JP6747433B2 - Thermosetting resin composition and homeotropic alignment retardation film - Google Patents

Description

The present invention relates to a thermosetting resin composition and a homeotropic alignment retardation film, and more specifically, a liquid crystal display (LCD), specifically a liquid crystal having a positive dielectric anisotropy (Δ). +C plate (positive C plate) used to improve the viewing angle characteristics of an IPS liquid crystal display device (In-plane Switching LCD (IPS-LCD); in-plane alignment switching LCD) filled with ε>0). The present invention relates to a thermosetting resin composition and a homeotropic oriented retardation film useful for preparing the composition.

The IPS-LCD is characterized in that the change in brightness/color change depending on the viewing angle is small because the liquid crystal molecules are not tilted in the vertical direction, but the weak point is that it is difficult to increase the contrast ratio and the brightness and response speed. Can be mentioned.
For example, as disclosed in Patent Document 1, the IPS-LCD in the initial proposal does not use a viewing angle compensation film, and the IPS-LCD that does not use such a viewing angle compensation film has a tilt angle. However, it has a disadvantage of exhibiting a low contrast ratio value due to relatively large light leakage in the dark state.

Patent Document 2 discloses an IPS-LCD compensation film using a +C plate and a +A plate (positive A plate). In this document, the liquid crystal display element described therein has the following configuration.
1) A liquid crystal layer having a horizontal alignment is sandwiched between both substrates supplied by electrodes capable of applying an electric field parallel to the liquid crystal layer surface.
2) One or more +A plate and +C plate are sandwiched between both polarizing plates.
3) The main optical axis of the +A plate is perpendicular to the main optical axis of the liquid crystal layer.
4) of the liquid crystal layer retardation value R _LC, + C plate retardation value R _{+ C,} + A retardation value R _{+ A} plate is determined so as to satisfy the following equation.
R _LC : R _+C : R _+A ≈ 1:0.5:0.25
5) The relationship between the retardation values of the +A plate and the +C plate and the retardation value in the thickness direction of the protective film of the polarizing plate is not shown (TAC, COP, PNB).

Further, Patent Document 3 provides an IPS-LCD having high contrast characteristics in the front and tilt angles and low color shift (Color Shift) by minimizing light leakage in a dark state at the tilt angle. Disclosed is an IPS-LCD having a +A plate and a +C plate.

As proposed in the related art, the +C plate is capable of compensating for light leakage in a polarizing plate with a wide viewing angle, and thus is very useful as an optical compensation film for an IPS-LCD. However, it is difficult to express the homeotropic orientation (positive C plate) by the conventionally known method of stretching.
Further, in the conventionally proposed method using a vertical alignment film using polyimide and a polymerizable liquid crystal, it is necessary to use a solvent for polyimide such as N-methyl-2-pyrrolidone in forming the film. For this reason, a glass substrate is not a problem, but when the substrate is a film, there is a problem that the substrate is damaged when the alignment film is formed. In addition, a vertical alignment film using polyimide needs to be baked at a high temperature, which causes a problem that the film base material cannot withstand the high temperature.
Therefore, there is a demand for a cured film-forming composition that can form a highly reliable retarder even on a resin film such as a TAC or COP film and can form a +C plate by a simple method.

As a means for solving such a problem, development of a new liquid crystal material capable of homeotropic alignment on a substrate without using a vertical alignment film is underway. For example, Patent Documents 4 to 6 disclose: As such a liquid crystal material, a side chain type liquid crystal polymer composed of a monomer unit (a) containing a liquid crystal fragment side chain and a monomer unit (b) containing a non-liquid crystal fragment side chain is disclosed. The polymer has a problem that it tends to become cloudy because the orientation direction of the liquid crystal is unstable.
Further, in order to improve this problem, it is disclosed that a liquid crystal monomer is added and ultraviolet curing is performed to fix the alignment of the liquid crystal, but an ultraviolet irradiation step was required.

JP-A-2-256023 JP-A-11-133408 JP, 2009-122715, A JP, 2002-174725, A JP, 2002-333642, A JP, 2002-365635, A

The present invention has been made in view of the above circumstances, and is capable of homeotropic alignment without using a vertical alignment film, and a cloudy (transparency), and a thermosetting film having improved surface tackiness. It is an object to provide a thermosetting resin composition and a homeotropic alignment retardation film to be given.

The present inventors have conducted intensive studies to achieve the above-mentioned object, and as a result, by using a polymer having a predetermined liquid crystal side chain, a vertical alignment group and a thermally crosslinkable group together with a crosslinking agent, vertical alignment is achieved. The present invention has been completed by finding that a thermosetting resin composition can be obtained which allows homeotropic alignment without using a film and gives a cured film having good transparency and no surface tack.

（式中、Ｘは、ＣＯＯ基またはＯＣＯ基を、Ｒは、水素原子、フッ素原子、シアノ基、炭素数１〜６のアルキル基、ヒドロキシ基、カルボキシル基、または炭素数１〜６のアルコキシ基を表し、ｎは、１〜１０の整数を、ｏおよびｐは、１または２の整数を表す。）
２． 前記熱架橋性基が、ヒドロキシ基、カルボキシル基、アミノ基、ブロックイソシアネート基、ビニル基、アリル基、（メタ）アクリル基、エポキシ基、オキセタニル基およびアルコキシシリル基から選ばれる１種または２種以上である１の熱硬化性樹脂組成物、
３． 前記垂直配向性基が、式（２）で表される１または２の熱硬化性樹脂組成物、

（式中、Ｙ¹は、単結合、または−Ｏ−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−ＣＯ−Ｏ−および−ＮＨ−ＣＯ−ＮＨ−から選ばれる結合基を表し、
Ｙ²は、単結合、炭素数１〜１５のアルキレン基または−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−基を表すか、ベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基を表し、前記環状基上の任意の水素原子が、Ｚで置換されていてもよく、
Ｙ³は、単結合または炭素数１〜１５のアルキレン基を表し、
Ｙ⁴は、単結合、ベンゼン環、シクロヘキサン環もしくは複素環から選ばれる２価の環状基、または炭素数１７〜３０のステロイド骨格を有する２価の有機基を表し、前記環状基上の任意の水素原子が、Ｚで置換されていてもよく、
Ｙ⁵は、ベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基を表し、これらの環状基上の任意の水素原子が、Ｚで置換されていてもよく、
ｍは、０〜４の整数を表し、ｍが２以上の場合、Ｙ⁵は互いに同一でも異なっていてもよく、
Ｙ⁶は、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のフッ化アルキル基、炭素数１〜１８のアルコキシ基または炭素数１〜１８のフッ化アルコキシ基を表し、
Ｚは、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ化アルキル基、炭素数１〜３のフッ化アルコキシ基またはフッ素原子を表し、
前記アルキレン基、アルキル基、フッ化アルキル基、アルコキシ基およびフッ化アルコキシ基は、結合基同士が隣り合わない限り、その中に１〜３の前記結合基を有していてもよく、
前記Ｙ²〜Ｙ⁶において、アルキレン基、−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−基、２価の環状基、ステロイド骨格を有する２価の有機基、アルキル基およびフッ化アルキル基は、それらに隣接する基と前記結合基を介して結合していてもよい。
ただし、Ｙ²〜Ｙ⁶が表す置換基の総炭素数は、６〜３０である。）
４． 前記Ｙ¹、Ｙ²およびＹ⁴が、単結合であり、前記Ｙ³が、炭素数１〜１５のアルキレン基であり、前記ｍが、０であり、前記Ｙ⁶が、炭素数１〜１８のアルキル基であり、前記Ｙ³およびＹ⁶の総炭素数が、６〜２０である３の熱硬化性樹脂組成物、
５． 前記ｎが、２〜８の整数を表し、前記ｏおよびｐが、１であり、前記Ｒが、炭素数１〜６のアルコキシ基である１〜４のいずれかの熱硬化性樹脂組成物、
６． 前記（Ｂ）成分が、メチロール基またはアルコキシメチル基を有する架橋剤である１〜５のいずれかの熱硬化性樹脂組成物、
７． （Ｄ）架橋触媒をさらに含有する１〜６のいずれかの熱硬化性樹脂組成物、
８． 前記（Ａ）成分１００質量部に対し、前記（Ｂ）成分１〜１００質量部含有する１〜７のいずれかの熱硬化性樹脂組成物、
９． 前記（Ａ）成分および（Ｂ）成分の合計１００質量部に対し、前記（Ｄ）成分０．０１〜２０質量部含有する７または８の熱硬化性樹脂組成物、
１０． １〜９のいずれかの熱硬化性樹脂組成物を熱硬化させて形成されるホメオトロピック配向位相差フィルム、
１１． １〜９のいずれかの熱硬化性樹脂組成物を熱硬化させた後、冷却後２４時間以上放置するホメオトロピック配向位相差フィルムの製造方法
を提供する。That is, the present invention is
1. (A) A thermosetting resin containing a liquid crystal side chain represented by the formula (1), a polymer having a vertical alignment group and a thermal crosslinking group, (B) a crosslinking agent, and (C) a solvent. Resin composition,

(In the formula, X is a COO group or an OCO group, R is a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxyl group, or an alkoxy group having 1 to 6 carbon atoms. Represents, and n represents an integer of 1 to 10, and o and p represent an integer of 1 or 2.)
2. The heat-crosslinkable group is one or more selected from a hydroxy group, a carboxyl group, an amino group, a blocked isocyanate group, a vinyl group, an allyl group, a (meth)acryl group, an epoxy group, an oxetanyl group and an alkoxysilyl group. 1 is a thermosetting resin composition,
3. The thermosetting resin composition according to 1 or 2 in which the vertical alignment group is represented by formula (2):

(In the formula, Y ¹ is a single bond or —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represents the selected linking group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or a —CH ₂ —CH(OH)—CH ₂ — group, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle. , Any hydrogen atom on the cyclic group may be substituted with Z,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond, a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and any of the above cyclic groups. A hydrogen atom may be replaced by Z,
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups may be substituted with Z,
m represents an integer of 0 to 4, and when m is 2 or more, Y ⁵ may be the same or different from each other,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 18 carbon atoms,
Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom,
The alkylene group, the alkyl group, the fluorinated alkyl group, the alkoxy group and the fluorinated alkoxy group may have 1 to 3 of the bonding groups therein as long as the bonding groups are not adjacent to each other,
In the above Y ^{2 to} Y ⁶ , an alkylene group, a —CH ₂ —CH(OH)—CH ₂ — group, a divalent cyclic group, a divalent organic group having a steroid skeleton, an alkyl group and a fluorinated alkyl group, It may be bonded to a group adjacent to them via the bonding group.
However, the total number of carbon atoms of the substituents represented by Y ^{2 to} Y ⁶ is ⁶ to 30. )
4. Each of Y ¹ , Y ² and Y ⁴ is a single bond, Y ³ is an alkylene group having 1 to 15 carbon atoms, m is 0, and Y ⁶ is 1 to 18 carbon atoms. A thermosetting resin composition of ³ , wherein the total number of carbon atoms of Y ³ and Y ⁶ is 6 to 20,
5. The thermosetting resin composition according to any one of 1 to 4, wherein n represents an integer of 2 to 8, o and p are 1, and R is an alkoxy group having 1 to 6 carbon atoms,
6. The thermosetting resin composition according to any one of 1 to 5, wherein the component (B) is a cross-linking agent having a methylol group or an alkoxymethyl group,
7. (D) the thermosetting resin composition according to any one of 1 to 6, further containing a crosslinking catalyst;
8. 1 to 100 parts by mass of the component (B), relative to 100 parts by mass of the component (A), the thermosetting resin composition according to any one of 1 to 7;
9. 7 or 8 thermosetting resin composition containing 0.01 to 20 parts by mass of the component (D) with respect to a total of 100 parts by mass of the component (A) and the component (B).
10. A homeotropic alignment retardation film formed by thermosetting the thermosetting resin composition according to any one of 1 to 9;
11. Provided is a method for producing a homeotropic alignment retardation film, which comprises heat-curing the thermosetting resin composition according to any one of 1 to 9 and then leaving it for 24 hours or more after cooling.

By using the thermosetting resin composition of the present invention, a homeotropic alignment retardation film can be produced without using a vertical alignment film, only by coating on a substrate and baking.
Further, the obtained cured film has excellent surface tackiness (no tack), little cloudiness, and excellent transparency.

Hereinafter, the present invention will be described in more detail.
The thermosetting resin composition according to the present invention contains (A) a polymer having a liquid crystalline side chain, a vertical alignment group and a thermally crosslinkable group, (B) a crosslinking agent, and (C) a solvent.
The polymer of the component (A) used in the present invention is not particularly limited, but a monomer having an unsaturated double bond such as a (meth)acrylic acid ester compound, a vinyl compound, a styrene compound, a maleimide compound is polymerized. The resulting copolymer is preferred.
In particular, the polymer of the component (A) of the present invention is preferably an acrylic copolymer having a liquid crystal group, a vertical alignment group and a heat crosslinkable group in the side chain, and the main polymer of the polymer constituting the acrylic copolymer is preferable. The chain skeleton and the types of other side chains are not particularly limited.

The weight average molecular weight of the polymer as the component (A) is not particularly limited, but it is required to exhibit good retardation, heat resistance due to thermosetting, good tackiness, and handling property due to solvent solubility. Considering this, 1,000 to 200,000 is preferable, 2,000 to 150,000 is more preferable, and 3,000 to 100,000 is even more preferable.
The weight average molecular weight in the present invention is an average molecular weight obtained in terms of standard polystyrene by high performance liquid chromatography analysis.

The liquid crystalline side chain is not particularly limited as long as it is a nematic liquid crystalline side chain and the obtained thermosetting film has homeotropic alignment, and can be appropriately selected from known ones and used. In the invention, those represented by the formula (1) are particularly preferable.

In the formula (1), X is a COO group or an OCO group, and a COO group is preferable.
R represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxyl group, or an alkoxy group having 1 to 6 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. It is a base.
The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl and s-butyl. , T-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1 ,1-Dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl , 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl. , 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl -N-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl , 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl , 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl -Cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl- Cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl group and the like can be mentioned.

Examples of the alkoxy group having 1 to 6 carbon atoms include a group in which an oxygen atom (-O-) is bonded to the alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propoxy and iso. Propoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl- n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl- n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n -Butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1 , 1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy group and the like. To be

Although n is an integer of 1 to 10, an integer of 2 to 8 is preferable, and an integer of 4 to 8 is more preferable.
o and p represent an integer of 1 or 2, but 1 is preferable for both.

The liquid crystalline side chain can be introduced into the polymer by using, for example, a (meth)acrylic-based monomer, a vinyl-based monomer, a styrene-based monomer, a maleimide-based monomer or the like having the above-mentioned liquid crystal side chain. As described above, it is preferable to introduce the (meth)acrylic monomer having the liquid crystal side chain into the polymer.
In addition, these monomers can be manufactured by a known method.

The vertical orientation group is not particularly limited, but a group containing a hydrocarbon group having about 6 to 20 carbon atoms is preferable, and specifically, a group represented by the formula (2) is preferable. Is.

In formula (2), Y ¹ is a single bond, or —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH. Represents a bonding group selected from —, Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or a —CH ₂ —CH(OH)—CH ₂ — group, a benzene ring, a cyclohexane ring or a heterocycle. Represents a divalent cyclic group selected from, any hydrogen atom on the cyclic group may be substituted with Z, Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y ⁴ is , A single bond, a benzene ring, a cyclohexane ring or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and an arbitrary hydrogen atom on the cyclic group is Z. Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups may be substituted with Z. , M represents an integer of 0 to 4, and when m is 2 or more, Y ⁵ may be the same or different from each other, Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or 1 to 1 carbon atom. Represents a fluorinated alkyl group having 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 18 carbon atoms, Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, Represents a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and the alkylene group, the alkyl group, the fluorinated alkyl group, the alkoxy group and the fluorinated alkoxy group are bonded to each other. May have 1 to 3 of the above-described bonding groups unless they are adjacent to each other, and in Y ^{2 to} Y ⁶ , an alkylene group, a —CH ₂ —CH(OH)—CH ₂ — group, and a divalent group. The cyclic group, the divalent organic group having a steroid skeleton, the alkyl group and the fluorinated alkyl group may be bonded to the group adjacent thereto through the above-mentioned bonding group. However, the total number of carbon atoms of the substituents represented by Y ^{2 to} Y ⁶ is ⁶ to 30.

The alkylene group having 1 to 15 carbon atoms is one obtained by removing one hydrogen atom from the alkyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 18 carbon atoms to be described later. Examples of the valent group include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and octamethylene groups.
Specific examples of the heterocycle include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, Pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like, Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring are preferable.

Specific examples of the divalent organic group having a steroid skeleton having 17 to 30 carbon atoms include cholesteryl, andsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl. Is a divalent organic group having a structure in which two hydrogen atoms are removed from a structure selected from the group consisting of mestranil, methyltestrosteryl, noretisteryl, pregnenoronyl, β-sitosteryl, stigmasteryl, testosteryl, and acetic acid cholesterol ester. Specific examples thereof include the divalent organic groups shown below, but the invention is not limited thereto.

（式中、＊は結合位置を表す。）

(In the formula, * represents a bonding position.)

Examples of the alkyl group having 1 to 18 carbon atoms include n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, and 3-methyl-n, in addition to the alkyl groups exemplified above with 1 to 6 carbon atoms. -Hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n -Pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1 -Methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl , 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl -N-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl , 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2. -Ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl , N-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl group and the like.
Examples of the fluorinated alkyl group having 1 to 18 carbon atoms include groups in which at least one hydrogen atom in the above alkyl group having 1 to 18 carbon atoms has been replaced by a fluorine atom, and specific examples thereof include fluoromethyl and difluoromethyl. , Trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2 ,2,2-Trifluoro-1-(trifluoromethyl)ethyl, nonafluorobutyl, 4,4,4-trifluorobutyl, undecafluoropentyl, 2,2,3,3,4,4,5 5,5-nonafluoropentyl, 2,2,3,3,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2,3,3,4,4,5,5,6 ,6,6-Undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6 6-nonafluorohexyl and the like can be mentioned.

Specific examples of the fluorinated alkoxy group having 1 to 18 carbon atoms include a group in which an oxygen atom (—O—) is bonded to the fluorinated alkyl group having 1 to 18 carbon atoms, and specific examples thereof include fluoro. Methoxy, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, heptafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3-tetra Fluoropropoxy, 2,2,2-trifluoro-1-(trifluoromethyl)ethoxy, nonafluorobutoxy, 4,4,4-trifluorobutoxy, undecafluoropentyloxy, 2,2,3,3,4 ,4,5,5,5-nonafluoropentyloxy, 2,2,3,3,4,5,5-octafluoropentyloxy, tridecafluorohexyloxy, 2,2,3,3,4 ,4,5,5,6,6,6-Undecafluorohexyloxy, 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy, 3,3,4 , 4,5,5,6,6,6-nonafluorohexyloxy group and the like.

In addition, as the C1-C3 alkyl group in the said Z, the C1-C3 thing is mentioned among the groups illustrated by the said C1-C6, and it is as a C1-C3 alkoxy group. Among the groups exemplified by the alkoxy group having 1 to 6 carbon atoms, those having 1 to 3 carbon atoms can be mentioned. As the fluorinated alkyl group having 1 to 3 carbon atoms, the fluorinated alkyl group having 1 to 18 carbon atoms can be mentioned. Among the groups exemplified as the group, those having 1 to 3 carbon atoms can be mentioned, and as the fluorinated alkoxy group having 1 to 3 carbon atoms, among the groups exemplified as the fluorinated alkoxy group having 1 to 18 carbon atoms, carbon The thing of several 1-3 is mentioned.

Of these, Y ¹ is preferably a single bond, Y ² is preferably a benzene ring or a cyclohexane ring, Y ³ is preferably an alkylene group having 1 to 15 carbon atoms, and has a carbon number from the viewpoint of ease of synthesis. 1-9 alkylene groups are more preferred, Y ⁴ is preferably a benzene ring, a cyclohexane ring or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and Y ⁵ is a benzene ring or a cyclohexane ring. Preferably, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 10 carbon atoms, and 1 carbon atom The alkyl group having 1 to 12 or the alkoxy group having 1 to 12 carbons is more preferable, and the alkyl group having 1 to 9 carbons or the alkoxy group having 1 to 9 carbons is even more preferable.
However, when Y ⁴ is a divalent organic group having a steroid skeleton, Y ⁶ is preferably a hydrogen atom.
Further, from the viewpoint of availability of raw materials, easiness of synthesis, and the like, m is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

The alkylene group, the alkyl group, the fluorinated alkyl group, the alkoxy group and the fluorinated alkoxy group may have 1 to 3 of the above-described bonding groups, unless the bonding groups are adjacent to each other. , Y ^{2 to} Y ⁶ , an alkylene group, a —CH ₂ —CH(OH)—CH ₂ — group, a divalent cyclic group, a divalent organic group having a steroid skeleton, an alkyl group and a fluorinated alkyl group, You may couple|bond with the group which adjoins them through the coupling group mentioned above.

The total carbon number of the substituents represented by Y ^{2 to} Y ⁶ is ⁶ to 30, but 6 to 20 is preferable.
In particular, in consideration of the vertical alignment property and coatability of the obtained liquid crystal polymer, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms.
Specific examples of the vertical alignment group include hydrocarbon groups having about 6 to 20 carbon atoms. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a linear, branched or cyclic alkyl group having 6 to 20 carbon atoms or a hydrocarbon group having 6 to 20 carbon atoms including an aromatic group.
Therefore, in the above formula (2), Y ¹ , Y ² and Y ⁴ are single bonds, and Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms (preferably an alkylene group having 1 to 15 carbon atoms). ), m is 0, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, and an alkyl group (a-1) having a total carbon number of 6 to 20 of Y ³ and Y ⁶ , is preferable, An alkyl group having a total carbon number of 7 to 18 is more preferable, and an alkyl group having a total carbon number of 8 to 15 is even more preferable.
Specific examples of such a vertical alignment group (a-1) include an n-nonadecyl group and an n-eicosinyl group, in addition to the alkyl group having 6 to 18 carbon atoms exemplified by the alkyl group having 1 to 18 carbon atoms described above. Etc.

In addition to the vertical alignment group (a-1), for example, Y ^{1 to} Y ⁴ are single bonds, m is 2 or 3, and Y ⁵ is a benzene ring or a cyclohexane ring. Also, the vertical alignment group (a-2) in which Y ⁶ is an alkyl group having 1 to 18 carbon atoms can also be suitably used.
Specific examples of such a vertical alignment group (a-2) include groups represented by the following (a-2-1) to (a-2-6), but are not limited thereto. Absent.

（式中、Ｙ⁶は上記と同じ。）

(In the formula, Y ⁶ is the same as above.)

Further, in addition to the vertical alignment groups (a-1) and (a-2), for example, Y ^{1 to} Y ³ are a single bond, and Y ⁴ is a divalent group having a steroid skeleton having 17 to 30 carbon atoms. The vertical group (a-3) in which m is 0 and Y ⁶ is a hydrogen atom can also be suitably used.
Examples of such a vertical alignment group (a-3) include, but are not limited to, the groups represented by the following (a-3-1) to (a-3-8). ..

（式中、＊は結合位置を表す。）

(In the formula, * represents a bonding position.)

The vertical alignment group described above should be introduced into the polymer using a monomer having an unsaturated double bond such as a (meth)acrylic monomer, a vinyl monomer, a styrene monomer, or a maleimide monomer having the same. However, also in this case, it is preferable to introduce the (meth)acrylic monomer having the above-mentioned vertical alignment group into the polymer.
Specific monomers include (meth)acrylic acid alkyl esters, alkyl vinyl ethers, 2-alkylstyrenes, 3-alkylstyrenes, 4-alkylstyrenes, and N-alkylmaleimides, in which the alkyl group has 6 to 20 carbon atoms. There are things.
These monomers can be produced by a known method, and some of them are commercially available.
In the case where a (meth)acrylic monomer having a vertically aligning group represented by the above formula (2) is used to introduce a vertically aligning group into a polymer, the vertically aligning side chain has the following formula (2′). ).

Further, the heat-crosslinkable group contained in the polymer of the component (A) used in the present invention includes a hydroxy group, a carboxyl group, an amino group, a blocked isocyanate group, a vinyl group, an allyl group, a (meth)acrylic group, an epoxy group, and oxetanyl. Group and an alkoxysilyl group.
Among these, a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group are preferable from the viewpoint of forming a thermosetting film at low temperature and in a short time.

These heat-crosslinkable groups can also be introduced into the polymer by using a monomer having an unsaturated double bond such as a (meth)acrylic monomer, a vinyl monomer, a styrene monomer, a maleimide monomer having the same. However, also in this case, it is preferable to introduce into the polymer by using a heat-crosslinkable group-containing alkyl ester of (meth)acrylic acid.

Examples of the monomer having a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group as the heat-crosslinkable group include, for example, 2-hydroxyethyl acrylate, 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 monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-( Methacryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, poly(ethylene glycol)ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6- Monomers having a hydroxy group such as hydroxynorbornene-2-carboxylic-6-lactone; acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy) Monomers having a carboxyl group such as ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)acrylamide, N-(carboxyphenyl)methacrylamide; hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-( Monomers having a phenolic hydroxy group such as hydroxyphenyl)methacrylamide and N-(hydroxyphenyl)maleimide; monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate; acryloyloxypropyltri Examples thereof include monomers having an alkoxysilyl group such as methoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltriethoxysilane.

Further, as long as the effects of the present invention are not impaired, in addition to the above-mentioned monomer having a liquid crystalline side chain, a monomer having a vertical alignment group, and a monomer having a thermally crosslinkable group, it is possible to copolymerize with these monomers. Other monomers having no liquid crystalline side chain, vertical alignment group and heat-crosslinkable group can be used in combination.
Specific examples of other monomers include (meth)acrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Hereinafter, specific examples of other monomers will be given, but the present invention is not limited thereto.
Specific examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl 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 and the like.

Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl 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, γ-butyrolactone methacrylate and the like. To be

Specific examples of the maleimide compound include maleimide, N-methylmaleimide, N-ethylmaleimide and the like.
Specific examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Specific examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene. , 1,7-octadiene monoepoxide and the like.

The component (A) polymer used in the present invention includes at least one selected from monomers having a liquid crystalline side chain, at least one selected from monomers having a vertical alignment group, and a monomer having a thermally crosslinkable group. It can be obtained by copolymerizing at least one selected from the above and other monomers as desired.
In this case, the amount of each monomer used is not particularly limited as long as the intended liquid crystal polymer can be obtained, but while ensuring good vertical alignment and thermosetting properties, the coatability of the liquid crystal polymer is ensured. In consideration of the above, 3 to 90 mol% of the monomer having a liquid crystalline side chain, 3 to 90 mol% of the monomer having a vertical alignment group, and 3 to 90 mol% of the monomer having a thermally crosslinkable group in all monomers, 0 It is preferable that the amount of the other monomer is ˜91 mol %, provided that the total amount of these monomers is 100 mol %.

The polymerization method is not particularly limited, and examples thereof include a method of reacting each of the above monomers in a solvent at 50 to 110° C. in the presence of a polymerization initiator.
The reaction solvent is not particularly limited as long as it has the ability to dissolve each monomer and the polymerization initiator to be used, and specific examples thereof include those listed as the solvent of the component (C) described later. Can be used.

The polymer of the component (A) obtained by the above reaction is usually in a solution state, but as described later, it can be used as it is as a polymer (solution) of the component (A).
Further, the polymer solution obtained by the above method is poured into agitated diethyl ether or water to reprecipitate, and the produced precipitate is filtered and washed, and then dried at normal temperature or under reduced pressure at room temperature or by heating. Alternatively, a powdery polymer may be used. By this operation, the remaining polymerization initiator and unreacted monomers can be removed, and as a result, a highly pure polymer powder can be obtained. When the purification is insufficient with a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
The purified polymer powder may be used as it is, or may be used in the form of a solution re-dissolved in a solvent of the component (C) described later.
Further, in the present invention, the polymer as the component (A) may be a mixture of plural kinds of polymers.

In addition, when all the (meth)acrylic-type monomers are used as said each monomer, as an example of the polymer of (A) component obtained, what is represented by a following formula is mentioned, for example.

（式中、Ｙ¹〜Ｙ⁶、Ｘ、Ｒ、ｍ、ｎ、ｏ、ｐは上記と同じ。Ｒ¹は、水素原子またはメチル基を表し、Ｒ²は、熱架橋性基を有するアルキル基を表し、Ｒ³は、炭素数１〜５のアルキル基を表し、ｚ¹〜ｚ⁴は、モノマー単位のモル％を表し、ｚ¹〜ｚ³は互いに独立して３〜９０の数を、ｚ⁴は０〜９１の数を表し、ｚ¹＋ｚ²＋ｚ³＋ｚ⁴＝１００を満たす。）

(In the formula, Y ^{1 to} Y ⁶ , X, R, m, n, o, and p are the same as above. R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having a thermally crosslinkable group. R ³ represents an alkyl group having 1 to 5 carbon atoms, z ^{1 to} z ⁴ represent mol% of the monomer unit, z ^{1 to} z ³ each independently represent a number of ³ to 90, z ⁴ represents a number from 0 to 91, and satisfies z ¹ +z ² +z ³ +z ⁴ =100.)

The cross-linking agent of the component (B) in the thermosetting resin composition of the present invention is not particularly limited as long as it is a group that forms a cross-link with the heat-crosslinkable group of the polymer of the component (A). In the present invention, a crosslinking agent having a methylol group or an alkoxymethyl group is preferable.
Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine and alkoxymethylated melamine.

Specific examples of the alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4. ,6-Tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples thereof include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.
These are also available as commercial products, for example, a glycoluril compound (trade name: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd., and a methylated urea resin (commodity). Name: UFR (registered trademark) 65), same butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin (manufactured by DIC Corporation) ( Highly condensed type, trade name: Beckamine (registered trademark) J-300S, P-955, N) and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine and the like.
These are also available as commercial products, for example, manufactured by Nippon Cytec Industries Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade name: Nikalac (registered trademark) BX-4000). , BX-37, BL-60, BX-55H) and the like.

Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like.
These are also available as commercial products, and for example, Nippon Cytec Industries Co., Ltd. methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (Brand name: Mycoat (registered trademark) 506, 508), Sanwa Chemical Co., Ltd. methoxymethyl type melamine compound (Brand name: Nicalac (registered trademark) MW-30, MW-22, MW-11) , The same MS-001, the same MX-002, the same MX-730, the same MX-750, the same MX-035), a butoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MX-45, the same MX-410, MX-302) and the like.

Further, the crosslinking agent used in the present invention may be a compound obtained by condensing a melamine compound in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group, a urea compound, a glycoluril compound and a benzoguanamine compound. ..
Specific examples of such compounds include high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310.

Further, as a cross-linking agent of the component (B), a hydroxymethyl group (that is, a methylol group) or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide or the like is used. Polymeric crosslinkers made using substituted acrylamide or methacrylamide compounds can also be used.

Examples of such a polymer crosslinking agent include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-. Examples thereof include a copolymer of ethoxymethyl methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
The weight average molecular weight of the polymer crosslinking agent is not particularly limited, but is usually about 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000. , And even more preferably 3,000 to 50,000.
The polymer crosslinking agent may be used as it is after the synthesis.
The above-mentioned various cross-linking agents can be used alone or in combination of two or more kinds.

The content of the cross-linking agent of the component (B) in the thermosetting resin composition of the present invention is (A) in consideration of the vertical alignment property and heat resistance of the resulting cured film, and also the surface tack property and transparency. 1 to 100 parts by mass is preferable, and 5 to 50 parts by mass is more preferable, relative to 100 parts by mass of the component polymer.

As the solvent of the component (C) used in the thermosetting resin composition of the present invention, the polymer of the component (A) described above, the cross-linking agent of the component (B), and other components used as necessary described below. As long as it can be dissolved, its type and structure are not particularly limited.

Specific examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol and n-pentanol; glycols such as diethylene glycol and propylene glycol; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, propylene Glycol esters such as glycol monomethyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone , 2-pentanone, 2-heptanone, and other ketones; γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutane. Methyl acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate And the like; ethers such as cyclopentyl methyl ether; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and these may be used alone or in combination of two or more. It can be used in combination.

When a cured film is formed on a resin film using the thermosetting resin composition of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl that does not adversely affect the base film is obtained. It is preferable to use -1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or the like.

The amount of the solvent used cannot be unconditionally specified because it varies depending on the type of the components (A) and (B) and the type of the solvent. The concentration (solid content concentration) is preferably about 1 to 90% by mass, more preferably about 5 to 70% by mass, and even more preferably about 10 to 60% by mass.
When a polymer solution is used as the component (A) or the component (B), it is preferable that the total amount of the solvent contained therein and the solvent of the component (C) be the above solid content concentration.

The thermosetting resin composition of the present invention may contain a crosslinking catalyst as the component (D) for the purpose of accelerating the thermosetting reaction of the polymer, in addition to the components (A) to (C).
As the crosslinking catalyst, it is preferable to use an acid or a thermal acid generator that thermally decomposes to generate an acid at a temperature during heat treatment (for example, about 80 to 250° C.).

Specific examples of the acid include 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-Perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid and other sulfonic acid group-containing compounds, and hydration thereof The thing or salt etc. are mentioned.

Specific examples of the thermal acid generator include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylenetris. (Methyl sulfonate), 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-hydroxybutyl p-toluenesulfonate, N- Examples thereof include ethyl-p-toluenesulfonamide and the like, compounds represented by the following formula, and the like.

The content of the component (D) in the thermosetting resin composition of the present invention is not particularly limited, but the thermosetting property, surface tackiness and transparency of the obtained cured film, and storage of the composition Considering stability and the like, 0.01 to 20 parts by mass is preferable, and 0.1 to 15 parts by mass is more preferable, with respect to 100 parts by mass in total of the polymer of the component (A) and the crosslinking agent of the component (B). It is even more preferably 0.5 to 10 parts by mass.

Furthermore, the thermosetting resin composition of the present invention, as long as it does not impair the effects of the present invention, if necessary, adhesion improver, silane coupling agent, surfactant, rheology modifier, pigment, dye, storage Stabilizers, defoamers, antioxidants and the like can be contained.

In the thermosetting resin composition of the present invention, the polymer of the component (A), the cross-linking agent of the component (B), the solvent of the component (C), the cross-linking catalyst of the component (D), which is optionally used, and the like are used. It can be prepared by mixing in order.
As an example of the preparation method, a solution of the component (A) dissolved in a solvent of the component (C) is mixed with the component (B) and optionally the component (D) at a predetermined ratio to obtain a uniform mixture. The method of making it into a solution is mentioned.

Further, as described above, the polymer solution of the component (A) obtained by the polymerization reaction or the like (that is, containing the component (A) and the component (C)) can be used as it is, but in this case, (A) The component (B) and the component (D) optionally used may be added to the polymer solution of the components as described above to form a uniform solution. At this time, a solvent of the component (C) may be further added for the purpose of adjusting the concentration. The solvent used for the polymer solution of the component (A) and the solvent for adjusting the concentration may be the same or different.
The prepared thermosetting resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

The thermosetting resin composition of the present invention described above is directly applied on a substrate (without using an alignment film) and then dried by heating with a hot plate or an oven to obtain a homeotropically aligned cured film (single film). A layer coating type homeotropic alignment film) can be formed.
Specific examples of the substrate include a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal (aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, an ITO substrate, and triacetyl cellulose (TAC). Examples thereof include resin film substrates such as films, polycarbonate (PC) films, cycloolefin polymer (COP) films, cycloolefin copolymer (COC) films, polyethylene terephthalate (PET) films, acrylic films and polyethylene films.
The coating method is not particularly limited, and it is possible to use various known coating methods such as bar coating, spin coating, flow coating, roll coating, slit coating, rotary coating following slit, inkjet coating, and printing. it can.

The condition of heat drying is not particularly limited as long as the crosslinking reaction with the crosslinking agent proceeds, and is, for example, 60 to 200° C., preferably 70 to 160° C., 0.4 to 60 minutes, preferably 0.5 to It may be appropriately selected from the range of 10 minutes.
After heating and drying, it is preferable to cool to about 20 to 30° C. and leave for about 24 hours.

The thickness of the obtained cured film is appropriately selected in consideration of the steps of the substrate to be used and the optical and electrical properties, but is usually 0.5 to 100 μm.

The single-layer coating type homeotropic alignment film of the present invention thus obtained may be peeled from the substrate and used as a film, or may be used as a liquid crystal alignment layer formed on the substrate.
Such a single-layer coating type homeotropic alignment film is a material having optical characteristics suitable for applications such as a display device and a recording material, and in particular, a polarizing plate for a liquid crystal display, an optical compensation film such as a retardation plate. Can be suitably used as.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measuring devices used in the examples are as follows.
[Measurement of average molecular weight]
Equipment: Shimadzu Corporation high-performance liquid chromatograph, Prominence
Column: Shodex (registered trademark) KF-803L+KF-804L
Column temperature: 40°C
Solvent: Tetrahydrofuran (flow rate 1 mL/min)
Detector: RI
Calibration curve: standard polystyrene [film thickness measurement]
Device: Mitutoyo Micrometer MEQ-30
[Evaluation of Rth and Δn]
Device: Axoscan manufactured by Axometrics
Rth: Retardation value in the thickness direction of the homeotropic liquid crystal layer Rth={(Nx+Ny)/2-Nz}*d [nm]
Refractive index in the direction showing the maximum in-plane refractive index of the liquid crystal layer: Nx
Refractive index in the direction orthogonal to it: Ny
Refractive index in the thickness direction: Nz
Liquid crystal layer thickness: d (nm)
Δn: Thickness direction refractive index Nz minus the average value of Nx and Ny

[Abbreviation]
The abbreviations used below have the following meanings.
Component (A): polymer raw material and polymerization catalyst LAA: lauryl acrylate HEMA: 2-hydroxyethyl methacrylate 6Be: 4-methoxyphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate MMA: methyl methacrylate AIBN: α, α'-azobisisobutyronitrile

Component (B): Crosslinking agent and raw material thereof CYM303: Hexamethoxymethylmelamine (CYMEL303, manufactured by Nippon Cytec Industries Co., Ltd.)
BMAA: N-butoxymethylacrylamide PBMAA: Poly(N-butoxymethylacrylamide)

Component (C): Solvent PM: Propylene glycol monomethyl ether CH: Cyclohexanone

Component (D): Crosslinking catalyst PTSA: p-toluenesulfonic acid monohydrate

[Synthesis Example 1] Synthesis of Polymer P1 (Component A) 6Be 7.0 g synthesized by the method described in Synthesis Example 3 of International Publication No. 2013/133078, LAA (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.0 g, HEMA ( 1.0 g of Tokyo Kasei Kogyo Co., Ltd. and 0.17 g of AIBN (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization catalyst were dissolved in 18.9 g of CH and reacted at 75° C. for 16 hours to prepare an acrylic copolymer solution. P1 (solid content concentration 35% by mass) was obtained. The number average molecular weight (hereinafter referred to as Mn) of the obtained acrylic copolymer was 16,500, and the weight average molecular weight (hereinafter referred to as Mw) was 35,800.

[Synthesis example 2] Synthesis of polymer P2 (component A) 6Be 6.5 g, LAA 2.5 g, HEMA 1.5 g, AIBN 0.17 g were dissolved in CH 18.9 g and reacted at 75° C. for 16 hours to carry out acrylic copolymer solution P2. (Solid content concentration 35% by mass) was obtained. The obtained acrylic copolymer had Mn of 15,300 and Mw of 33,200.

[Synthesis Example 3] Synthesis of Polymer P3 (Comparative Example) 7.0 g of 6Be, 2.0 g of MMA, 1.0 g of HEMA, and 0.17 g of AIBN were dissolved in 18.9 g of CH and reacted at 75°C for 16 hours to prepare an acrylic copolymer solution P3. (Solid content concentration 35% by mass) was obtained. The acrylic copolymer obtained had Mn of 16,900 and Mw of 36,500.

[Synthesis Example 4] Synthesis of Polymer P4 (Component B) 25.0 g of BMAA (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.04 g of AIBN were dissolved in 48.4 g of PM and reacted at 85° C. for 20 hours to obtain an acrylic copolymer. A solution P4 (solid content concentration 35% by mass) was obtained. The acrylic copolymer obtained had Mn of 4,800 and Mw of 3,100.

[Examples 1-1 to 1-4, Comparative examples 1-1 to 1-3]
The components (A) to (D) were mixed in the proportions shown in Table 1 to prepare the thermosetting resin compositions of Examples 1-1 to 1-4 and Comparative examples 1-1 to 1-3. In addition, P1 to P3 in the component (A) represent the usage amount (g) of the acrylic copolymer solution, and P4 in the component (B) represents the usage amount (g) of the acrylic copolymer solution.

[Examples 2-1 to 2-4, Comparative examples 2-1 to 2-3]
Each thermosetting resin composition prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3 was applied onto a 25 μm-thick COP film at a wet film thickness of 50 μm using a bar coater. did. Then, each was heat-dried at a temperature of 110° C. for 120 seconds in a heat circulation type oven to form a thermosetting film on the COP film, and then left at 23° C. for 24 hours to obtain a laminated film.

[Evaluation of film thickness]
The thickness of the laminated film produced in Examples 2-1 to 2-4 and Comparative examples 2-1 to 2-3 was measured. The value obtained by subtracting the thickness of the COP film from the measured value was defined as the film thickness of the thermosetting film.

[Evaluation of Rth and Δn]
Rth of the fast axis of the laminated film produced in Examples 2-1 to 2-4 and Comparative examples 2-1 to 2-3 was measured. The value obtained by dividing the obtained Rth by the film thickness was taken as Δn of the thermosetting film.

[Evaluation of coating film]
The presence or absence of white turbidity was determined by visually observing the laminated films produced in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3.

[Tack evaluation]
A finger was contacted with the surface of the thermosetting film of each of the laminated films prepared in Examples 2-1 to 2-4 and Comparative examples 2-1 to 2-3, and it was determined whether or not contact marks remained on the surface. Those with a contact mark remained were tacked.
Table 2 also shows the above evaluation results.

As shown in Table 2, the cured films (Examples 2-1 to 2-4) obtained from the thermosetting resin compositions of Examples 1-1 to 1-4 are all high at 0.008 or more. It shows Δn, and it is understood that a transparent and tack-free coating film is obtained.
On the other hand, it was confirmed that the coating films of Comparative Examples 2-1 and 2-2 containing no component (B) became cloudy and had tack. Therefore, the Rth was not evaluated.
In addition, it can be seen that although a cured coating film of Comparative Example 2-3 using a polymer having no vertical alignment group produced a transparent and tack-free coating film, sufficient Rth was not obtained.

Claims (11)

(A) A polymer having a liquid crystalline side chain represented by the formula (1), a vertical alignment group and a heat crosslinkable group,
A thermosetting resin composition for producing a homeotropic alignment retardation film without using a vertical alignment film, which comprises (B) a crosslinking agent and (C) a solvent.

(In the formula, X is a COO group or an OCO group, R is a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxyl group, or an alkoxy group having 1 to 6 carbon atoms. Represents, and n represents an integer of 1 to 10, and o and p represent an integer of 1 or 2.) The heat-crosslinkable group is one or more selected from a hydroxy group, a carboxyl group, an amino group, a blocked isocyanate group, a vinyl group, an allyl group, a (meth)acryl group, an epoxy group, an oxetanyl group and an alkoxysilyl group. The thermosetting resin composition according to claim 1, which is The thermosetting resin composition according to claim 1, wherein the vertical alignment group is represented by formula (2).

(In the formula, Y ¹ is a single bond or —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represents the selected linking group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or a —CH ₂ —CH(OH)—CH ₂ — group, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle. , Any hydrogen atom on the cyclic group may be substituted with Z,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond, a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and any of the above cyclic groups. A hydrogen atom may be replaced by Z,
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups may be substituted with Z,
m represents an integer of 0 to 4, and when m is 2 or more, Y ⁵ may be the same or different from each other,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 18 carbon atoms,
Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom,
The alkylene group, the alkyl group, the fluorinated alkyl group, the alkoxy group and the fluorinated alkoxy group may have 1 to 3 of the bonding groups therein as long as the bonding groups are not adjacent to each other,
In the above Y ^{2 to} Y ⁶ , an alkylene group, a —CH ₂ —CH(OH)—CH ₂ — group, a divalent cyclic group, a divalent organic group having a steroid skeleton, an alkyl group and a fluorinated alkyl group, It may be bonded to a group adjacent to them via the bonding group.
However, the total number of carbon atoms of the substituents represented by Y ^{2 to} Y ⁶ is ⁶ to 30. ) Each of Y ¹ , Y ² and Y ⁴ is a single bond, Y ³ is an alkylene group having 1 to 15 carbon atoms, m is 0, and Y ⁶ is 1 to 18 carbon atoms. The thermosetting resin composition according to claim ³ , wherein the total number of carbon atoms of Y ³ and Y ⁶ is 6 to 20. The thermosetting according to any one of claims 1 to 4, wherein the n represents an integer of 2 to 8, the o and p are 1, and the R is an alkoxy group having 1 to 6 carbon atoms. Resin composition. The thermosetting resin composition according to any one of claims 1 to 5, wherein the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group. The thermosetting resin composition according to claim 1, further comprising (D) a crosslinking catalyst. The thermosetting resin composition according to any one of claims 1 to 7, which comprises 1 to 100 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). The thermosetting resin composition according to claim 7 or 8, wherein the component (D) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B). A homeotropic alignment retardation film formed by thermosetting the thermosetting resin composition according to claim 1. A method for producing a homeotropic alignment retardation film, which comprises heat-curing the thermosetting resin composition according to any one of claims 1 to 9 and then leaving it for 24 hours or more after cooling.