liquid crystal aligning agent preparation by adding a lower alcohol as a solvent composition.

The cured film forming composition according to the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display device or an optically anisotropic film provided inside or outside a liquid crystal display device, and in particular, patterning retardation of 3D display It is suitable as a material for forming ash. Furthermore, materials for forming cured films such as protective films, planarization films, and insulating films in various displays such as thin film transistor (TFT) liquid crystal display elements and organic EL elements, in particular, interlayer insulating films of TFT-type liquid crystal elements, protective films of color filters Alternatively, it is also suitable as a material for forming an insulating film or the like of an organic EL device.

Claims (15)

(A) a compound having any one substituent selected from a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group;
(B) a hydrophilic polymer having one or more substituents selected from a hydroxyl group, a carboxyl group and an amino group;
(C) a polymer obtained by polymerizing a monomer containing an N-hydroxymethyl compound or an N-alkoxymethyl (meth)acrylamide compound;
(D) a crosslinking catalyst, and
The cured film formation composition characterized by containing the solvent containing both C1-C5 alcohol and C1-C4 alkylester of a C1-C4 fatty acid. The method of claim 1,
(A) The photo-alignment group of component is a functional group of the structure to photodimerize or photoisomerize, The cured film formation composition characterized by the above-mentioned. 3. The method of claim 1 or 2,
(A) Photo-alignment group of component is cinnamoyl group, The cured film formation composition characterized by the above-mentioned. 3. The method of claim 1 or 2,
(A) Photo-alignment group of component is group of azobenzene structure, The cured film formation composition characterized by the above-mentioned. 5. The method according to any one of claims 1 to 4,
(A) Component has 2 or more hydroxyl groups, The cured film formation composition characterized by the above-mentioned. 6. The method according to any one of claims 1 to 5,
(B) Component is at least 1 sort(s) of polymer chosen from the group which consists of polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol, The cured film formation composition characterized by the above-mentioned. 6. The method according to any one of claims 1 to 5,
(B) Component is cellulose or its derivative(s), The cured film formation composition characterized by the above-mentioned. 6. The method according to any one of claims 1 to 5,
(B) Component is an acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxy group, A cured film forming composition characterized in that . 6. The method according to any one of claims 1 to 5,
(B) Component is an acrylic polymer which has a hydroxyalkyl group in a side chain, The cured film formation composition characterized by the above-mentioned. 10. The method according to any one of claims 1 to 9,
(E) As a component, it further contains an adhesion improving component, The cured film formation composition characterized by the above-mentioned. 11. The method according to any one of claims 1 to 10,
(A) Ratio of component and (B) component is 5:95-60:40 by mass ratio, The cured film formation composition characterized by the above-mentioned. 12. The method according to any one of claims 1 to 11,
(A) Based on 100 mass parts which is the total amount of the compound of component and (B) component, 10 mass parts - 150 mass parts (C)component are contained, The cured film formation composition characterized by the above-mentioned. 13. The method according to any one of claims 9 to 12,
(A) The cured film formation composition containing 0.01 mass parts - 10 mass parts (D)component with respect to 100 mass parts which are the total amounts of the compound of a component and the polymer of (B)component. It is obtained using the cured film formation composition in any one of Claims 1-13, The orientation material characterized by the above-mentioned. It is formed using the cured film obtained from the cured film formation composition in any one of Claims 1-13, The retardation material characterized by the above-mentioned.