KR20220012859A - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

[Problem] An alignment material that has excellent orientation sensitivity and excellent alignment uniformity, has resistance to solvents in liquid crystal solution even when it is a thin film, and can function as a protective layer to protect a film substrate, and a cured film for obtaining it A composition is provided.
[Solutions] The cured film forming composition is (A) a compound having one substituent selected from the group consisting of a photo-alignment group, a hydroxyl group, a carboxyl group and an amino group, (B) at least N-alkoxymethyl (meth)acrylamide A polymer formed by polymerizing a monomer containing a compound, and (C) a polymer formed by polymerizing a monomer containing at least an N-hydroxyalkyl (meth)acrylamide compound, and optionally a crosslinking catalyst as component (D) and (E) an adhesion improving component as a component. 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, alignment material and retardation material

TECHNICAL FIELD This invention relates to a cured film formation composition, an orientation material, and retardation material.

In the case of a circularly polarized glasses type 3D display, it is common that a phase difference material is 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 comprises the patterned phase difference material. On the other hand, 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 a 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 of optical orientation is provided on a substrate, and two types of polarized light having different polarization directions are irradiated thereon. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid-crystal alignment regions having different orientation control directions of liquid crystal 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 polarizing plate and a quarter-wave retardation plate, and the extraneous light directed to the panel surface of the image display panel is converted into linearly polarized light by the linear polarizing plate, followed by a quarter-wave retardation plate converted to circular polarization by Here, extraneous light due to 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, this reflected light is converted from the quarter-wave retardation plate to linearly polarized light in the direction blocked by the linear polarizing plate, and then blocked by the continuous linear polarizing plate. emission is significantly suppressed.

Regarding this quarter-wave retardation plate, in Patent Document 2, a quarter-wave retardation plate is constituted by combining a half-wave plate and a quarter-wave plate, whereby this optical film is constructed according to the reverse dispersion characteristics. A method is proposed. In the case of this method, in a wide wavelength band provided for 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.

Also, in recent years, as a liquid crystal material applicable to this retardation layer, one having an inverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such inverse dispersion characteristics, the retardation layer is formed by a single layer instead of forming a quarter-wave retardation plate by two retardation layers by combining a half-wave plate and a quarter-wave plate. In this way, reverse dispersion characteristics can be secured, and accordingly, an optical film capable of 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 the alignment layer, for example, a rubbing method or a photo-alignment method are 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 alignment material using the photo-alignment method, 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 as a usable photo-alignment material. 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 irradiating with polarized UV light (refer to Patent Documents 5 to 7).

Moreover, solvent resistance is calculated|required by an orientation layer other than liquid-crystal orientation ability. For example, an orientation layer may be exposed to a heat|fever or a solvent in the manufacturing process of a phase difference material. When the alignment layer is derived from a solvent, there is a fear that the liquid crystal alignment ability is remarkably lowered.

Accordingly, in Patent Document 8, for example, in order to obtain a stable liquid crystal alignment ability, a liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking by light and a structure to be crosslinked by heat, and a crosslinking reaction by light A liquid crystal aligning agent containing a polymer component having this possible structure and a compound having a structure crosslinked by heat has been proposed.

Japanese Patent Laid-Open No. 2005-49865 Japanese Patent Laid-Open No. H10-68816 US Patent No. 8119026 Specification 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 Japanese Patent No. 4207430

As mentioned above, the retardation material laminates|stacks the layer of the hardened|cured polymeric liquid crystal on the photo-alignment film which is an orientation material, and is comprised. Accordingly, there is a need for development of an alignment material that is compatible with excellent liquid crystal alignment and solvent resistance.

However, according to the examination of the present inventors, it is known that sufficient characteristics are not obtained when the acrylic resin which has photodimerization sites, such as a cinnamoyl group and a chalcone group, in a side chain is applied to formation of retardation material. In particular, in order to form an orientation material by irradiating these resin with polarized light UV, and to produce the retardation material which consists of a polymerizable liquid crystal using the orientation material, a large polarization|polarized-light UV exposure amount is required. The polarized UV exposure amount is significantly higher than the polarized UV exposure dose sufficient to orient the liquid crystal for a normal liquid crystal panel (for example, about 30 mJ/cm ² .).

The reason that the amount of polarized UV exposure increases, in the case of retardation material formation, unlike the liquid crystal for liquid crystal panels, a polymerizable liquid crystal is used in the state of a solution, and it is mentioned that it is apply|coated on the alignment material.

When an alignment material is formed using an acrylic resin having a photodimerization site such as a cinnamoyl group in the side chain, and the polymerizable liquid crystal is to be oriented, in the acrylic resin, photocrosslinking by photodimerization reaction is performed. do And it is necessary to perform polarized light irradiation with a large exposure amount until resistance with respect to a polymeric liquid crystal solution is expressed. In order to orientate the liquid crystal of a liquid crystal panel, it is good to dimerize only the surface of the orientation material of a photo-alignment property normally. However, when it is intended to express solvent resistance in an orientation material using conventional materials, such as an acrylic resin mentioned above, it is necessary to make it react to the inside of an orientation material, and more exposure amount is required. As a result, there existed a problem that the orientation sensitivity of the conventional material became very small.

In addition, in order to express such solvent resistance to the resin which is the above-mentioned conventional material, the technique of adding a crosslinking agent is known. However, it is known that after thermosetting reaction with a crosslinking agent, a three-dimensional structure is formed inside the formed coating film, and the photoreactivity is lowered. That is, the orientation sensitivity is greatly reduced, and even if a crosslinking agent is added to the conventional material and used, the desired effect cannot be obtained.

Furthermore, although various organic solvents are used for liquid crystal ink, as a substrate, a film with low resistance to organic solvents is sometimes used, and for the reason of film protection, an alignment film with high solvent resistance is required.

From the above, a cured film forming composition that can be used as a liquid crystal aligning agent for photo-alignment used in the formation of a photo-alignment technique that can improve the orientation sensitivity of the orientation material and reduce the amount of polarized UV exposure and the orientation material is required. In addition, there is a demand for a technique capable of providing a phase difference material with high efficiency.

The objective of this invention was achieved based on the above knowledge and examination result. That is, an object of the present invention is to provide an alignment material that has excellent alignment sensitivity, excellent alignment uniformity, and has resistance to solvents in liquid crystal solutions even if it is a thin film, and can function as a protective layer to protect the film substrate It is to provide a cured film forming composition that can be used as a liquid crystal aligning agent for optical alignment.

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 a photo-alignment group and one substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group;

(B) a polymer formed by polymerizing a monomer containing at least an N-alkoxymethyl (meth)acrylamide compound, and

(C) It contains the polymer formed by polymerizing the monomer containing at least N-hydroxyalkyl (meth)acrylamide compound, It relates to the cured film formation composition characterized by the above-mentioned.

1st aspect of this invention WHEREIN: It is preferable that the photo-alignment group of (A) component is a functional group of the structure into which photodimerization or photoisomerization is carried out.

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: As (D)component, it is preferable to contain a crosslinking catalyst further.

1st aspect of this invention WHEREIN: 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 total amount of (B) component and (C)component is 100-3000 mass parts based on 100 mass parts of (A) component.

1st aspect of this invention WHEREIN: It is preferable that mass ratio of (B)component and (C)component is 1:99-99:1.

1st aspect of this invention WHEREIN: Based on 100 mass parts of total amounts of (B) component and (C)component, it is preferable to contain 0.01 mass part - 10 mass parts (D)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, an alignment material that has excellent alignment sensitivity and excellent alignment uniformity, has resistance to solvents in liquid crystal solutions even in thin films, and can function as a protective layer to protect the film substrate The cured film formation composition for providing can be provided.

According to the second aspect of the present invention, an alignment material that has excellent alignment sensitivity and excellent alignment uniformity, has resistance to solvents in liquid crystal solutions even in thin films, and can function as a protective layer to protect the film substrate can provide

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 a film substrate and can be optically patterned.

<Cured film forming composition>

The cured film forming composition of the present invention is a compound having one substituent selected from the group consisting of a photo-alignment group as the component (A), a hydroxyl group, a carboxyl group, and an amino group (hereinafter, also referred to as a “low-molecular photo-alignment component”. ) and a polymer formed by polymerizing a monomer containing at least N-alkoxymethyl (meth)acrylamide compound as component (B), and at least N-hydroxyalkyl (meth)acrylamide compound as component (C) A polymer formed by polymerizing a monomer is contained. In addition to (A) component, (B) component, and (C)component, the cured film formation composition of this invention also contains the component which improves the adhesiveness of a cured film as a crosslinking catalyst and (E) component as (D)component further can do. 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 invention is the above-mentioned low molecular photo-alignment component.

And the low-molecular photo-alignment component which is (A) component is a compound which has a photo-alignment group and one substituent selected from the group which consists of a hydroxyl group, a carboxyl group, and an amino group. In the compound having one substituent selected from the group consisting of a photo-alignment group, a hydroxyl group, a carboxyl group, and an amino group, the photo-alignment group reacts to light to form a hydrophobic photo-alignment part, as described above, and a hydroxyl group and the like constitute a hydrophilic thermal reaction zone.

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 irradiation with light, 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 from the height of 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 formulas [A1] to [A5], A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and X ¹ is a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, or A divalent group formed by bonding 1 to 3 groups selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination thereof through one or more bonds selected from combinations thereof. 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 to the benzene ring 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, a phenyl group, a phenoxy group or a biphenoxy group. X ⁷ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent group obtained by removing two hydrogen atoms from an aromatic ring, or a divalent group obtained by removing two hydrogen atoms from an aliphatic ring. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

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

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.

Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pene Tyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group , 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl -n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1, 2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- Heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pene Tyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl- n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 -Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-hep group Tyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n- Hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n -Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pene Tyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group , n-undecyl group, n-dodecyl group, n-tridecyl group , n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group etc. are mentioned.

Examples of the alkylene group having 1 to 18 carbon atoms include a divalent group obtained by removing one hydrogen atom from the above-mentioned alkyl group.

Examples of the alkyl group having 1 to 4 carbon atoms include a group having the corresponding number of carbon atoms among the groups mentioned above.

As the alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the alkylthio group having 1 to 10 carbon atoms, a group having the corresponding number of carbon atoms among the above-mentioned alkyl groups oxidized or thiolated can be heard

Examples of the alkylene group having 1 to 20 carbon atoms include a divalent group obtained by removing one hydrogen atom from the alkyl group and an alkyl group having 1 to 20 carbon atoms, such as the n-nonadecyl group and n-eicosyl group.

(A) As a specific example of the compound which has the photo-alignment group which is a component and a hydroxyl group, 4-(8-hydroxyoctyloxy) methyl cinnamic acid, 4-(6-hydroxyhexyloxy) methyl cinnamate, for example 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) hydroxypropyloxy) 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-(dimethylamino) cinnamic acid and the like.

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

(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 low-molecular photo-alignment component as component (A) is a compound having a photo-alignment group and a hydroxyl group, as component (A), a compound having two or more photo-alignment groups and/or two or more hydroxyl groups in the molecule It is possible to use 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 low-molecular-weight photo-alignment component which is (A) component becomes possible. As a result, as described later, when the low-molecular photo-alignment component as component (A) and the polymer as component (B) and the polymer as component (C) thermally react, the low-molecular photo-alignment component of component (A) sublimates can be restrained And the cured film formation composition of this invention 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 invention, it has a photo-alignment group, and one substituent chosen from the group which consists of a hydroxyl group, a carboxyl group, and an amino group, The mixture of several types of compounds it may be

<(B) component>

(B) component contained in the cured film formation composition of this invention is a polymer formed by polymerizing the monomer containing at least an N-alkoxymethyl (meth)acrylamide compound. In addition, N-alkoxy methyl (meth)acrylamide means both N-alkoxy methyl acrylamide and N-alkoxy methyl methacrylamide.

Examples of such a polymer include a polymer obtained by copolymerizing an N-alkoxymethyl (meth)acrylamide compound alone or with a copolymerizable monomer. Examples of such polymers include poly(N-butoxymethylacrylamide), poly(N-ethoxymethylacrylamide), poly(N-methoxymethylacrylamide), N-butoxymethylacrylamide and A copolymer of styrene, a copolymer of N-butoxymethyl acrylamide and methyl methacrylate, a copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl methacrylic and a copolymer of lactate and 2-hydroxypropyl methacrylate.

The method for obtaining the polymer as component (B) used in the present invention is not particularly limited, but for example, in a solvent in which an N-alkoxymethyl (meth)acrylamide compound, a copolymerizable monomer and a polymerization initiator, etc. are coexisted as needed. , obtained by polymerization at a temperature of 50 to 110 °C. In that case, the solvent used will not be specifically limited if it dissolves an N-alkoxy methyl (meth)acrylamide compound, a copolymerizable monomer, a polymerization initiator, etc. as needed. As a specific example, it describes in the <solvent> mentioned later.

The polymer obtained by the said method is the state of the solution melt|dissolved in the solvent normally.

In addition, the polymer solution obtained by the above method is poured into diethyl ether or water while stirring to precipitate, and the resulting precipitate is filtered and washed, then dried at room temperature or heat-dried under normal pressure or reduced pressure, and polymer powder (粉体) can be done. By the above operation, the polymerization initiator and unreacted monomer coexisting with the polymer can be removed, and as a result, a purified polymer powder 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.

In this invention, the polymer which is (B) component can also be used in the form of a powder or the form of the solution which melt|dissolved the refined powder again in the solvent mentioned later.

In addition, in this invention, the mixture of several types of polymers may be sufficient as the polymer which is (B) component.

In the present invention, when the above-mentioned copolymerizable monomer is used for producing the polymer as component (B), the amount of the copolymerizable monomer used is based on the total number of moles of the monomer used for preparing the polymer of component (B). Therefore, it is preferably 1 mol% to 200 mol%, and more preferably 10% to 100 mol%.

The weight average molecular weight of the polymer which is such (B) component is 1,000-500,000, Preferably, it is 2,000-200,000, More preferably, it is 3,000-150,000, More preferably, it is 3,000-50,000. On the other hand, the weight average molecular weight is a value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

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

<(C)component>

(C) A component is a polymer formed by polymerizing the monomer containing at least an N-hydroxyalkyl (meth)acrylamide compound. In addition, N-hydroxyalkyl (meth)acrylamide means both N-hydroxyalkyl acrylamide and N-hydroxyalkyl methacrylamide.

When thermosetting the composition of this invention as a coating film, the N-alkoxymethyl group of (B)component and the hydroxyl group of (C)component react, and a bond is formed. Thereby, the coating film becomes strong, and solvent resistance is acquired.

Examples of the N-hydroxyalkyl (meth)acrylamide compound include N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, and N-(2-hydroxypropyl)acrylamide. , N- (2-hydroxypropyl) methacrylamide, N- (4-hydroxybutyl) acrylamide, N- (4-hydroxybutyl) methacrylamide, N- (2,3-dihydroxypropyl ) acrylamide, N-(2,3-dihydroxypropyl) methacrylamide, etc. are mentioned.

In this invention, when manufacturing the polymer of (C)component, monomers other than the said N-hydroxyalkyl (meth)acrylamide compound (it also describes as "other monomers" below.) can also be copolymerized.

In the present invention, in the case of using other monomers when producing the polymer that is the component (C), the usage amount of the other monomers is preferably based on the total number of moles of the monomers used for producing the polymer of the component (C). is 30 mol% to 90 mol%, more preferably 30% to 70 mol%.

Examples of the other monomer include an industrially available monomer capable of radical polymerization.

Specific examples of the other monomer include unsaturated carboxylic acid, acrylic acid ester compound, methacrylic acid ester compound, amide group-containing monomer, maleimide compound, acrylonitrile, maleic anhydride, styrene compound, and vinyl compound.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2, 2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate , tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylic Rate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acrylic Royloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, acryloylethyl isocyanate, and 8 -Ethyl-8-tricyclodecyl acrylate, glycidyl acrylate, etc. are mentioned.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate. acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ- Butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl Ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, methacryloylethyl isocyanate, and 8-ethyl-8-tricyclodecylmethacrylic rate, glycidyl methacrylate, and the like.

Examples of the amide group-containing monomer include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth) ) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N- (methoxymethyl) (meth) ) acrylamide, N-(methoxybutyl)(meth)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-(isobutoxymethyl) (meth)acrylamide, N-(isobutoxyethyl)(meth)acrylamide, N-vinylphthalimide, N-vinylsuccinimide, etc. are mentioned.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl Vinyl ether etc. are mentioned.

As said styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene etc. are mentioned, for example.

As said maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

As said acrylonitrile compound, acrylonitrile etc. are mentioned, for example.

The method for obtaining the polymer as component (C) used in the present invention is not particularly limited, but in the method for producing the polymer as component (B), N-hydroxyalkyl ( A meth)acrylamide compound may be used.

The weight average molecular weight of the polymer which is such (C)component is 1,000-500,000, Preferably it is 2,000-200,000, More preferably, it is 3,000-150,000, More preferably, it is 3,000-100,000. On the other hand, the weight average molecular weight is a value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

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

As content of the polymer which is (B) component in the cured film formation composition of this invention, and the polymer which is (C)component, based on 100 mass parts of (A) component, (B) component and (C)component It is preferable that a total amount is 100-3000 mass parts, It is more preferable that it is 200-2500 mass parts, It is especially preferable that it is 300-2000 mass parts.

Moreover, it is preferable that mass ratio of (B)component and (C)component is 1:99-99:1, It is still more preferable that it is 5:95-95:5, It is especially that it is 10:90-90:10 desirable.

<(D)component>

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

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

Examples of the acid include a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof. In addition, the thermal acid generator is not particularly limited as long as it is a compound that is thermally decomposed to generate an acid during pre-baking or post-baking, that is, a compound that is thermally decomposed at a temperature of 80°C to 250°C to generate an acid.

The acid includes, for example, hydrochloric acid or a salt thereof; Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid , 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluoro Sulfonic acids such as octanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or hydrates or salts thereof can be heard

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-toluenesulfonic acid 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 a compound represented by the following formula; and the like.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

Preferably content of (D)component in the cured film formation composition of this invention is 0.01 mass part - 10 mass parts based on 100 mass parts of total amounts of the polymer of (B) component, and the polymer of (C)component and more preferably 0.1 parts by mass to 6 parts by mass, and still more preferably 0.5 parts by mass to 5 parts by mass. (D) By making content of a component into 0.01 mass part or more, sufficient thermosetting and solvent tolerance can be provided, and also the high sensitivity with respect to light irradiation can also be provided. However, when more than 10 mass parts, the storage stability of a composition may fall.

<(E) component>

The cured film formation composition of this invention may contain the component (it is also hereafter called an adhesion improvement 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 crosslinking 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 high-temperature and high-quality conditions, 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 N-alkoxymethyl group and a (meth)acryl group, the polymer etc. which have an N-alkoxymethyl group and a (meth)acryl group are mentioned. Specific examples are shown below, respectively.

(E) As an example of a component, the polyfunctional acrylate containing a hydroxyl group (Hereinafter, 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 (meth)acryl group and one or more hydroxyl groups is also mentioned.

Moreover, as a compound of (E)component, the compound which has at least one polymeric group containing a C=C double bond in 1 molecule, and at least one 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 9]

(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)

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pene Tyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group , 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl -n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1, 2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- Heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pene Tyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl- n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 -Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-hep group Tyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n- Hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n -Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pene Tyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like.

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 and N-alkoxymethyl group containing C=C double bond of component, Preferably, the following compound is mentioned, for example.

[Formula 10]

Content of (E) component in the cured film formation composition of this invention is based on 100 mass parts of the low molecular photo-alignment component which is (A) component, Preferably it is 1 mass part - 100 mass parts, More preferably Preferably, it is 5 mass parts - 70 mass parts.

<solvent>

The cured film formation composition of this invention is mainly used in the solution state melt|dissolved in the solvent. The solvent used in that case should just be able to melt|dissolve (A) component, (B) component, and (C)component, and (D)component, (E)component and/or other additives mentioned later as needed, the kind and structures are not particularly limited.

As a specific example of a solvent, 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-pentane One, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl -3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate , butyl lactate, N,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 invention is a sensitizer, a silane coupling agent, surfactant, a rheology adjusting agent, a pigment, dye, a storage stabilizer, an antifoaming agent, oxidation as needed, unless the effect of this invention is impaired. inhibitors, etc. may be contained.

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

As a sensitizer which is an example of another additive, benzophenone, anthracene, anthraquinone, thioxanthone, its derivative(s), a nitrophenyl compound, etc. are mentioned. Among these, a benzophenone derivative and a nitrophenyl compound 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, it is possible to use a sensitizer individually or in combination of 2 or more types of compounds.

It is preferable that the usage-rate of the sensitizer in the cured film formation composition of this invention is 0.1 mass part - 20 mass parts based on 100 mass parts of the low molecular photo-alignment component of (A) component, 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 transmittance|permeability may fall and a coating film may become rough.

<Preparation of a cured film formation composition>

The cured film forming composition of the present embodiment comprises a polymer formed by polymerizing a monomer containing at least an N-alkoxymethyl (meth)acrylamide compound as the component (A) and a low-molecular photo-alignment component as the component (B), ( C) The polymer formed by polymerizing the monomer containing at least N-hydroxyalkyl (meth)acrylamide compound as a component is contained. And, if necessary, the crosslinking catalyst as component (D), the adhesion improving component as component (E) and/or other additives may be contained.

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

Although the ratio of solid content in the cured film formation composition of this invention 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 % - 60 It is 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 invention is not specifically limited. As a preparation method, (A) component, (C)component and as needed (D)component, (E)component are mixed in predetermined ratio with the solution of (B)component melt|dissolved in a solvent, for example, and it is uniform A method of preparing a single solution, or a method of mixing by adding other additives as necessary in an appropriate step of the preparation method is exemplified.

In preparation of the cured film formation composition of this invention, the polymer solution obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, (C)component (A)component and (B)component and (D)component and (E)component are put into the solution of (C)component as needed, and it is set as a uniform solution. At this time, a solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the production|generation process of (C)component and the solvent used for density|concentration adjustment of a cured film formation composition may be the same, and may differ.

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

<Cured film, alignment material and phase difference material>

A solution of the cured film forming composition of the present invention is applied to a substrate (eg, 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, a quartz substrate) , ITO substrate, etc.) or film (e.g., triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), bar coat, spin coating, drip coating, A cured film can be formed by 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 should proceed to such an extent that the component of the alignment material formed from 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 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 cured film formation composition of this invention is 0.05 micrometer - 5 micrometers, for example, 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 a vertical or oblique direction at room temperature or in a heated state.

Since the alignment material formed from the cured film forming composition of the present invention has solvent resistance and heat resistance, a phase difference material made of a polymerizable liquid crystal solution is applied on the alignment material, and then the phase difference material is heated to the phase transition temperature of the liquid crystal to bring the phase difference material into a liquid crystal state. and oriented on the orientation material. And by hardening the retardation material which became an orientation state as it is, 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 invention 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, in the case of manufacturing the patterned retardation material used for 3D display, from the cured film forming composition of the present invention to the cured film formed by the above method, through a mask of a line and space pattern, from a predetermined standard, for example For example, polarized UV exposure is carried out in a direction of +45 degrees, and then, after removing the mask, polarized UV exposure is exposed in a direction of -45 degrees 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 retardation material which has become an orientation state as it is, the patterned retardation material in which two types of retardation areas from which retardation characteristics differ are each arrange|positioned regularly and plural can be obtained.

In addition, using two substrates having the alignment material of the present invention formed as described above, and bonding the alignment materials on both substrates to face each other through a spacer, liquid crystal is injected between the substrates, so that the liquid crystal is It can also be set as the liquid crystal display element which aligned.

Thus, the cured film formation composition of this invention 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 should not be construed as being limited thereto.

[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

MMA: methyl methacrylate

HEAA: N-(2-hydroxyethyl)acrylamide

MAIB: Dimethyl 2,2-azobisisobutyrate

<Component A>

MCA: 4-methoxycinnamic acid

[Formula 11]

<Component B>

PB-1: It is represented by the following structural formula.

[Formula 12]

<C component>

PC-1: It is represented by the following structural formula.

[Formula 13]

PC-2: It is represented by the following structural formula.

[Formula 14]

<Component D>

PTSA: p-toluenesulfonic acid monohydrate

<E component>

E-1: A compound having an N-alkoxymethyl group and an acryl group represented by the following structural formula

[Formula 15]

<solvent>

Each resin composition of an Example and a comparative example contained a solvent, and propylene glycol monomethyl ether (PM) and butyl acetate (BA) were used as the solvent.

<Measurement of molecular weight of polymer>

For the molecular weight of the acrylic copolymer in the polymerization example, a gel permeation chromatography (GPC) apparatus (HLC-8320) manufactured by Tosoh Corporation, and a column manufactured by Tosoh Corporation (TSKgel ALPHA4000, TSKgel ALPHA3000) were used, and the following were used. 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)

<Synthesis of component B>

<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, filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Synthesis of C component>

<Polymerization Example-2>

7.0 g of MMA, 5.8 g of HEAA, and 0.23 g of MAIB as a polymerization catalyst were dissolved in 13.0 g of PM. An acrylic polymer solution was obtained by adding a solution in which 6.50 g of PM was previously added to a four-neck flask and dissolved in a dropping tank heated to 85°C over 3 hours, followed by reacting under reflux for 3 hours. Mn of the obtained acrylic polymer was 12,600, and Mw was 43,100. A 40% PM solution of the target polymer (PC-1) was obtained.

<Synthesis of C component>

<Polymerization Example-3>

47.10 g of BMAA, 34.5 g of HEAA, and 0.829 g of MAIB as a polymerization catalyst were dissolved in 82.50 g of PM. An acrylic polymer solution was obtained by adding 41.25 g of PM to a four-neck flask in advance and dissolving it in a dropping tank heated to 85°C over 3 hours, and then reacting for 5 hours after the dropwise addition. Mn of the obtained acrylic polymer was 6,500, and Mw was 17,000. A 40% PM solution of the target polymer (PC-2) was obtained.

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

<Preparation Example 1>

(A) 0.079 g of MCA as component, 0.66 g of PB-1 obtained in polymerization example-1 as (B) component, and 0.26 40% PM solution of the polymer (PC-1) obtained in polymerization example-2 as (C) component g, 0.056 g of E-1 (94.6% BA solution manufactured by Junsei Chemical Co., Ltd.) as component (E), 0.021 g of PTSA as component (D), and 6.65 g of PM as a solvent and 1.62 g of BA are added thereto After stirring for 1 hour, it was confirmed that the solution was 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 pore diameter of 0.2 micrometer.

<Preparation Examples 2 to 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 each liquid crystal aligning agent (A-2) - (A-4), (B-1), (B -2) was prepared.

[Table 1]

APEPO-1: RFK-505 (manufactured by Kawasaki Chemical Industry Co., Ltd.)

PEPO-1: Polylite 8651 (manufactured by DIC Corporation)

<Preparation of polymerizable liquid crystal solution for horizontal alignment>

<Production Example 1>

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

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

<Example 1>

The liquid crystal aligning agent (A-1) prepared in Preparation Example 1 was applied on a triacetyl cellulose (TAC) film as a substrate using a bar coater to a wet film thickness of 6 μm. Heat-drying was performed at 130 degreeC for 2 minute(s) in a thermal 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, under nitrogen, by irradiating a non-polarized light of 365 nm vertically at an exposure amount of 300 mJ/cm ² to cure the polymerizable liquid crystal, a retardation film was produced.

<Examples 2 to 4>

Using (A-2) to (A-4) as a liquid crystal aligning agent, a retardation film was prepared in the same manner as in Example 1.

<Comparative Example 1>

The liquid crystal aligning agent (B-1) prepared in Preparation Example 1 was applied on a TAC film as a substrate to a wet film thickness of 4 μm using a bar coater. Heat-drying was performed at 130 degreeC for 2 minute(s) in a thermal 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, under nitrogen, by irradiating a non-polarized light of 365 nm vertically at an exposure amount of 300 mJ/cm ² to cure the polymerizable liquid crystal, a retardation film was produced.

<Comparative Example 2>

(B-1) was used as a liquid crystal aligning agent, and was operated in the same manner as in Comparative Example 1 to prepare a retardation film.

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 by 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" as (circle) the thing in which the phase difference was expressed without defect, and the thing in which the phase difference was not expressed was x.

<TAC protection>

When the retardation film containing the prepared TAC film was not curled, it was denoted by ○, and curled ones were denoted by ×, and it was described in the “Protection” column.

[Table 2]

From the results of Table 2, by using a polymer obtained by polymerizing a monomer containing an N-hydroxyalkyl (meth)acrylamide compound as the component (C), the orientation with respect to the liquid crystal solution containing NMP can be obtained, It is clear that damage to the TAC film by NMP can also be protected.

Industrial Applicability

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, in particular, patterning retardation of 3D display It is suitable as a material for forming ashes. Furthermore, materials for forming cured films such as protective films, flattening 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 suitable as a material for forming an insulating film or the like of an organic EL device.

Claims (11)

(A) a compound having a photo-alignment group and one substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group;
(B) a polymer formed by polymerizing a monomer containing at least an N-alkoxymethyl (meth)acrylamide compound, and
(C) The cured film formation composition characterized by containing the polymer formed by polymerizing the monomer containing at least N-hydroxyalkyl (meth)acrylamide compound. 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,
(D) As a component, it further contains a crosslinking catalyst, The cured film formation composition characterized by the above-mentioned. 6. The method according to any one of claims 1 to 5,
(E) As a component, it further contains a close_contact|adherence improving component, The cured film formation composition characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
(A) Based on 100 mass parts of component, the total amount of (B)component and (C)component is 100-3000 mass parts, The cured film formation composition characterized by the above-mentioned. 8. The method according to any one of claims 1 to 7,
(B) Mass ratio of component and (C)component is 1:99-99:1, The cured film formation composition characterized by the above-mentioned. 9. The method according to any one of claims 5 to 8,
(B) The cured film formation composition containing 0.01 mass parts - 10 mass parts (D)component based on 100 mass parts of total amounts of a component and (C)component. It is obtained using the cured film formation composition in any one of Claims 1-9, 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 1-9, The retardation material characterized by the above-mentioned.