TWI535773B - Resin composition, liquid crystal alignment material and retardation material - Google Patents

Description

Resin composition, liquid crystal alignment material, and phase difference material

The present invention relates to a resin composition, a liquid crystal alignment material, and a phase difference material.

For the purpose of compensating the viewing angle of the liquid crystal display, the retardation film is often disposed outside the liquid crystal cell. In this case, the type of the retardation film differs depending on the display mode of the liquid crystal in the liquid crystal display.

For example, in the case of a VA mode liquid crystal display, a two-axis polarizing plate having a refractive index different in three directions such as in-plane x and y directions and a thickness direction of a film is used as a retardation film alone, or uniaxially stretched. The method of combining the positive A polarizing plate and the negative C polarizing plate produced as a retardation film is used as the compensation of the viewing angle. The former is produced by using a two-axis extension, and the latter is produced by a single-axis extension. In the case where the refractive index in the x and y directions of the film of the polarizing plate is nx and ny, and the refractive index in the thickness direction is nz, the positive A polarizing plate is a retardation film having a characteristic of nx>ny=nz. Further, the negative C polarizing plate is a retardation film having a characteristic of nx=ny>nz.

In recent years, various studies have been conducted for the purpose of introducing a phase difference material into a liquid crystal cell of a liquid crystal display to achieve high contrast, low cost, or light weight. Subsequently, there is a proposal to form a phase difference material and use a polymerizable liquid crystal solution. Specifically, a polymerizable liquid crystal solution is applied to an appropriate portion of the liquid crystal cell, and after the desired alignment is performed, the phase difference material is formed by photocuring.

In the case of a positive A polarizing plate, a polymerizable liquid crystal exhibiting horizontal alignment is used. Further, in the case of a negative C polarizing plate, a polymerizable liquid crystal exhibiting a Cholesteric alignment or a discotic alignment property is used. Further, in the case of the biaxial polarizing plate, it is a polymerizable liquid crystal which exhibits biaxial alignment. Therefore, when introducing a phase difference material having a two-axis phase difference into a liquid crystal cell, it is necessary to display a polymerizable liquid crystal having biaxial alignment properties, or a polymerizable liquid crystal exhibiting cholesterol alignment property and a polymerizable liquid crystal exhibiting horizontal alignment. Laminated for use.

However, it has been known that a polymerizable liquid crystal having a biaxial alignment property is not easily formed into a thick film, and a material which exhibits a necessary phase difference characteristic has not been found. Further, in the case of laminating a polymerizable liquid crystal exhibiting cholesterol alignment and a polymerizable liquid crystal exhibiting horizontal alignment, the manufacturing steps are complicated, and there are problems such as an increase in manufacturing cost or a decrease in productivity.

Fig. 2 is a schematic view showing a configuration of a liquid crystal cell in which a liquid crystal alignment film is formed by a conventional technique. In the figure, the liquid crystal layer 208 is sandwiched between two substrates 201 and 211. On the substrate 211, an ITO 210 and an alignment film 209 are formed. Further, on the substrate 201, a filter film 202, an overcoat (hereinafter also referred to as a CF protective film) 203 of a filter film (CF), an alignment film 204, and a phase difference material 205 are formed. ITO 206, and alignment film 207.

In the conventional liquid crystal cell, in order to form the phase difference material, it is necessary to form an alignment before the polymerizable liquid crystal is cured. Therefore, the lower layer needs to have a film which can align the liquid crystal, that is, an alignment film must be separately provided. The alignment film is formed by a step such as rubbing treatment or polarized light irradiation. In other words, as shown in FIG. 2, a film of the alignment film 204 is formed on the CF protective film 203, and a phase difference material 205 obtained by forming a polymerizable liquid crystal such as a liquid crystal monomer is generally used as a general method. . That is, after the filter film 202 is formed, it is necessary to form two layers of the CF protective film 203 and the alignment film 204, which complicates the manufacturing process.

Based on the above requirements, it is highly desirable to provide a film that can simultaneously satisfy different demand characteristics, and a material that forms the same. Specifically, for example, a film which can balance both the alignment film and the CF protective film and a material which forms the film are sought. In this way, the liquid crystal display can enjoy the advantages of low cost, reduced number of processes, and improved productivity.

Further, in the case of a film having both the alignment film and the CF protective film, it is required to shorten the time required for the alignment treatment. However, in the manufacturing step of the alignment film, it is necessary to use it in the photoalignment technique. Therefore, in the case of a film having both an alignment film and a CF protective film, a material which can use photoalignment is strongly required as a constituent content.

Further, in the film having both the alignment film and the CF protective film, a larger birefringence is also required. When the birefringence is increased, the characteristics of the negative C polarizer can be imparted. Further, when the high birefringence property is provided, the film thickness of the biaxially oriented polymerizable liquid crystal laminated thereon can be made thinner, and when only the horizontally oriented polymerizable liquid crystal is applied, the biaxial characteristics can be obtained.

In general, in the CF protective film, an acrylic resin having high transparency is used. Subsequently, when the acrylic resin is cured by heat or light, heat resistance or solvent resistance can be produced (for example, Patent Document 1 or 2).

However, it has been found by the inventors of the present invention that a CF protective film composed of a thermosetting or photocurable acrylic resin can obtain transparency or solvent resistance, but it is irradiated with polarized UV. Also, there is no way to obtain sufficient liquid crystal alignment. Therefore, it has been confirmed that the conventional CF protective film is not applied to the film having the alignment film and the CF protective film as described above.

Further, it is known that a polyamic acid formed by using a tetracarboxylic dianhydride having a biphenyl skeleton and a diamine having an alicyclic structure can provide a report of a highly transparent polyhistamine having a high birefringence. (Patent Document 3). However, even when the polyacrylic acid is irradiated with polarized light, sufficient liquid crystal alignment property cannot be obtained. That is, these high refractive index polyamic acids cannot be applied to the film having the alignment film and the CF protective film as described above.

Further, an acrylic resin having a photodimerization site such as a cinnabar base or a chalcone group in the side chain has been proposed, and when the polarized UV is irradiated, a sufficient liquid crystal alignment property can be obtained (Patent Document 4). However, according to studies by the inventors of the present invention, even when a normal liquid crystal for a display is aligned and a sufficient amount of polarized UV exposure (for example, 100 mJ/cm ² ) is applied, the alignment film and the CF are not sufficiently provided. The function of the membrane of the protective film. Specifically, for example, when the polarizing UV is applied to the acrylic resin and the polymerizable liquid crystal solution is applied thereon, the resistance to the acrylic resin solution is lowered, and the film of the lower acrylic resin is dissolved. Therefore, sufficient alignment properties cannot be obtained for the polymerizable liquid crystal.

Moreover, when a large amount of polarized UV exposure amount of 1 J/cm ² or more is used, the reaction rate of the photodimerization reaction in the above acrylic resin can also be improved. Therefore, increasing the exposure amount has a possibility of improving the alignment of the polymerizable liquid crystal. However, in order to perform various alignment treatments, it has been found that when the optical alignment technique is performed for the purpose of shortening the time, it is known that the exposure amount is increased for a long period of time, and the increase in the exposure amount is still limited.

Further, according to the findings of the present inventors, it has been found that even when the photodimerization reaction for the purpose of generating liquid crystal alignment is performed even if the reaction rate is increased, the crosslinking reaction is not sufficiently performed, and the film is not required to have a film. Fully heat resistant. In other words, when the film formed of the above acrylic resin is confirmed, when the reaction rate is increased, the film shrinkage is caused to a large extent in the heat treatment for the purpose of producing a liquid crystal cell.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2000-103937

[Patent Document 2] JP-A-2000-119472

[Patent Document 3] WO2008010483A1

[Patent Document 4] License No. 4011652

The present invention is an invention based on the above findings and research. That is, the object of the present invention is to form a high-sensitivity polymerizable liquid crystal to form an alignment by thermal alignment using a photo-alignment technique, and to provide a resin composition having high birefringence, high solvent resistance, heat resistance, and high transparency. Things.

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

According to a first aspect of the present invention, there is provided a resin composition characterized by comprising

(A) an acrylic copolymer having a photodimerization site formed by a hydrophobic group and a thermal crosslinking site formed by a hydrophilic group, and

(B) a polyimide precursor having an aromatic ring moiety, and

(C) A crosslinking agent which crosslinks the component (A) and the component (B).

In the first aspect of the invention, the component (A) is preferably an acrylic copolymer obtained by polymerizing a monomer mixture containing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.

In the first aspect of the present invention, the component (A) is a monomer mixture containing 25 to 20 mol% of a monomer having a photodimerization site, relative to the total amount of the all monomer mixture. The acrylic copolymer obtained by the polymerization reaction is preferred.

In the first aspect of the present invention, the photodimerization site of the component (A) is preferably a cinnamyl group.

In the first aspect of the present invention, the thermally crosslinked portion of the component (A) is preferably a hydroxyl group or a carboxyl group.

In the first aspect of the invention, the polyimine precursor of the component (B) preferably has a biphenyl structure in the main chain.

In the first aspect of the invention, the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, and a tetracarboxylic dianhydride and a diamine. It is preferred that at least one of the compounds is a biphenyl structure.

In the first aspect of the present invention, the tetracarboxylic dianhydride is preferably biphenyltetracarboxylic dianhydride.

In the first aspect of the invention, the component (B) is preferably a polyimine precursor having a trifluoromethyl group in a structural unit.

In the first aspect of the present invention, the polyimine precursor of the component (B) preferably has an alicyclic structure in the main chain.

In the first aspect of the invention, the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, and a tetracarboxylic dianhydride and a diamine compound. At least one of them is preferably an alicyclic structure.

In the first aspect of the invention, the crosslinking agent of the component (C) is preferably a crosslinking agent having a methylol group or an alkoxymethylol group.

In the first aspect of the present invention, it is preferred to contain 10 to 100 parts by mass of the component (C) based on 100 parts by mass of the total of the components (A) and (B).

In the first aspect of the present invention, it is preferred that the acid or the thermal acid generator further contains the component (D).

In the first aspect of the invention, it is preferred to contain 0.1 to 10 parts by mass of the component (D) based on 100 parts by mass of the total of the components (A) and (B).

According to a second aspect of the present invention, there is provided a liquid crystal alignment material obtained by using the resin composition of the first aspect of the present invention.

According to a third aspect of the present invention, there is provided a phase difference material formed by using a cured film obtained by using the resin composition of the first aspect of the present invention.

[Effects of the Invention]

In the resin composition of the first aspect of the present invention, a cured film having a high refractive index, high transparency, high solvent resistance, and high heat resistance can be obtained, and light alignment of the liquid crystal can be formed.

According to the second aspect of the present invention, a liquid crystal alignment material having high birefringence and excellent light transmittance, solvent resistance and alignment property can be obtained.

According to the third aspect of the present invention, a phase difference material which is disposed in the liquid crystal cell can be obtained. The liquid crystal cell of the phase difference material can be used to increase the contrast ratio.

The present invention relates to a resin composition, a liquid crystal alignment material formed using the resin composition, and a phase difference material formed by using a cured film obtained by using the resin composition. More specifically, it relates to a resin composition which can form a cured film having high birefringence, high transparency, liquid crystal alignment energy, high solvent resistance, and heat resistance, and is formed by using the resin composition. The invention relates to a liquid crystal alignment material and a phase difference material formed by using the liquid crystal alignment material. The resin composition of the present invention is suitable as a film for a function as a CF protective film in a liquid crystal display, and has an alignment function for a polymerizable liquid crystal for forming a phase difference layer, and is therefore suitable for forming a built-in phase difference layer. .

Hereinafter, the resin composition, the liquid crystal alignment material, and the phase difference material of the present invention will be described in detail by way of specific examples.

The resin composition of the present embodiment is intended to form a resin composition for forming a thermosetting film having photo-alignment properties, that is, a resin composition for forming a photo-alignment thermosetting film. Further, the thermosetting film having photo-alignment properties means a cured film which is cured by heating and which is subjected to polarized light exposure to cause alignment properties of liquid crystal.

The resin composition of the present embodiment is an acrylic copolymer containing a photodimerization site and a thermal crosslinking site of the component (A), and a polybendimimine precursor of the component (B), and a component of the component (C). Joint agent.

More specifically, in the component (A), the photodimerization site of the acrylic copolymer is formed of a hydrophobic group, and the thermal crosslinking site of the acrylic copolymer is formed of a hydrophilic group. Further, the polyimine precursor of the component (B) is a member having an aromatic ring moiety. Further, the crosslinking agent of the component (C) is a component which can crosslink the component (A) and the component (B).

That is, the resin composition of the present embodiment contains,

(A) an acrylic copolymer having a photodimerization site formed by a hydrophobic group and a thermal crosslinking site formed by a hydrophilic group, and

(B) a polyimide precursor having an aromatic ring moiety, and

(C) A composition comprising a crosslinking agent which crosslinks the component (A) and the component (B).

Further, the resin composition of the present embodiment may further contain an acid or photoacid generator of the component (D) in addition to the components (A), (B) and (C), and/or (E) component. The sensitizer.

In the resin composition of the present embodiment, when the component (A) is contained, the cured film obtained by using the resin composition can impart liquid crystal alignment performance via photo-alignment treatment. In other words, the acrylic copolymer of the component (A) can be thermally crosslinked as described later when it is heated at the time of heat transfer by a photodimerization site formed by a hydrophobic group and a hydrophilic group. It is hardened by a thermal crosslinking reaction. At this time, the photodimerization site formed by the hydrophobic group exists in addition to the vicinity of the surface of the cured film, and also exists in a free state protruding from the surface. When the photodimerization reaction is carried out by polarized UV exposure or the like based on this state, excellent liquid crystal alignment performance can be produced in the vicinity of the surface of the cured film. Therefore, when a polymerizable liquid crystal is applied onto the cured film, a highly hydrophobic polymerizable liquid crystal is formed, and the photodimerization site formed by the hydrophobic group of the acrylic copolymer is efficiently interacted to achieve high sensitivity. Liquid crystal alignment.

Further, the component (A) has a thermally crosslinked portion. The thermally crosslinked portion may be formed of a hydrophilic group, and thus an efficient thermal crosslinking reaction may be generated between the crosslinking agent of the component (C) described later. As a result, in addition to the photodimerization site, the crosslinked portion can be introduced via a thermal reaction to increase the number of crosslinked sites. Therefore, dissolution of the cured film can be prevented by applying a polymerizable liquid crystal solution to the cured film. Further, in the heating environment in the manufacturing process of the liquid crystal cell, the heat shrinkage phenomenon of the cured film can also be suppressed.

Further, in the resin composition of the present embodiment, when the component (B) is contained, the birefringence of the cured film obtained by using the resin composition can be adjusted. That is, the polyimine precursor of the component (B) forms a polyimine by thermal reaction to form a cured film, and the main chain of the polyimide precursor is selected to include a benzene ring structure or a biphenyl structure. In the case of the molecular structure, high-birefringence can be imparted to the cured film.

Moreover, in this case, there is still a concern that the light transmittance of the cured film, that is, the transparency is lowered, and when the molecular structure of the compound constituting the polyimide precursor is selected, the decrease in the transmittance can be suppressed. For example, a compound constituting a polyimide precursor can impart high transparency to a cured film when a compound having an alicyclic structure is selected. That is, by appropriately designing the molecular structure of the polyimide precursor, the cured film can simultaneously impart both high birefringence and high transparency.

Further, since the resin composition of the present embodiment contains the component (C), the cured film obtained by using the resin composition can be introduced into the crosslinked portion via a thermal reaction. That is, as described above, the (C) component generates a thermal crosslinking reaction with the component (A). Further, between the component (B) and the component (B), a crosslinking reaction occurs between the carboxyl group and the component (C) of the polyimide precursor.

When the carboxyl group content in the polyimide precursor is adjusted, the crosslinking reaction between the component (B) and the component (C) can be controlled, and the crosslinking reaction between the component (A) and the component (C) can be controlled. . As a result, in the entire cured film obtained from the resin composition, an efficient crosslinking reaction can be realized by a thermal reaction, and a strong cured film can be formed by introducing a crosslinking portion.

Hereinafter, the components (A) to (C) will be described in detail.

<(A) component>

The component (A) in the present embodiment is an acrylic copolymer having a photodimerization site and a thermal crosslinking site. The photodimerization site of the acrylic copolymer of the component (A) is formed of a hydrophobic group, and the thermally crosslinked site is formed of a hydrophilic group. Hereinafter, the contents will be specifically illustrated by enumeration.

In the present embodiment, the acrylic copolymer is a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylate, methacrylate or styrene.

The acrylic copolymer (hereinafter, also referred to as a specific copolymer) having a photodimerization site and a thermal crosslinking site of the component (A) may be an acrylic copolymer having the structure, and may constitute a high acrylic copolymer. The skeleton of the main chain of the molecule and the kind of the side chain are not particularly limited.

The photodimerization site is a site where a dimer is formed by light irradiation, and specifically, for example, a cinnamyl group, a chalcone group, a cumene group, a fluorenyl group or the like. Among these, it is preferable to have high transparency in the visible light region and cinnabar base having photodimerization reactivity. A partial structure of a particularly preferred cinnabar base is as shown in the following formula [A1] and formula [A2].

[Chemical 1]

In the above formula, X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. Among them, the phenyl group and the biphenyl group may be each substituted by either a halogen atom or a cyano group. X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. Among them, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, a guanamine bond or a urea bond.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.

The thermal crosslinking site is a site to which a crosslinking agent is bonded via heating, and specifically, for example, a hydroxyl group, a carboxyl group or a glycidyl group.

The acrylic copolymer of the component (A) preferably has a weight average molecular weight of 3,000 to 200,000, preferably 4,000 to 150,000, and most preferably 5,000 to 100,000. When the weight average molecular weight is an excessively large substance exceeding 200,000, the solubility to the solvent is lowered, and the controllability is lowered. Further, when the weight average molecular weight is too small as less than 3,000, the hardening may cause insufficient hardening, and the solvent resistance and heat resistance may be lowered.

As described above, the side chain of the component (A) has a method of synthesizing an acrylic copolymer having a photodimerization site and a thermal crosslinking site, and a monomer having a photodimerization site and a monomer having a thermal crosslinking site. The method of performing copolymerization is preferred.

A monomer having a photodimerization site, for example, a monomer having a cinnamyl group, a chalcone group, a cumene group or a fluorenyl group. Among these, it is preferred that the visible light region has transparency and a monomer having a cinnamyl group having good photodimerization reactivity. In particular, a monomer having a cinnamyl group having the structure represented by the above formula [A1] or formula [A2] is preferred. Specific examples of the monomer are, for example, the following formula [A3] and formula [A4].

[Chemical 2]

In the above formula, X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. Among them, the phenyl group and the biphenyl group may be each substituted by either a halogen atom or a cyano group. X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. Among them, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group and a cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, a guanamine bond or a urea bond. X ³ and X ⁵ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group or an alicyclic group. Among them, the alkylene group having 1 to 20 carbon atoms may be branched or linear. X ⁴ and X ⁶ represent a polymerizable group. Specific examples of the polymerizable group include, for example, an acrylonitrile group, a methacryl fluorenyl group, a styryl group, a maleimine group, a decyl amide group, and a decylamino group.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group. For example, methyl 4-(6-methylpropoxyhexyl-1-oxy) cinnamate and 6-(acryloxy)hexyl-3-(4-methoxyphenyl)acrylate.

Monomer having a thermally crosslinked moiety, for example, ethyl 2-hydroxyacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethyl Acrylate, caprolactone 2-(acryloxy)ethyl ester, caprolactone 2-(methacryloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(B) Glycol) ethyl ether methacrylate, 5-propenyl oxo-6-hydroxynorbornene-2-decanoate-6-lactone and 5-methyl propylene oxo-6-hydroxyl Monomer having a hydroxyl group such as borneol-2-phthalate-6-lactone, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl) phthalate, single -(2-(methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylate amide and N-( Carboxyl group, hydroxystyrene, N-(hydroxyphenyl)methacrylate a monomer having a phenolic hydroxyl group such as N-(hydroxyphenyl)acrylic acid decylamine, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide, and a glycidyl group A monomer having a glycidyl group such as methacrylate or glycidyl acrylate.

Further, in the present embodiment, in addition to a monomer having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group), a specific copolymer may be used together with the monomer. Copolymers, but monomers having no specific functional groups, are used in combination.

Specific examples of the monomer having no specific functional group as described above, for example, an acrylate compound, a methacrylate compound, a maleimide compound, a decylamine compound, acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. . Specific examples thereof include the following. But it is not limited to this content.

Acrylate compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl acrylate, phenyl acrylate, glycidyl acrylate, acrylic acid 2, 2, 2-Trifluoroethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, acrylic acid 2-Aminoethyl ester, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, Acrylic 8-A Base-8-tricyclodecyl ester and 8-ethyl-8-tricyclodecyl acrylate.

A methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, methacrylic acid armor Ester, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate , 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydroanthracene methacrylate Base ester, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate And 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate.

Vinyl compounds, for example, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbitol, allyl glycidyl ether, 3-vinyl-7-oxabis [4.1.0 Heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, and the like.

Styrene compounds, for example, styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.

Maleic imine compounds, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The amount of each monomer used in the preparation of the specific copolymer is from 25 to 90 mol% of the monomer having a photodimerization site, and from 10 to 75 mol%, based on the total amount of all monomers. The monomer of the thermal crosslinking site, preferably 0 to 65 mol% of a monomer having no specific functional group. When the content of the monomer having a photodimerization site is less than 25 mol%, it is difficult to impart high sensitivity and good liquid crystal alignment. Moreover, when the content of the monomer having a thermal crosslinking portion is less than 10 mol%, it is difficult to impart sufficient thermosetting property, and it is difficult to maintain high liquid crystal alignment with high sensitivity.

In the present embodiment, the method for producing a specific copolymer is not particularly limited. For example, in the presence of a monomer having a specific functional group, a desired monomer having no specific functional group, and a polymerization initiator or the like, the polymerization reaction is carried out at a temperature of 50 to 110 ° C, that is, A specific copolymer can be obtained. The solvent to be used at this time is not particularly limited as long as it can dissolve a monomer having a specific functional group, a monomer having no specific functional group, and a solvent such as a polymerization initiator. Further, the solvent is also described in the <solvent> column described later.

The specific copolymer obtained by the above method is usually in the form of a solution obtained by dissolving in a solvent.

Further, the solution of the specific copolymer obtained by the above method is added to diethyl ether or water under stirring, and then reprecipitated, and the resulting precipitate is filtered, washed, and then subjected to normal pressure or reduced pressure. It is dried at room temperature or dried by heating to form a powder of a specific copolymer. As a result of the above operation, the polymerization initiator and the unreacted monomer which are present in the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. In the case where the purification is not sufficiently performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

In the embodiment of the present invention, the specific copolymer may be in the form of a powder, or may be in the form of a solution obtained by redissolving the purified powder in a solvent to be described later.

Further, in the present embodiment, the specific copolymer of the component (A) may be a mixture of a plurality of specific copolymers.

<(B) component>

The component (B) in the present embodiment is a polyimine precursor. The polyimine precursor of the component (B) is one having an aromatic ring moiety. For the purpose of achieving high birefringence, it is preferred that the polyimine precursor has a polyimine precursor having a structural unit represented by the following formula (1).

[Chemical 3]

In the above formula (1), A ₁ is an organic group having at least one structure having an aromatic ring moiety such as a skeleton which is directly bonded to one to three alicyclic structures or a benzene ring, a naphthalene ring skeleton, and an anthracene ring skeleton, B ₁ is an organic group having a structure having an aromatic ring moiety such as a benzene ring containing an alicyclic structure or a trifluoromethyl group or a trifluoromethyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon atom. An organic group of 1 to 7. In the formula (1), at least one of A ₁ or B ₁ is an organic group having a structure having an aromatic ring moiety.

Specific examples of A ₁ in the formula (1) include an organic group or the like having a structure represented by T1 to T9 shown in Table 1 below. However, it is not limited to this content.

In the present embodiment, B ₁ in the formula (1) is an organic group containing at least one benzene ring having an alicyclic structure or a trifluoromethyl group or a trifluoromethyl group. Specific examples of the organic group of the benzene ring having an alicyclic structure or a trifluoromethyl group or a trifluoromethyl group are, for example, the organic groups represented by S1 to S7 shown in Table 2 below.

In the present embodiment, the polyimine precursor of the component (B) may contain other structural units than the structural unit represented by the above formula (1). Among them, other structural units are not particularly limited. Further, it may contain one or more structural units other than the structural unit represented by the formula (1).

The polyimine precursor of the component (B) has a weight average molecular weight of from 1,000 to 100,000, preferably from 1,500 to 60,000. When the weight average molecular weight of the polyimide precursor is less than 1,000, the solvent resistance is lowered to reduce the alignment sensitivity. Further, when the weight average molecular weight of the polyimide precursor exceeds 100,000, the viscosity of the solution is too high, and the controllability is lowered.

<Method for producing (B) component>

In the present embodiment, the polyimine precursor of the component (B) is obtained by copolymerizing a tetracarboxylic dianhydride and a diamine compound.

a tetracarboxylic dianhydride having a tetracarboxylic dianhydride containing at least one alicyclic structure, a tetracarboxylic dianhydride having at least one structure directly bonded by 1 to 3 benzene rings, or at least one A naphthalene ring tetracarboxylic dianhydride is preferred.

Specific examples of the above acid dianhydride include, for example, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4 ,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,5,6-nonanedicarboxylic dianhydride, 3,3',4,4 '-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride and 2,3,3',4'-biphenyltetracarboxylic dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride or the like.

In the present embodiment, the tetracarboxylic dianhydride component may contain other tetracarboxylic dianhydrides than the above. In this case, the other tetracarboxylic dianhydride may be contained in one type or in a plurality of types.

Specific examples of other tetracarboxylic dianhydrides, for example, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid Dihydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,5-dicarboxymethyl terephthalic acid Dihydride, 4,6-dicarboxymethylisophthalic dianhydride, 4-(2,5-dioxatetrahydro-3-furanyl) phthalic anhydride, 1,4-double (2,5 -dioxatetrahydro-3-furanyl)benzene, 1,4-bis(2,6-dioxatetrahydro-4-pyranyl)benzene, 1,4-bis(2,5-dioxo) Heterotetrahydro-3-methyl-3-furanyl)benzene, 1,4-bis(2,6-dioxatetrahydro-4-methyl-4-pyranyl)benzene, 1,2-di Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 , 4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic acid dianhydride, 4-(2,5-dioxatetrahydro-3-furanyl)-cyclohexane-1,2-dicarboxylic anhydride, tetracyclo[2,2,1,1,1]decane -2,3,7,8-tetracarboxylic acid Dihydride, 5-(2,5-dioxatetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-7 -ene-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5,6-norbornanetetracarboxylic acid Dihydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, tricyclo[4.2.1.0 ^2,5 ]decane-3,4,7,8-tetracarboxylic dianhydride, tetracyclic [4.4.1.0 ^2,5 .0 ^7,10 ] undecane-3,4,8,9-tetracarboxylic dianhydride, hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic dianhydride, 1,4-bis(2,5-dioxatetrahydro-3-furanyl)hexane, 1, 4-bis(2,6-dioxatetrahydro-4-pyranyl)hexane, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1 ,2-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4,5,6,7,8-octahydro-2,3,6,7 - 蒽 tetracarboxylic dianhydride and the like.

The diamine component which is a raw material of the polyimine precursor of the component (B) is preferably a diamine compound having an alicyclic structure or a trifluoromethyl group, and may be used in combination with a diamine compound other than the diamine compound. Specific examples of the diamine compound are, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino group- 3-methylcyclohexyl)methane, 1,4'-dicyclohexyldiamine, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl -4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl) Hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, and 1,3-bis(4-aminophenoxy)propane.

In the present embodiment, in addition to the above diamine compound, one type or a plurality of other diamine compounds may be used in combination.

Other diamine compounds, for example, bis(4-aminophenyl)anthracene, bis(3-aminophenyl)anthracene, bis(4-amino-3-carboxyphenyl)anthracene, bis(4-amine 3-,5-dicarboxyphenyl)anthracene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl碸, bis[4-(3-aminophenoxy)phenyl]indole, bis(3-amino-4-hydroxyphenyl)indole, bis(4-amino-3-hydroxyphenyl)indole , bis(4-amino-3,5-dihydroxyphenyl)anthracene, 3,3'-diamino-4,4'-dichlorodiphenylanthracene, p-phenylenediamine, m - phenyldiamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-dimethyl-1,3-diaminobenzene , 2,5-dimethyl-1,4-diaminobenzene, 2,3,5,6-tetramethyl-1,4-diaminobenzene, 2,4-diaminophenol, 2, 5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, N,N-diallyl-2, 4-Diaminoaniline, N,N-diallyl-2,5-diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2-(4-aminophenyl Ethylamine, 2-(3-aminophenyl)ethylamine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4' -diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3, 3'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenyl Amine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'- Diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-Diaminobenzimidamide, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 4,4'-diamine Diphenylacetylene, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 2,2-bis(4-amine Phenyl)propane, 2,2-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxyl) Octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1,11-bis(4-aminobenzene Oxy) undecane, 1,12-bis(4-aminophenoxy)dodecane, bis(4-aminophenyl)propane diphenyl (dioate), bis(4-aminophenyl) Butane dibasic, bis(4-aminophenyl)pentane dibase, bis(4-aminophenyl)hexanediyl, bis(4-aminophenyl)heptane diyl, bis (4) -aminophenyl)octanediyl, bis(4-aminophenyl)decanediyl, bis(4-aminophenyl)decanediyl, 1,4-bis(4-aminobenzene) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, bis(4-aminophenyl)terephthalate, double (3) -aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl) Phthalate, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1, 3-phenylphenylbis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4) -aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3 - phenyl bis(3-aminobenzoate), N,N'-(1,4-phenylene) bis(4-aminobenzophthalamide), N,N'-(1, 3-phenylene) bis(4-aminobenzoguanamine), N,N'-(1,4-phenylene)bis(3-aminobenzophthalamide), N,N'-( 1,3-phenylene)bis(3-aminobenzophthalamide), bis(4-aminophenyl)terephthalamide, bis(3-aminophenyl)terephthalic acid Amine, bis(4-aminophenyl)isophthalamide, bis(3-aminophenyl)isophthalamide, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,6-diaminoacridine, 2,4-diaminoacridine, 2,4- Diamino-1,3,5-triazine, 2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, 3,6-diaminodibenzofuran, 2 ,6-diaminocarbamide, 2,7- Amino carbitol, 3,6-diaminocarbitol, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-amino group Phenyl)-1,3,4-oxadiazole, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamine Hexyl, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diamine 1,10-decane and 1,12-diaminododecane.

The composition ratio of the total amount of the tetracarboxylic dianhydride (the total amount of the acid components) to the total amount of the diamine compounds (the total amount of the diamine components) of the polyimine precursor of the component (B), that is, <Total Molar Number of Diamine Compound> / <Total Molar Number of Tetracarboxylic Acid dianhydride Compound> It is preferably from 0.5 to 1.5. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polyimine precursor formed, and the molecular weight is increased.

The terminal of the polyimine precursor of the component (B) is changed by the composition ratio of the acid component to the diamine component, and thus is not particularly limited in the embodiment.

In the case where polymerization is carried out using an excess of the diamine component, the terminal amine group is reacted with the carboxylic acid anhydride to protect the terminal amine group. Examples of the carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, and clothing. Kang anhydride and tetrahydrophthalic anhydride.

In the production of the polyimine precursor of the above component (B), the reaction temperature of the acid component and the diamine component may be selected at any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C. For example, the reaction temperature is set to 5 to 40 ° C, and the reaction time is set to 1 to 48 hours to prepare a polyimide precursor. Further, the reaction temperature in the case where the terminal amine group is protected by an acid anhydride can be selected at any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C.

The acid component and the diamine component are reacted therewith, usually in a solvent. The solvent used at this time, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-A Benzoamine, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl hydrazine, m-cresol, γ-butyrolactone, methyl 3-methoxypropionate, 2 Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, B Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether , dipropylene glycol monoethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. These may be used singly or in combination. Further, even if the solvent of the polyimide precursor is not dissolved, it can be used in combination with the above solvent as long as it does not precipitate the range of the polyimide precursor formed by the polymerization reaction.

The solution containing the polyimide precursor obtained by the above method can be used to form a resin composition for forming a thermosetting film without processing. Further, the polyimide precursor can also be recovered after being precipitated in a poor solvent such as water, methanol or ethanol.

<(C) component>

The component (C) in the present embodiment is a crosslinking agent. The crosslinking agent is a component which can crosslink the component (A) and the component (B).

The crosslinking agent of the component (C), for example, an epoxy compound, a methylol compound or an isocyanate compound, is preferably a methylol compound having two or more methylol groups or alkoxymethylol groups.

Specific examples thereof include compounds such as methoxymethylated acetylene urea, methoxymethylated benzoguanamine, and methoxymethylated melamine. Also, for example, hexamethoxymethylmelamine, tetramethoxymethylbenzamine, 1,3,4,6-tetrakis(butoxymethyl)acetyleneurea, 1,3,4,6-tetra(hydroxyl Methyl)acetylene urea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetra(methoxymethyl) Urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-tetrahydroimidazolidone and 1,3-bis(methoxymethyl)-4,5-dimethoxy- 2-tetrahydroimidazolium and the like. In addition, commercially available products such as methoxymethyl melamine compounds (trade names Saimer 300, Semel 301, Saimer 303, Saimer 350), butoxymethyl groups, are manufactured by the Japanese technology industry. a compound such as a melamine compound (trade name: McTea 506, McTerm 508), an acetylene urea compound (trade name: Semel 1170, Paulin 1174), a methylated urea resin (trade name UFR65), butylated urea Resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV) and DIC (stock) urea/formaldehyde resin (high condensation type, trade name Becker J-300S, Beckham P-955, Beckham N) and so on. Further, a compound obtained by condensing a melamine compound, a urea compound, an acetylene urea compound, and a benzoguanamine compound in which a hydrogen atom of the amine group is substituted with a methylol group or an alkoxymethyl group may also be used. For example, a high molecular weight compound produced by a melamine compound (trade name Saimer 303) and a benzoguanamine compound (trade name Saimel 1123) described in U.S. Patent No. 6,323,310.

Further, as the component (C), N-hydroxymethyl methacrylate, N-methoxymethyl methacrylate, N-ethoxymethyl decylamine or N-butoxymethyl may also be used. A polymer produced by a decylamine compound or a methacrylic acid methacrylate compound substituted with a hydroxymethyl group such as decylamine methacrylate or an alkoxymethyl group. Such polymers, for example, poly(N-butoxymethyl decyl amide), copolymer of N-butoxy methacrylate and styrene, N-hydroxymethyl methacrylate and methacrylic acid Copolymer of methyl ester, copolymer of N-ethoxymethyl methacrylate and benzyl methacrylate, and N-butoxy methacrylate and benzyl methacrylate and 2-hydroxyl a copolymer of propyl methacrylate or the like. The weight average molecular weight of the polymers is, for example, from 1,000 to 500,000, or such as from 2,000 to 200,000, or from 3,000 to 150,000, or from 3,000 to 50,000.

The crosslinking agent of the component (C) exemplified above may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the total amount of the acrylic copolymer having at least the photodimerization site and the thermal crosslinking site of the component (A) and the polyamidimide precursor of the component (B) is 100 parts by mass. The content of the crosslinking agent of the component (C) is preferably from 10 to 100 parts by mass. When the ratio is less than 10 parts by mass, the solvent resistance or heat resistance of the cured film obtained by the resin composition is lowered, and the sensitivity at the time of photoalignment is lowered. Further, when it is more than 100 parts by mass, in addition to lowering the optical alignment, there is a fear that the storage stability is lowered.

<(D) component>

In the resin composition of the present embodiment, the component (D) may contain an acid or a thermal acid generator. The component (D) is effective in promoting the thermosetting property of the resin composition of the present embodiment.

The acid or thermal acid generator of the component (D) is a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, and a compound which is thermally decomposed during calcination or post-baking to produce an acid, that is, as long as it is at 80 to 250 ° C. The compound which thermally decomposes to generate an acid is not specifically limited. The compound, for example, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, decanoic acid, Trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, 1,3,5-trimethylbenzenesulfonic acid, p-toluene-2-sulfonic acid, m-toluene-2-sulfonic acid, 4-B Benzobenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, heptafluorobutane-1-sulfonic acid a sulfonic acid such as dodecylbenzenesulfonic acid or a water or a salt thereof.

a compound which generates an acid via heat, for example, bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyltoluenesulfonate Acid ester, o-nitrobenzyl tosylate, 1,2,3-phenylphenyl tris(methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate , p-toluenesulfonate ethyl ester, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenylethyl p-toluenesulfonate , cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluene Other than the guanamine, for example, a compound represented by the following formulas (5) to (9), and formula (14) to formula (49).

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemistry 7]

[化8]

In the resin composition of the present embodiment, the content of the component (D) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When it is less than 0.01 part by mass, the thermosetting property is lowered to make the solvent resistance poor, and the sensitivity of the perceived light irradiation may be lowered. Moreover, when it exceeds 5 mass parts, the storage stability of a composition may fall.

<(E) component>

In the present embodiment, a sensitizer of the component (E) may be contained. The component (E) is effective in promoting the photodimerization reaction after the formation of the thermosetting film of the present embodiment.

A sensitizer of the component (E), such as benzophenone, anthraquinone, anthracene, thioxanthone and a derivative thereof, and a nitrophenyl compound. Among them, benzophenone derivatives and nitrophenyl compounds are particularly preferred. Specifically, for example, N,N-diethylaminobenzophenone, 2-nitroguanidine, 2-nitrofluorenone, 5-nitroguanidine, 9-hydroxymethylhydrazine, 4-nitro Cinnamic acid or 4-nitrobiphenyl. In particular, N,N-diethylaminobenzophenone of the benzophenone derivative is preferred. Further, the sensitizer is not limited to the above. Further, the sensitizer may be used singly or in combination of two or more kinds of compounds.

In the present embodiment, the use ratio of the sensitizer of the component (E) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the component (A). When the ratio is much less than 0.1 part by mass, there is a case where the effect as a sensitizer cannot be sufficiently obtained. Further, when it is more than 20 parts by mass, there is a case where the transmittance is lowered and the coating film is cracked.

<solvent>

The resin composition of the present embodiment is used in the form of a solution obtained by dissolving in a solvent. The solvent to be used is obtained by dissolving the component (B) and the component (C). Further, when the component (D) or the component (E) is contained as necessary, it is also a nighttime solution obtained by dissolving the same, and when it contains other additives described later, it is also a dissolved night obtained by dissolving it. When there is a solvent having a dissolving power, the type, structure, and the like are not particularly limited. Specifically, for example, a solvent used in the polymerization of the component (A) or the component (B), and the like. These solvents may be used alone or in combination of two or more.

<Other additives>

Further, in the case where the effect of the present invention is not impaired, the resin composition of the present embodiment may further contain, if necessary, a decane coupling agent, a surfactant, a flow regulator, a pigment, a dye, a storage stabilizer, an antifoaming agent, and Other additives such as antioxidants.

<Resin composition>

The resin composition of the present embodiment is a crosslinking agent containing the (2) component, the acrylic copolymer having a photodimerization site and a thermal crosslinking site, the polyimine precursor of (B), and the component (C). Further, it may further contain an acid or thermal acid generator of the component (D) and a sensitizer of the component (E), and may further contain one or more additives selected from other additives. Further, the resin composition is usually a solution obtained by dissolving in the solvents.

In the resin composition, the composition ratio of the component (A) to the component (B) is preferably 5:95 to 60:40 by mass. When the content of the component (A) is significantly lower than the composition ratio, there is a concern that alignment failure occurs. Further, when the content of the component (A) is significantly higher than the composition ratio, in addition to the decrease in the birefringence, the coating film is also cloudy.

Further, the hydroxyl value of the component (A) is usually from 1 to 3 mmol/g, and the acid value of the component (B) is usually from 2 to 4 mmol/g, and in the above range, the composition ratio of the component (A) to the component (B) In the case of the range of 5:95 to 40:60, the alignment component of the upper layer can be made to increase the alignment sensitivity, thereby obtaining a high birefringence.

Here, the hydroxyl value of the component (A) means the number of mmoles of calcium hydroxide required for neutralizing acetic acid when the free hydroxyl group contained in 1 g of the component (A) is acetonitrile. Further, the acid value of the component (B) means the number of mmoles of calcium hydroxide required to neutralize the free acid group contained in 1 g of the component (B).

Preferred examples of the resin composition of the present embodiment are as follows.

[1] The resin composition of the component (C) is contained in an amount of 10 to 100 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

[2] A resin composition containing 10 to 100 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the total of the component (A) and the component (B).

[3]: a resin containing 10 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (D), and a solvent, based on 100 parts by mass of the total of the components (A) and (B). Composition.

In the case where the resin composition of the present embodiment is used as a solution, the composition ratio, the production method, and the like are described in detail below.

In the resin composition of the present embodiment, the ratio of the solid component is not particularly limited as long as the components are uniformly dissolved in the solvent, and the solid content ratio is usually from 1 to 80% by mass. Among them, it is preferably from 3 to 60% by mass, more preferably from 5 to 40% by mass. Here, the solid content means a component obtained by removing the entire component of the resin composition from a solvent.

The method for producing the resin composition of the present embodiment is not particularly limited. For example, a method in which the component (A) is dissolved in a solvent, and the component (B) is further added to the component (C) and the component (D) is mixed in a specific ratio to form a homogeneous solution. Further, in an appropriate stage of the production method, a method of mixing other additives, mixing, and the like may be added in accordance with the necessity.

In the production of the resin composition of the present embodiment, the solution of the acrylic polymer obtained by the polymerization reaction in the solvent can be used without processing. In this case, in the solution of the component (A), the components (B), (C) and (D) are added in the same manner as described above to form a homogeneous solution. At this time, when adjusting the concentration or the like, a solvent may be added. The solvent used in the production of the acrylic polymer and the solvent used for adjusting the concentration during the production of the resin composition may be the same solvent or may be selected from different suitable solvents.

A solution of the resin composition of the present embodiment obtained by the above method. It is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film, cured film, and liquid crystal alignment layer>

Using the resin composition of the present embodiment, a coating film was formed by the following method.

First, a resin composition is applied onto the substrate by a method such as spin coating, flow coating, roll coating, slit coating, slit, spin coating, paint spray coating, or printing. Subsequently, the film is formed by pre-drying (pre-baking) on a hot platen or an oven or the like. Thereafter, the cured film is formed by heat treatment (post-baking) of the coating film.

As the substrate on which the resin composition is applied, for example, a ruthenium/ruthenium dioxide-coated substrate, a tantalum nitride substrate, a glass substrate, a quartz substrate, an ITO substrate, or the like can be used. Further, for example, a substrate coated with a metal such as aluminum, molybdenum or chromium may be used. Further, for example, a resin film such as a triacetyl cellulose film, a polyester film, or an acrylic film is used as a substrate.

The pre-baking conditions of the coating film, for example, a heating temperature and a heating time which are appropriately selected from the range of temperature 70 to 160 ° C and time 0.3 to 60 minutes can be employed. The heating temperature and the heating time are preferably 80 to 140 ° C for 0, 5 to 10 minutes.

The baking condition after the film coating is generally a heating temperature appropriately selected by a heating method such as a temperature in the range of 140 to 250 °C. Further, the heating time is also the same, for example, 5 to 30 minutes on the hot platen, 30 to 90 minutes in the oven, and the like.

By the curing of the resin composition of the present embodiment, the retardation of the substrate caused by the filter film (CF) or the like can be sufficiently covered by the above-mentioned conditions to obtain a flattening effect and can also be formed. Highly transparent cured film. Further, the film thickness of the cured film may be, for example, 0.1 to 30 μm, which may be appropriately selected in consideration of the step difference or optical and electrical properties of the substrate to be used.

The cured film obtained by the above method is a liquid crystal alignment material which can be subjected to polarized light irradiation, that is, a function of a liquid crystal alignment layer which can form a liquid crystal compound. At this time, the polarized light used for the polarized light irradiation is preferably UV (ultraviolet). Polarized UV, usually using ultraviolet light with a wavelength of 150 to 450 nm. Subsequently, the hardened film at room temperature or in a heated state is irradiated with linear polarization in a vertical or oblique direction.

The phase difference material is applied onto the liquid crystal alignment layer formed of the resin composition of the present embodiment by the above method, and then heated to a liquid crystal phase transition temperature to form a liquid crystal state of the phase difference material, followed by photocuring. Thus, a layer having optical anisotropy can be formed on the liquid crystal alignment layer, that is, a phase difference material can be formed. The content of the phase difference material disposed in the liquid crystal cell by this method is compared with the conventional configuration in which the phase difference material is disposed outside the liquid crystal cell, and it is found that the contrast ratio of the liquid crystal cell can be improved.

As the phase difference material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, or the like can be used. In the case where the substrate on which the liquid crystal alignment layer is formed is a film, it is suitable as an optical anisotropic film. The phase difference materials are materials having an alignment property such as horizontal alignment, cholesterol alignment, vertical alignment, mixed alignment, and biaxial alignment, which can be used in combination with a desired phase difference.

Moreover, the two substrates having the liquid crystal alignment layer formed as described above can be bonded to each other via the distance adjuster so that the liquid crystal alignment layers face each other, and then the liquid crystal is injected between the substrates. It can be used as a liquid crystal display element for forming a liquid crystal alignment.

As described above, the resin composition of the present embodiment is suitably used for constituting various optical anisotropic films or liquid crystal display elements.

In addition, the resin composition of the present embodiment is suitable as a material for forming a cured film such as a protective film, a flat film, or an insulating film of various displays such as a thin film transistor (TFT) liquid crystal display device and an organic EL device. In addition to the protective film material (CF protective film material) of the filter film (CF), it is suitable as a material which can form an interlayer insulating film of a TFT type liquid crystal element, or an insulating film of an organic EL element.

When the resin composition of the present embodiment is used as a CF protective film material, the obtained CF protective film has a function of a liquid crystal alignment material in addition to the step of covering the filter film to flatten it. Therefore, it can also be used as an CF protective film having an alignment property.

Fig. 1 is a view showing the configuration of a liquid crystal cell mode in the embodiment. In the figure, the liquid crystal layer 108 is sandwiched between two substrates 101 and 111. On the substrate 111, an ITO 110 and an alignment film 109 are formed. Further, on the substrate 101, a filter film 102, a CF protective film 103, a phase difference material 105, an ITO 106, and an alignment film 107 are sequentially formed. In this case, since the CF protective film 103 functions as an alignment film, it is not necessary to use a film corresponding to the alignment film 204 of Fig. 2 .

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples.

[Abbreviation used in the examples]

The abbreviations used in the following examples have the following meanings.

<acrylic polymer>

HEMA: 2-hydroxyethyl methacrylate

CIN: methyl 4-(6-methylpropoxyhexyl-1-oxy) cinnamate

AIBN: α, α'-azobisisobutyronitrile

<Polyimide precursor>

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

ODPA: 4,4'-oxophthalic anhydride

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

TFMB: 2,2'-trifluoromethyl-4,4'-diaminobiphenyl

<crosslinker>

CYM: Saimer 303 (Mitsui Technology)

<Acid or thermal acid generator>

PTSA: p-toluenesulfonic acid 1 water and substance

<solvent>

CHN: cyclohexanone

NMP: N-methylpyrrolidone

The number average molecular weight and the weight average molecular weight of the acrylic copolymer obtained by the following synthesis examples were obtained by using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation, and the solvent tetrahydrofuran was dissolved in the tube. The value measured under the conditions in which the column (column temperature: 40 ° C) was flow-dissolved at a flow rate of 1 ml/min. Further, the following average molecular weight (hereinafter also referred to as Mn) and weight average molecular weight (hereinafter also referred to as Mw) are expressed in terms of polystyrene.

Further, the Mn and Mw of the polyimide precursor are a GPC apparatus (Shodex (registered trademark) column KD803 and KD805) manufactured by Shodex Co., Ltd., and the solvent N, N,-dimethylformamide (additive, Lithium bromide-water (LiBr‧H ₂ O) is 30 mmol/L, phosphoric acid ‧ anhydrous crystals (o-phosphoric acid is 30 mmol/L, tetrahydrofuran is 10 ml/L), in a column (column temperature 50 ° C) The flow rate was measured at a flow rate of 1 ml/min for dissolution. Further, the following Mn and Mw are represented by polyethylene glycol and polyethylene oxide equivalent values.

<Synthesis Example 1>

42.0 g of CIN, 18.0 g of HEMA, and 1.3 g of AIBN were dissolved in 166.8 g of CHN, and reacted at 80 ° C for 20 hours to obtain an acrylic polymer solution (the obtained solid content concentration was 27% by mass) (P1). The obtained acrylic polymer had an Mn of 8,500 and a Mw of 16,500.

<Synthesis Example 2>

16.0 g of TFMB was dissolved in 114.1 g of NMP. Subsequently, 12.5 g of BPDA was added, and the reaction was carried out at 40 ° C for 20 hours to obtain a polyimide precursor solution (the obtained solid content concentration was 20% by mass) (P2). The obtained polyimine precursor had an Mn of 12,600 and a Mw of 27,500.

<Synthesis Example 3>

5.1 g of TFMB was dissolved in NMP 72.2 g. Subsequently, 4.7 g of ODPA was added, and the mixture was reacted at room temperature for 20 hours to obtain a polyimide precursor solution (the obtained solid content concentration was 12% by mass) (P3). The obtained polyimide intermediate precursor had an Mn of 7,000 and a Mw of 15,800.

<Synthesis Example 4>

233.8 g of TFMB was dissolved in NMP 2111.6 g. Subsequently, 142.9 g of CBDA was added, and the mixture was reacted at room temperature for 20 hours to obtain a polyimide precursor solution (the obtained solid content concentration was 15% by mass) (P4). The obtained polyimine precursor had an Mn of 12,400 and a Mw of 43,000.

<Example 1 to Example 3 and Comparative Example 1 to Comparative Example 4>

Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was produced according to the composition shown in Table 3, and the solvent resistance, transmittance, alignment, and birefringence were evaluated, respectively.

[Evaluation of Solvent Resistance]

Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto a ruthenium wafer using a spin coater, and then preheated on a hot plate at a temperature of 80 ° C for 120 seconds. Baked. Subsequently, this coating film was baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes, and then baked to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

Next, the cured film was immersed in CHN or NMP for 60 seconds, and then dried at a temperature of 100 ° C for 60 seconds, respectively, and then the film thickness was measured. The film thickness after immersion of CHN or NMP was not changed, and the film thickness after immersion was observed to be "x".

[Evaluation of light transmittance (transparency)]

Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then preliminarily heated on a hot plate at a temperature of 80 ° C for 120 seconds. Baked. Subsequently, the coating film was baked in a hot air circulating oven, and baked at a temperature of 230 ° C for 30 minutes to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

Next, the cured film was measured by using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 (model) manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 400 nm was measured.

[Evaluation of alignment sensitivity]

Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto an ITO substrate using a spin coater, and then calcined on a hot plate at a temperature of 80 ° C for 120 seconds. Baked. Subsequently, this coating film was baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes, and then baked to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

Next, the linear light having a polarization wavelength of 313 nm was polarized and irradiated in a direction perpendicular to the cured film on the ITO substrate. Subsequently, the phase difference material solution formed of the liquid crystal monomer is coated on the substrate using a spin coater, and then pre-baked at 80 ° C for 60 seconds on a hot plate to form a film thickness of 1.4 μm. Coating film. Next, the coating film on the substrate was exposed to UV light of 1,000 mJ/cm ² in a nitrogen atmosphere to cure the phase difference material. The substrate 制 obtained in this manner was sandwiched between the polarizing plates, and the phase difference state of the hardened phase difference material was confirmed, and the exposure amount of the polarized light UV necessary for forming the cured film to obtain the alignment property was determined as the alignment sensitivity. Further, even if exposure is performed using UV light of 3,000 mJ/cm ² , the alignment is not indicated by "x".

[Evaluation of birefringence]

Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then pre-baked at a temperature of 80 ° C for 120 seconds on a hot platen. . Subsequently, this coating film was baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes, and then baked to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

This cured film was measured for a birefringence at a wavelength of 590 nm using a retardation film measuring apparatus (Axo Scan manufactured by AXOMETRICS Inc.).

[evaluation result]

The results of the above evaluation are shown in Table 4.

The cured films formed from the compositions of Examples 1 to 3 exhibited high alignment sensitivity. Therefore, the compositions of Examples 1 to 3 were known to form an efficient liquid crystal alignment material. In addition, it is also confirmed to have high transparency and to be resistant to any of CHN and NMP. Also, high birefringence is also exhibited.

Further, the cured film formed of the composition of Comparative Example 1 had low birefringence and solvent resistance, and in order to obtain the alignment property, it was necessary to have an exposure of 300 times with respect to the cases of Examples 1 to 3. the amount. Further, the cured films formed of the compositions of Comparative Examples 2 to 4 had high birefringence and solvent resistance, but did not exhibit alignment.

As described above, the cured film obtained by the resin composition of the present invention has a high birefringence and excellent light transmittance, solvent resistance and alignment. Therefore, the resin composition of the present invention can provide a cured film which is used for various excellent properties as described above, that is, it can be used for a liquid crystal alignment material, and a phase difference material can also be formed.

[Industrial use]

The resin composition of the present invention is excellent as a liquid crystal alignment material for an optically anisotropic film or a liquid crystal display element, and is also suitable as a liquid crystal display element or an organic EL element in various displays such as a thin film transistor (TFT) type liquid crystal display element. A material for forming a cured film such as a protective film, a flat film, or an insulating film is particularly suitable as a material for forming an interlayer insulating film of a TFT-type liquid crystal element, a protective film of a filter film, or an insulating film of an organic EL element.

101. . . Substrate

102. . . Filter film

103. . . CF protective film

105. . . Phase difference material

106. . . ITO

107. . . Orientation film

108. . . Liquid crystal layer

109. . . Orientation film

110. . . ITO

111. . . Substrate

202. . . Filter film

204. . . Orientation film

205. . . Phase difference material

Fig. 1 is a structural schematic view showing a liquid crystal cell obtained in the present embodiment.

Fig. 2 is a structural schematic view of a conventional liquid crystal cell.

101. . . Substrate

102. . . Filter film

103. . . CF protective film

105. . . Phase difference material

106. . . ITO

107. . . Orientation film

108. . . Liquid crystal layer

109. . . Orientation film

110. . . ITO

111. . . Substrate

Claims (16)

A resin composition comprising (A) an acrylic copolymer having a photodimerization site formed by a hydrophobic group and a thermal crosslinking site formed by a hydrophilic group, and having a (B) main chain a polyphenylenimine precursor of a phenyl structure, and (C) a crosslinking agent which crosslinks the component (A) with the component (B). The resin composition of claim 1, wherein the component (A) is an acrylic acid obtained by polymerizing a monomer mixture having a photodimerization site and a monomer having a thermal crosslinking site. Copolymer. The resin composition of claim 2, wherein the component (A) is a monomer having a photodimerization site in an amount of from 25 mol% to 90 mol% based on the total amount of the total monomer mixture. The acrylic copolymer obtained by polymerization of the monomer mixture. The resin composition of claim 1, wherein the photodimerization site of the component (A) is cinnabarinyl. The resin composition of claim 1, wherein the thermally crosslinked portion of the component (A) is a hydroxyl group or a carboxyl group. The resin composition of claim 1, wherein the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, the tetracarboxylic acid At least one of the acid dianhydride and the diamine compound is a compound having a biphenyl structure. For example, the resin composition of claim 6 of the patent scope, wherein The tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride. The resin composition of claim 6, wherein the component (B) is a polyimine precursor having a trifluoromethyl group as the structural unit. The resin composition of claim 1, wherein the polyimine precursor of the component (B) has an alicyclic structure as a main chain. The resin composition of claim 9, wherein the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, and the fourth At least one of the carboxylic acid dianhydride and the diamine compound is one having an alicyclic structure. The resin composition of claim 1, wherein the crosslinking agent of the component (C) is a crosslinking agent having a methylol group or an alkoxymethylol group. The resin composition of the first aspect of the invention, wherein the component (C) is contained in an amount of 10 to 100 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). The resin composition of claim 1 which further contains the acid or thermal acid generator of the component (D). The resin composition of claim 13 which contains 0.1 to 10 parts by mass of the component (D) based on 100 parts by mass of the total of the component (A) and the component (B). A liquid crystal alignment material obtained by using the resin composition of any one of claims 1 to 14. A phase difference material characterized by the use of a patent application The cured film obtained from the resin composition of any one of items 1 to 14 is formed.