JP6733840B2 - Polymerizable composition, cured product thereof, photo spacer, overcoat for display element, interlayer insulating material for display element, and liquid crystal display element - Google Patents

Description

The present invention provides a photo spacer for a liquid crystal display device, and a polymerizable composition useful as a liquid crystal-polymer composite for a light control device, a liquid crystal display, an organic light emitting display, a member for a display device such as a micro light emitting display, a liquid crystal- The present invention relates to a polymer composite and a liquid crystal display device having a photo spacer obtained by curing the polymerizable composition.

Since the display element members such as the alignment film, the sealant, and the photo spacers in the liquid crystal display are in direct contact with the liquid crystal composition, they affect the image quality of the liquid crystal display element, such as the transmittance and the contrast.

Among these display element members, the alignment film has been actively developed as a display element member that affects the transmittance and the contrast. With respect to the sealant, the rise of the organic light emitting display element has recently been studied to increase the contrast, particularly to reduce the transmittance when the voltage is OFF. On the other hand, with regard to the photo spacer, since the original purpose of use is to keep the thickness and distance between the two substrates in the liquid crystal display element, that is, the liquid crystal layer constant, the adhesion characteristic of the photo spacer is the original. There are known techniques for improving the voltage retention, which is one of the characteristics that affect the liquid crystal composition, or to improve the transparency, transparency, flatness, etc. (see Patent Documents 1 to 3 below) (see below) See Patent Document 4).

However, the area where one photo spacer contacts the liquid crystal composition in the liquid crystal display element is 3 to 4 times the area calculated from the width of the spacer and the thickness of the liquid crystal layer. Further, in the liquid crystal display element, basically, the number of photo spacers corresponding to each pixel is present, and as a result, a liquid crystal composition having an area equal to or larger than that of the sealant comes into contact with the photo spacers. However, as described above, since the improvement of the photo spacer has been the improvement of the adhesiveness, the transparency, the flatness, or the voltage holding ratio, the photo spacer improves the contrast of the liquid crystal display element, The current situation is that no technique has been studied for improving response speed.

JP, 2014-146018, A JP, 2009-98637, A JP, 2012-37677, A JP, 2013-221954, A

The problem to be solved by the present invention is to improve the contrast of a liquid crystal display element when used as a liquid crystal display member, and particularly to improve not only the contrast as a material for a photo spacer but also the response speed of liquid crystal. Another object of the present invention is to provide a functional composition, and various liquid crystal display members and liquid crystal-polymer composites using the composition.

The present inventors have conducted extensive studies in order to solve the above problems, and as a result, by introducing a mesogenic structure into the polymer structure that constitutes the photo spacer for a liquid crystal display device, the contrast and response speed are significantly improved. The present invention has been completed and the present invention has been completed.

That is, the present invention comprises (A) an alkali-soluble resin and (B) a polymerizable compound having at least one polymerizable functional group in the molecular structure as essential components. The present invention relates to a polymerizable composition characterized in that at least one of the resin (A) and the compound (B) has a mesogenic skeleton.

The present invention further relates to a cured product obtained by coating the above-mentioned polymerizable composition on a substrate and developing and immobilizing it by a photolithography method.
The present invention further relates to a photo spacer composed of a cured product.
The present invention further relates to an overcoat for a display device, which is obtained by applying a polymerizable composition onto a substrate and curing the composition.
The present invention further relates to an interlayer insulating material for a display device, which is made of the polymerizable composition.
The present invention further relates to a liquid crystal display device provided with the photo spacer.
The present invention further relates to a liquid crystal-polymer composite comprising the above polymerizable composition.

According to the present invention, the contrast of the liquid crystal display device is improved when used as a liquid crystal display member, not only as a contrast particularly as a material for the photo spacer, but also a polymerizable composition capable of improving the response speed of the liquid crystal, Also, various liquid crystal display members using the composition can be provided.

The polymerizable composition of the present invention is also useful as an overcoat material for protecting a substrate of a display element, an interlayer insulating material for a display element used in a flexible display and the like. Further, it is also useful as a material for a liquid crystal-polymer composite used in a light control device having a transmission-scattering property.

As described above, the polymerizable composition of the present invention contains (A) an alkali-soluble resin and (B) at least one of the polymerizable compound having at least one polymerizable functional group in the molecular structure, or both. It has a mesogenic skeleton. The polymerizable composition of the present invention is an alkali developable polymerizable composition having alkali developability.

In the present invention, since the mesogenic skeleton is introduced into the polymer, when used as a member of a liquid crystal display element, a high contrast can be obtained by reducing the difference in refractive index between the liquid crystal composition and other members. In particular, when used as a photo spacer for a liquid crystal display element, the response speed of the liquid crystal display element can be increased.

The polymerizable composition of the present invention is used not only for liquid crystal display devices but also for organic light-emitting devices and microlight-emitting devices, in which the difference in refractive index with peripheral members is reduced and luminous efficiency is improved. Further, it is also useful as a material for forming an overcoat layer for protecting the substrate of a display element, an interlayer insulating material for a display element used in a flexible display, etc. because of its excellent smoothness after coating.

Further, since the mesogen skeleton is introduced into the polymer, it is also useful as a liquid crystal-polymer composite material used for a light control device having a transmission-scattering property.

The alkali-soluble resin (A) used in the polymerizable composition of the present invention is a resin having alkali solubility. Here, the alkali solubility refers to the property of being dissolved in an aqueous solution of an alkali compound (developing solution). Specifically, for example, a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) is formed on a substrate to form a resin film having a film thickness of 1 μm, and a KOH aqueous solution having a concentration of 0.05% by mass is used for 1 minute. It is possible to exemplify the property of dissolving at a film thickness of 0.01 μm or more when immersed.

The alkali-soluble resin (A) is not particularly limited as long as it is soluble in an alkali developing solution, but at least one acid group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and a sulfonic acid group or a salt thereof ( Hereinafter, a resin having this acid group or a salt thereof is simply referred to as "acid group") is preferable.

Examples of the alkali-soluble resin (A) include, for example, a photo-curable alkali-soluble resin (a photo-curable group-free alkali-soluble resin) and a photo-curable alkali-soluble resin (a photo-curable group-containing resin). Alkali-soluble resin) and the like.

Examples of the alkali-soluble resin containing no photocurable group include the following resins (A1) to (A5).

Resin (A1): An alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having an acid group as an essential component.

Resin (A2): a polymer having no acidic group, which is obtained by polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component, and having reactivity with the reactive group. An alkali-soluble resin obtained by reacting a compound having a reactive group and an acid group.

On the other hand, examples of the photocurable group-containing alkali-soluble resin include the following resins.

Resin (A3): To a copolymer of an epoxy group-containing (meth)acrylate and another polymerizable monomer, an unsaturated monocarboxylic acid is added to at least a part of the epoxy groups of the copolymer. And an alkali-soluble resin obtained by further subjecting an acid anhydride of a polycarboxylic acid to an addition reaction of at least a part of hydroxyl groups generated by the addition reaction of an unsaturated monocarboxylic acid.

Resin (A4): An α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is added to an epoxy resin, and further reacted with a polybasic acid anhydride. A so-called acid pendant type epoxy (meth)acrylate resin obtained by.

Resin (A5): Cardo type resin (A5) having a carboxyl group and a polymerizable unsaturated group
In each of the above resins (A1) to (A5), by introducing a mesogenic skeleton into the resin structure, when a polymerizable composition containing the resin is used for a member of a liquid crystal display element, High contrast can be realized by reducing the difference in refractive index between the liquid crystal composition and other members. In addition, when the polymerizable composition containing the resin is used for the photo spacer, the response speed of the liquid crystal display device can be increased. Further, even when the polymerizable composition containing the resin is used as a member of an organic light emitting device or a micro light emitting device, the luminous efficiency can be improved by reducing the difference in refractive index from the peripheral members.

Hereinafter, the resins (A1) to (A5) will be described in detail.

Examples of the alkali-soluble resin (A1) include an acid group-containing polymerizable monomer, for example, a (meth)acrylic polymerizable monomer having a carboxyl group and a (meth)acrylic polymerizable monomer having a sulfonic acid group. Examples thereof include alkali-soluble resins obtained by polymerizing a polymerizable monomer such as a monomer as an essential component. Above all, an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component is preferable.

Here, in order to introduce a mesogenic structure into the alkali-soluble resin (A1), a method of copolymerizing the above-mentioned acid group-containing polymerizable monomer and the polymerizable liquid crystal compound (a) can be mentioned.

Examples of the (meth)acrylic polymerizable monomer having a carboxyl group include (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, 2-(meth)acryloyloxyethyl. Succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2 -(Meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxypropyl hydrophthalic acid, 2-(meth)acryloyl Oxypropyl phthalic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl maleic acid, 2-(meth)acryloyloxybutyl hydrophthalic acid, Polymerizable monomer such as 2-(meth)acryloyloxybutylphthalic acid; a polymerizable monomer obtained by adding lactone such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to acrylic acid Body; a polymerizable monomer obtained by adding succinic acid, maleic acid, phthalic acid, or an acid anhydride thereof to hydroxyalkyl (meth)acrylate. These (meth)acrylic polymerizable monomers having a carboxyl group may be used alone or in combination of two or more. Among the (meth)acrylic polymerizable monomers having a carboxyl group, (meth)acrylic acid and 2-(meth)acryloyloxyethylsuccinic acid are preferable.

Examples of the (meth)acrylic polymerizable monomer having a sulfonic acid group include, for example, 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, and 2-hydroxy-3-(meth). ) Acryloxypropane sulfonic acid, 2-(meth)acrylamido-2-methylpropane sulfonic acid or salts thereof, and the like.

On the other hand, the polymerizable liquid crystal compound (a) that can be copolymerized with the acid group-containing polymerizable monomer is a polymerizable liquid crystal compound (a-1) having one or two or more polymerizable functional groups. It is preferable because it is excellent in alkali developability.

Here, as the polymerizable liquid crystal compound (a-1) having one or two or more polymerizable functional groups, specifically, compounds represented by the following general formula (1) can be mentioned.

(In the formula, P represents a polymerizable functional group,
Sp represents an alkylene group having 0 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms or CN, and one CH ₂ group present in this group or not adjacent to it) Two or more CH ₂ groups are each independently of the other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N(CH ₃ )—, —CO—, It may be replaced by -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-),
m represents 0 or 1,
MG represents a mesogenic group,
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an isocyano group, a thioisocyano group, a hydroxy group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group is one or more halogen atoms or It may be substituted by CN, and one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other. _{, -O -, - S -,} - NH -, - N (CH 3) -, - CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or -C≡C- Or R ¹ is represented by the general formula (1-a)

(In the formula, P represents a reactive functional group, Sp represents a spacer group having 0 to 18 carbon atoms, and m represents 0 or 1.). ).

Here, the polymerizable functional group may be any functional group that can be copolymerized with the acid group-containing polymerizable monomer, and examples thereof include a vinyl group, a vinyl ether group, an acryl group, a methacryl group, and a maleimide group. However, from the viewpoint of reactivity with the acid group-containing polymerizable monomer, a vinyl group, a vinyl ether group, an acryl group and a (meth)acryl group are preferable, and an acryl group and a (meth)acryl group are particularly preferable.

The mesogen group represented by MG has the general formula (1-b)

(In the formula, A1, A2 and A3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene -2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b:4,5 -B']diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2, 7-diyl group, or a fluorene-2,7-diyl group, one or more F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, Alkanoyl group, alkanoyloxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, alkenoyl group, alkenoyloxy group, or the general formula (1-c).

(Wherein, P is represents a reactive functional group, A is, -O -, - COO -, - OCO -, - OCH 2 -, - CH 2 O -, - CH 2 CH 2 OCO -, - COOCH 2 CH ₂ —, —OCOCH ₂ CH ₂ —, or a single bond, Sp represents a spacer group having 0 to 18 carbon atoms, n represents 0 or 1, and m represents 0 or 1.). You can
Z0, Z1, Z2 and Z3 are each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C- , -CH = CHCOO -, - CF = CF -, - CF 2 O -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH _{2 CH 2 -, - CONH -} , - NHCO-, represents an alkyl group or a single bond have a halogen atom having 2 to 10 carbon atoms,
n represents 0, 1 or 2. ).

Among the compounds represented by the general formula (1), a monofunctional compound having one polymerizable functional group in the molecule is represented by the following general formula (1-1) and general formula (1-2). The compounds represented may be mentioned.

(In the formula, Z ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an isocyano group, a thioisocyano group, a hydroxy group, or a hydrocarbon group having 1 to 18 carbon atoms,
Z ⁵ represents a hydrogen atom or a methyl group, t represents 0 or 1, and
B, C and D are each independently a 1,4-phenylene group, a 1,4-phenylene group in which a non-adjacent CH group is substituted with nitrogen, a 1,4-cyclohexylene group, one or two non-adjacent groups. 1,4-cyclohexylene group in which CH ₂ group is substituted with oxygen or sulfur atom, 1,4-cyclohexenyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6 -Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2 , 6-naphthylene group and 1,4-naphthylene group are shown, and these groups may be substituted with one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms. well,
Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—. , -CF = CF -, - CF 2 O -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - _{CH 2 CH 2 CH = CH -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 - or -OCOCH ₂ CH ₂ - the stands, Y ⁵ is single bond, -O -, - COO -, - OCO- or an -CH = CHCOO-. ).

(In the formula, Z ⁶ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an isocyano group, a thioisocyano group, a hydroxy group, or a hydrocarbon group having 1 to 18 carbon atoms,
Z ⁷ represents a hydrogen atom or a methyl group,
W ³ being a single _{bond, -OCH 2 -, - COO -} , - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - CF 2 O -, - OCH 2 CH 2 CH 2 _{-, - CH = CHCH 2 CH} 2 -, - CH = CHCOO -, - OCOCH = CH -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or an -O-,
v represents an integer of 1 to 18,
u represents 0 or 1,
E, F and G are each independently a 1,4-phenylene group, a 1,4-phenylene group in which a non-adjacent CH group is replaced by a nitrogen atom, a 1,4-cyclohexylene group, one or two non-adjacent 2 1,4-cyclohexylene group in which one CH ₂ group is substituted with an oxygen atom or a sulfur atom, 1,4-cyclohexenyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2 ,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group , 2,6-naphthylene group and 1,4-naphthylene group, which are substituted with one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms. Ok,
Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—. , -CF = CF -, - CF 2 O -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - _{CH 2 CH 2 CH = CH -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 - or -OCOCH ₂ CH ₂ - the stands, ^{Y 8} represents a single bond, -O -, - COO -, - OCO- or an -CH = CHCOO-. ).

Exemplary compounds represented by the general formula (1-1) and the general formula (1-2) are shown below, but are not limited thereto.

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

The use amount of the monofunctional compound having one polymerizable functional group in the molecule is 10 to 80% by mass in the monomer components constituting the alkali-soluble resin (A) when the photospacer is used. It is preferable from the viewpoint of excellent effect of improving the response speed, and it is preferably 1 to 60% by mass from the viewpoint of obtaining good alkali solubility, and particularly preferably 10 to 60% by mass.

Among the compounds represented by the general formula (1), R ¹ is a bifunctional compound having two polymerizable functional groups in the molecule represented by the general formula (1-a), and the following general formula ( The compound represented by 2-1) is mentioned.

(In the formula, m represents 0 or 1, n represents 0, 1 or 2,
W ¹ and W ² are each independently a single bond, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—, —CF═CF—, —CF ₂ O—, _{-OCH 2 CH 2 CH 2 -,} - CH = CHCH 2 CH 2 -, - CH = CHCOO -, - OCOCH = CH -, - COOCH 2 CH 2 - or -OCOCH ₂ CH ₂ - or an -O-,
Y ¹ and Y ² are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—. , -CF = CF -, - CF 2 O -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - _{CH 2 CH 2 CH = CH -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 - or -OCOCH ₂ CH ₂ - And a plurality of Y ^2's may be the same or different,
A represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a naphthalene-2,6-diyl group, and when there are a plurality of A, they may be the same or different,
Z ⁸ and Z ⁹ represent a hydrogen atom or a methyl group,
r and s each independently represent an integer of 1 to 18,
R ^{3 to} R ¹⁰ are each selected from a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. ).

Exemplary compounds represented by formula (2-1) are shown below, but the invention is not limited thereto.

The amount of the compound represented by the general formula (2-1) used is 5 to 80% by mass in the monomer component constituting the alkali-soluble resin (A), which improves the response speed when the photospacer is used. It is preferable from the standpoint of excellent effect, preferably 1 to 50% by mass from the viewpoint of obtaining good alkali solubility, and particularly preferably 5 to 50% by mass.

When preparing the alkali-soluble resin (A1), in addition to the acid group-containing polymerizable monomer, or in addition to the acid group-containing polymerizable monomer and the polymerizable liquid crystal compound (a), You may use together another polymerizable monomer. Examples of the other monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth). Acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate. (Meth)acrylic acid ester such as glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate (Meth)acrylic acid ester having a hydroxyl group such as hydroxyalkyl (meth)acrylate and glycerol mono(meth)acrylate; aromatic vinyl compounds such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide; N-substituted maleimides such as N-phenylmaleimide and N-benzylmaleimide; polymethyl (meth)acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth)acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, Examples thereof include macromonomers such as polycaprolactone macromonomers. The other polymerizable monomers may be used alone or in combination of two or more.

Among the above-mentioned other polymerizable monomers, styrene, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxy. Propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide are excellent in transparency of the resin itself and have a good contrast improving effect as a display device. Is preferable in that it is expressed in.

The amount of these other polymerizable monomers used is preferably 0 to 60% by mass in the monomer components constituting the alkali-soluble resin (A).

The acid value of the alkali-soluble resin (A1) is preferably in the range of 30 to 500, more preferably in the range of 40 to 350, and even more preferably in the range of 50 to 300. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (C1) measured by GPC is preferably 2,000 to 80,000, more preferably 3,000 to 50,000. The range of 4,000 to 30,000 is more preferable.

In addition, in the alkali-soluble resin (A1), an epoxy group-containing unsaturated compound is added to the carboxyl group of a carboxyl group-containing alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component. The alkali-soluble resin (A1-1) added with can also be used as an alkali-soluble resin containing a photocurable group.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso)crotonic acid glycidyl ether, and N-(3,5-dimethyl). -4-Glycidyl)benzyl acrylamide, 4-hydroxybutyl (meth)acrylate glycidyl ether and the like can be mentioned.

A known method can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing alkali-soluble resin. For example, a carboxyl group-containing alkali-soluble resin and an epoxy group-containing unsaturated compound are used as tertiary amines such as triethylamine and benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethyl. Quaternary ammonium salt such as ammonium chloride; in the presence of a catalyst such as pyridine or triphenylphosphine, the reaction is carried out in an organic solvent at a reaction temperature of 50 to 150°C for several hours to several tens of hours to give an epoxy group to the carboxyl group of the resin. Containing unsaturated compounds can be added.

The acid value of the alkali-soluble resin (A1-1) is preferably in the range of 10 to 200, more preferably in the range of 20 to 150, still more preferably in the range of 30 to 150. The polystyrene-equivalent weight average molecular weight of the alkali-soluble resin (A1-1) measured by GPC is preferably in the range of 2,000 to 100,000, more preferably in the range of 4,000 to 50,000, The range of 000 to 30,000 is more preferable.

Further, among the alkali-soluble resins (A1), the alkali-soluble resin (A1-2) obtained by using (meth)acrylic acid ester having an alicyclic structure such as an ether dimer or an adamantyl group as a polymerizable monomer Is preferred.

Examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-). Propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2 , 2'-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-butyl)-2,2'- [Oxybis(methylene)]bis-2-propenoate, di(t-amyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2′-[oxybis(methylene) )] Bis-2-propenoate, di(lauryl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2′-[oxybis(methylene)]bis- 2-propenoate, di(1-methoxyethyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis- 2-propenoate, dibenzyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diphenyl-2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2'-[ Oxybis(methylene)]bis-2-propenoate, di(t-butylcyclohexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(dicyclopentadienyl)-2,2′- [Oxybis(methylene)]bis-2-propenoate, di(tricyclodecanyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isobornyl)-2,2'-[oxybis( Methylene)]bis-2-propenoate, diadamantyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene) ] Bis-2-propenoate etc. are mentioned. Among these, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2'-[ Oxybis(methylene)]bis-2-propenoate and dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate are preferred. These ether dimers can be used alone or in combination of two or more.

When an ether dimer is used as a raw material of the alkali-soluble resin (A1-2), the proportion of the ether dimer in the polymerizable monomer is controlled because gelation is suppressed and a low-molecular weight alkali-soluble resin is obtained. The range of 2 to 60 mass% of the mass of the polymerizable monomer is preferable, the range of 5 to 55 mass% is more preferable, and the range of 5 to 50 wt% is further preferable.

On the other hand, when a (meth)acrylic acid ester having an alicyclic structure such as an adamantyl group is used as the raw material of the alkali-soluble resin (A1-2), the ratio of the (meth)acrylic acid ester used is such that the total polymerizable monomer The range of 0.5 to 60 mass% of the mass of the body is preferable, the range of 1 to 55 mass% is more preferable, and the range of 5 to 50 wt% is further preferable.

The method for producing the alkali-soluble resin (A1) used in the present invention is not particularly limited and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and the polymerization concentration (polymerization concentration=[total weight of polymerizable monomer/(total weight of polymerizable monomer+solvent weight)]×100) are determined by the type of polymerizable monomer used and The ratio depends on the target molecular weight of the alkali-soluble resin. The polymerization temperature is preferably in the range of 40 to 150°C, more preferably in the range of 60 to 130°C. The polymerization concentration is preferably in the range of 5 to 50%, more preferably 10 to 40%.

The solvent used in the solution polymerization method may be the one used in a usual radical polymerization reaction. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform; dimethyl sulfoxide, etc. Are listed. These solvents may be used alone or in combination of two or more.

When polymerizing the polymerizable monomer, a polymerization initiator may be used if necessary. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2. -Organic peroxides such as ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2′-azobis(2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis(2-methylpropionate). These polymerization initiators may be used alone or in combination of two or more. The amount of these polymerization initiators used may be appropriately set according to the combination of the monomers used, the reaction conditions, the target molecular weight of the alkali-soluble resin (A1), and the like, but is not particularly limited, but gelation occurs. Since an alkali-soluble resin having a weight average molecular weight of several thousand to tens of thousands can be obtained without any matter, the range of 0.1 to 15 mass% is preferable, and the range of 0.5 to 10 mass% is based on the total polymerizable monomer components. Is more preferable.

A chain transfer agent may be added to adjust the molecular weight. Examples of the chain transfer agent include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer, and the like, but the chain transfer effect is high and remains in the reaction system. N-dodecyl mercaptan and mercaptoacetic acid are preferable because they can reduce the amount of polymerizable monomers and are easily available. The amount used in the case of using a chain transfer agent may be appropriately set depending on the combination of the monomers used, the reaction conditions, the molecular weight of the target monomer, etc., and is not particularly limited, but gelation is required. Since it is possible to obtain an alkali-soluble resin having a weight average molecular weight of several thousand to several tens of thousands, a range of 0.1 to 15% by mass is preferable, and a range of 0.5 to 10% by mass is more preferable, based on all monomers. preferable.

The alkali-soluble resin (A2) used in the present invention is a polymer having no acidic group obtained by polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component, It is obtained by reacting a compound having a group reactive with a group and an acid group. Examples of the alkali-soluble resin (A2) include the following alkali-soluble resins.

After obtaining a polymer using a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate as an essential component, an acid such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An alkali-soluble resin obtained by adding an anhydride.

-After obtaining a polymer using a polymerizable monomer having an epoxy group such as glycidyl (meth)acrylate as an essential component, it has an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol. An alkali-soluble resin obtained by adding a compound.

-After obtaining a polymer using a polymerizable monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate as an essential component, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid is added. The resulting alkali-soluble resin.

The weight average molecular weight of the alkali-soluble resin (A2) is 1,000 to 200,000 as a polystyrene equivalent weight average molecular weight measured by GPC because a coating film having good film formation and excellent heat resistance can be obtained. Is preferable, the range of 2,000 to 50,000 is more preferable, and the range of 2,000 to 30,000 is further preferable. If necessary, the polymerizable monomer used for preparing the alkali-soluble resin (A1) may be used in combination to obtain the alkali-soluble resin (A2).

The alkali-soluble resin (A3) used in the present invention is a copolymer of an epoxy group-containing (meth)acrylate and another polymerizable monomer, and has at least a part of the epoxy groups contained in the copolymer. It can be obtained by adding a saturated monocarboxylic acid and further adding an acid anhydride of a polycarboxylic acid to at least a part of hydroxyl groups generated by the addition reaction of an unsaturated monocarboxylic acid.

Examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth). ) Acrylic glycidyl ether and the like can be mentioned. Of these, glycidyl (meth)acrylate is preferable. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

Further, as the polymerizable monomer other than the epoxy group-containing (meth)acrylate that is a raw material of the alkali-soluble resin (A3), a monomer having an alicyclic structure such as a norbornene skeleton or a dicyclopentadiene skeleton is used. Is also preferable.

Further, a polymerizable monomer having no alicyclic structure may be used as a polymerizable monomer other than the epoxy group-containing (meth)acrylate. Examples of such a polymerizable monomer include vinyl aromatics such as styrene, α-, o-, m-, p-alkyl of styrene, nitro, cyano, amide and ester derivatives; butadiene and 2,3-dimethyl. Dienes such as butadiene, isoprene, chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, (meth)acrylic acid- n-butyl, (meth)acrylic acid-s-butyl, (meth)acrylic acid-t-butyl, (meth)acrylic acid pentyl, (meth)acrylic acid neopentyl, (meth)acrylic acid isoamyl, (meth)acrylic acid Hexyl, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate , (Meth)acrylic acid dicyclohexyl, (meth)acrylic acid isobornyl, (meth)acrylic acid adamantyl, (meth)acrylic acid propargyl, (meth)acrylic acid phenyl, (meth)acrylic acid naphthyl, (meth)acrylic acid anthracenyl, Anthraninonyl (meth)acrylate, piperonyl (meth)acrylate, salicyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, (meth)acrylic acid Pyranyl, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, -1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, ( Perfluoro-n-propyl (meth)acrylate, perfluoro-iso-propyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, (meth)acrylic acid-3-(N, (Meth)acrylic acid esters such as N-dimethylamino)propyl, (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid-N,N-di-i-propylamide, (meth ) (Meth)acrylic acid amide such as acrylic acid anthracenylamide; ( Vinyl compounds such as (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, maleic acid Unsaturated dicarboxylic acid diesters such as diethyl, diethyl fumarate, and itaconic acid diethyl; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide; N- Examples thereof include (meth)acryloylphthalimide.

Among the above other polymerizable monomers, it is preferable to use at least one selected from styrene, benzyl (meth)acrylate, and monomaleimides because the heat resistance and mechanical strength of the cured product can be improved. The use ratio of styrene, benzyl (meth)acrylate and monomaleimides is preferably 1 to 70 mol% and more preferably 3 to 50 mol% based on the total amount of other polymerizable monomers.

A known polymerization method such as a solution polymerization method using a radical polymerization initiator can be used for the copolymerization reaction of the epoxy group-containing (meth)acrylate with the other polymerizable monomer. The solvent used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

The copolymer of the epoxy group-containing (meth)acrylate and the other polymerizable monomer includes a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth)acrylate, and another radical polymerizable monomer. The repeating unit derived from 10 to 95 mol% is preferable, the former 20 to 80 mol% and the latter 80 to 20 mol% are more preferable, and the former 30 to 70 mol% and the latter 70 are preferable. What is comprised from -30 mol% is more preferable.

The alkali-soluble resin (A3) contains an unsaturated monocarboxylic acid (polymerizable component) and a polycarboxylic acid at the epoxy group portion of the copolymer of the epoxy group-containing (meth)acrylate and another polymerizable monomer. It is obtained by reacting an acid anhydride (an alkali-soluble component) of an acid.

Examples of the unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position being a haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano. Examples thereof include monocarboxylic acids such as (meth)acrylic acid substituted with a group or the like. Among these, (meth)acrylic acid is preferable. These unsaturated monocarboxylic acids may be used alone or in combination of two or more. By using this unsaturated monocarboxylic acid, the alkali-soluble resin (A3) can be imparted with polymerizability.

Usually, the unsaturated monocarboxylic acid is preferably added to 10 to 100 mol% of the epoxy groups contained in the copolymer, more preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. It is more preferable to add.

Examples of the acid anhydride of the polycarboxylic acid include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and carboxylic acid anhydrides of dicarboxylic acids such as chlorendic anhydride. Carboxylic acid anhydrides having three or more carboxyl groups such as trimellitic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable. These polycarboxylic acid anhydrides may be used alone or in combination of two or more. By using the acid anhydride of this polycarboxylic acid, alkali solubility can be imparted to the alkali soluble resin (A3).

Usually, the acid anhydride of the polycarboxylic acid is preferably added to 10 to 100 mol% of the hydroxyl group generated by adding the unsaturated monocarboxylic acid to the epoxy group of the copolymer, preferably 20 to 90. More preferably, it is added to mol%, and further preferably added to 30 to 80 mol%.

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A3) measured by gel permeation chromatography (GPC) is preferably in the range of 3,000 to 100,000, and in the range of 5,000 to 50,000. Is more preferable. The dispersity (Mw/Mn) of the alkali-soluble resin (A3) is preferably in the range of 2.0 to 5.0.

The epoxy (meth)acrylate resin (A4) is obtained by, for example, adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to the epoxy resin, It is obtained by reacting a polybasic acid anhydride.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; bisphenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, xylenol. Novolak type epoxy resins such as novolac type epoxy resins; dicyclopentadiene-modified epoxy resins; naphthols such as naphthol and binaphthol and naphthalene skeleton epoxy resins obtained by epoxidizing novolaks of these naphthols; polyvalent carboxylic acid Glycidyl ester type resin, linear aliphatic epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate and its derivatives, epoxy resin derived from xylenol, phenol aralkyl epoxy resin, naphthalene aralkyl epoxy resin, zilock type epoxy resin, etc. Can be mentioned.

The epoxy resin has a molecular weight of 200 to 200, as a polystyrene-equivalent weight average molecular weight measured by GPC, because it can form a coating film well and prevent gelation during the addition reaction of α,β-unsaturated monocarboxylic acid. The range of 000 is preferable, and the range of 300 to 100,000 is more preferable.

Examples of the α,β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, and the like. Acrylic acid and methacrylic acid are preferable, and acrylic acid has good reactivity. To more preferable. Examples of the α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include 2-succinoyloxyethyl acrylate, 2-malenoyloxyethyl acrylate, 2-phthaloyloxyethyl acrylate, 2-Hexahydrophthaloyloxyethyl acrylate, 2-succinoyloxyethyl methacrylate, 2-maleinoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthalomethacrylate Iloxyethyl, 2-succinoyloxyethyl crotonic acid, etc. are preferred, 2-maleinoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate are preferred, and 2-malenoyloxyethyl acrylate is preferred. More preferable. These α,β-unsaturated monocarboxylic acids and α,β-unsaturated monocarboxylic acid esters may be used alone or in combination of two or more.

A known method can be used for the addition reaction of the α,β-unsaturated monocarboxylic acid or its ester with the epoxy resin. For example, a method of reacting at a temperature of 50 to 150° C. in the presence of an esterification catalyst is used. Can be mentioned. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used.

The amount of the α,β-unsaturated monocarboxylic acid or its ester used is preferably in the range of 0.5 to 1.2 equivalents, and 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy groups of the raw material epoxy resin. Is more preferable.

Examples of the polybasic acid anhydride to be further added to the epoxy resin to which α,β-unsaturated carboxylic acid or its ester has been added include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Acid, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Biphenyl tetracarboxylic dianhydride etc. are mentioned. Among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, trimellitic dianhydride, biphenyltetracarboxylic dianhydride is preferable. More preferred are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These polybasic acid anhydrides may be used alone or in combination of two or more.

A known method can be used for the addition reaction of the polybasic acid anhydride, and the reaction can be continuously performed under the same conditions as the addition reaction of the α,β-unsaturated carboxylic acid or its ester. The amount of the polybasic acid anhydride used is preferably such that the acid value of the resulting epoxy (meth)acrylate resin is in the range of 10 to 150, since the alkali developability and the coating film formation can be improved. More preferably, the amount will be in the range of 20-140.

Further, as an epoxy (meth)acrylate resin having a carboxyl group, a naphthalene-containing resin described in JP-A-6-49174; JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331, The fluorene-containing resin described in JP 2001-354735 A; resins described in JP 2005-126674 A, JP 2005-55814 A, JP 2004-295084 A and the like can also be exemplified. Moreover, as a commercial item, "ACA-200M" by Daicel Chemical Industries Ltd. etc. can be illustrated.

The cardo resin type resin (A5) is a generic name for resins having a structure in which a cyclic group is directly bonded to a polymer main chain. However, due to the presence of a bulky substituent in the main chain, Rotational constraint of the chain, (2) conformational regulation of main chain and side chain, (3) inhibition of intermolecular packing, (4) increase of aromaticity by introduction of aromatic substituent on side chain, etc. are expressed. .. Furthermore, it has high heat resistance, solvent solubility, and high transparency as physical properties.

Preferred examples of the cardo type resin (A5) include resins represented by the following general formula (3).

In the formula, X is a group represented by the following chemical formula (4), Y is a residue obtained by removing a carboxylic acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride, and Z is tetracarboxylic acid. It is a residue obtained by removing two carboxylic acid anhydride groups from an acid dianhydride. n is an integer of 0-20. )

Specific examples of the Y-derived dicarboxylic acid anhydride (the dicarboxylic acid anhydride before removing the carboxylic acid anhydride group) include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride and the like.

Specific examples of the tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride before removing two carboxylic acid anhydride groups) that induces Z include, for example, pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride. Examples thereof include tetracarboxylic dianhydrides such as anhydrides, biphenyltetracarboxylic dianhydrides and biphenylethertetracarboxylic dianhydrides.

The polystyrene-equivalent weight average molecular weight (Mw) of the cardo resin measured by weight gel permeation chromatography (GPC) is preferably from 1,000 to 1,000,000, more preferably from 3,000 to 50,000. Most preferred is 1,000 to 15,000.

Among the above alkali-soluble resins (A1) to (A5), the alkali-soluble resin (A) is particularly excellent in compatibility with the polymerizable compound (B) having at least one polymerizable functional group in the molecular structure. Therefore, the alkali-soluble resin (A1) is preferable, and the resin having a mesogenic structure in the resin structure is particularly preferable.

Further, as the alkali-soluble resin (A) used in the present invention, an alkali-soluble resin other than the above-mentioned alkali-soluble resins (A1) to (A5) may be used. As such a resin, for example, an alkali-soluble resin obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acidic group as an essential component, or a polymerizable monomer having a sulfonic acid group as an acidic group is an essential component. Examples of the alkali-soluble resin obtained by using Here, examples of the polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like. Further, one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers were substituted with an alkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or an amide group. A compound etc. are also mentioned. Examples of the polymerizable monomer having a sulfonic acid group as an acidic group include vinyl sulfonic acid, styrene sulfonic acid, (meth)allyl sulfonic acid, 2-hydroxy-3-(meth)allyloxypropane sulfonic acid, Examples thereof include 2-(meth)acrylic acid-2-sulfoethyl, or salts thereof.

The content ratio of the alkali-soluble resin (A) in the polymerizable composition in the present invention is 0.1 to 80% by mass based on the total solid content because the appearance of the coating film and the adhesion to the substrate are good. The range is preferable, and the range of 1 to 60 mass% is more preferable.

Next, examples of the polymerizable compound (B) having at least one polymerizable functional group in the molecular structure used in the present invention include, for example, the polymerizable monomer used in the preparation of the alkali-soluble resin (A) described above. Can be used, but among them, (meth)acrylic acid ester or the polymerizable liquid crystal compound (a) is preferable.

Examples of the (meth)acrylic acid ester include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di( (Meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloyl) Roxyethyl) ether, ethoxylated bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate and the like. To be

Examples of the polymerizable compound (B3) having three ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth). Acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone modified pentaerythritol tri(meth)acrylate, Caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride And the like.
Examples of the polymerizable compound (B4) having four ethylenically unsaturated bonds include pentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, and the like. To be

Examples of the polymerizable compound (B5) having five or more ethylenic unsaturated bonds include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripenta. Erythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, tripentaerythritol hepta(meth)acrylate And acid anhydride caprolactone modified trimethylolpropane tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified tri(meth)acrylate Pentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate Examples thereof include acrylates and acid anhydrides.

Among them, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth), for example, when used as an overcoat material, the cured film has excellent hardness. ) Trifunctional or higher polyfunctional (meth)acrylates such as acrylate and pentaerythritol tetra(meth)acrylate are preferable.

In the present invention, as described above, as the polymerizable compound (B) having at least one polymerizable functional group in the molecular structure, particularly the polymerizable liquid crystal compound (a) having a mesogenic structure in the molecular structure is used. In particular, it is possible to obtain a high contrast by reducing the difference in refractive index between the liquid crystal composition and other members. In particular, when it is used as a photo spacer for a liquid crystal display element, the response speed of the liquid crystal display element is increased. It is preferable because it can

Here, the polymerizable liquid crystal compound (a) having a mesogenic structure in the molecular structure may be the above-mentioned monofunctional or bifunctional polymerizable liquid crystal compound (a-1), but in particular, The polymerizable liquid crystal compound (a-2) having two or more functional groups represented by the general formula (I-1) has excellent solvent resistance of the cured product and also has good hardness. It is preferable that the compound has three or more functional groups, and a compound having three or more functional groups is particularly preferable because these properties are remarkable.

In the formula, P ¹¹ and P ¹² each independently represent a polymerizable functional group, and Sp ¹¹ and Sp ¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond. one -CH ₂ in the - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO- or may be substituted by --OCO-O- , One or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ¹¹ and X ¹² are each independently. _{and, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO _{-O -, - CO-NH -} , - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - _{CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH- , -N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond (provided ^{that, P 11 -Sp 11, P 12} -Sp 12, Sp 11 -X ¹¹ and Sp ¹² -X ¹² do not include a direct bond between heteroatoms), q1 and q2 each independently represent 0 or 1, q3 and q4 each represent 1 to 3, and MG ¹² Represents a mesogenic group.

It is preferable that P ¹¹ and P ¹² each independently represent a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20).

Of these polymerizable functional groups, from the viewpoint of enhancing the polymerizability, formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

MG ¹² represents a mesogen group and has the general formula (Ib).

(In the formula, A1, A2 and A3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene -2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b:4,5 -B']diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2, 7-diyl group, or a fluorene-2,7-diyl group, one or more _F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, carbon atoms 1-8 alkoxy group, alkanoyl group having 1-8 carbon atoms, alkanoyloxy group having 1-8 carbon atoms, alkoxycarbonyl group having 1-8 carbon atoms, alkenyl group having 2-8 carbon atoms, carbon It may have an alkenyloxy group having 2 to 8 atoms, an alkenoyl group having 2 to 8 carbon atoms, and/or an alkenoyloxy group having 2 to 8 carbon atoms, and Z1 and Z2 are each independently. Te, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH _{-, - CH 2 CH 2 COO} -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C -, - CONH -, - NHCO _{-, - C (CF 3)} 2 -, a halogen atom represents a (fluorine atom, chlorine atom, bromine atom, iodine atom) alkyl group or a single bond may C2-10 have a, Z1 and Z2 Are independently -COO-, -O _{CO -, - CH 2 CH 2} -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 _{COO -, - CH 2 CH 2} OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or preferably a single bond, -COO -, - OCO -, - OCH 2 -, - CH 2 O _{-, - CH 2 CH 2 O} -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or more preferably a single bond, r1 is 0, 1, 2 or 3 When a plurality of A1 and Z1 are present, they may be the same or different, but when q3 represents 2 or 3, any one of A1, A2 and A3 is -(X. ¹² -Sp ¹²⁾ having one or two _q2 -P ¹² groups. ). Of these, it is preferable that A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.
(Bifunctional polymerizable liquid crystal compound)
The polymerizable liquid crystal compound represented by the above general formula (I-1) having two or more polymerizable functional groups in the molecule is represented by the following general formula (I- It is preferable to use the bifunctional polymerizable liquid crystal compound represented by 1-1).

(In the formula, P ¹¹ and P ¹² each independently represent a polymerizable functional group, and Sp ¹¹ and Sp ¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond; Even if one —CH ₂ — or two or more non-adjacent —CH ₂ — in the group are independently substituted by —O—, —COO—, —OCO— or —OCO—O—. Well, one or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ¹¹ and X ¹² are respectively _{independently, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O- _{CO-O -, - CO-} NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond and represents ^{(where, P 11 -Sp 11, P 12} -Sp 12, Sp ^11- X ¹¹ and Sp ¹² -X ¹² do not include a direct bond between heteroatoms), q1 and q2 each independently represent 0 or 1, and MG ¹² represents a mesogen group.)
Here, it is preferable that P ¹¹ and P ¹² each independently represent a substituent selected from the polymerizable groups represented by the above formulas (P-2-1) to (P-2-20). .. Among these polymerizable functional groups, from the viewpoint of enhancing the polymerizability, formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

Further, Sp ¹¹ and Sp ¹² each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more — which are not adjacent to each other. Each CH ₂ — may be independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or two or more hydrogen atoms contained in the alkylene group are halogen atoms. (Fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group may be substituted, and it is more preferable that Sp ¹¹ and Sp ¹² each independently represent an alkylene group having 1 to 12 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - substituted OCO- or by --OCO-O- May be.

X ¹¹ and ^{X 12} are each, _{independently, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- _{, -COO-CH 2 CH 2 -} , - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 - _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single Preferably, it represents a bond, and X ¹¹ and X ¹² are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—. _{O -, - CF 2 O -} , - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH _{2 CH 2 -, - OCO-} CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 - _{COO -, - CH 2 -OCO -} , - CH = CH -, - CF = CF -, - C≡C- or more preferably a single bond.
MG ¹² represents a mesogen group and has the general formula (I-1-b).

In the formula, A1, A2 and A3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3 -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 ,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene- group 2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b:4,5- b′]diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2,7 - represents a diyl group, or a fluorene-2,7-diyl group, one or more _F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, carbon atoms 1 ~8 alkoxy group, alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, carbon atom It may have an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and/or an alkenoyloxy group having 2 to 8 carbon atoms, and Z1 and Z2 are each independently. , -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH- _{, -CH 2 CH 2 COO -,} - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C -, - CONH -, - NHCO- , —C(CF ₃ ) ₂ —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a single bond, and Z1 and Z2 are each Independently -COO-, -OC _{O -, - CH 2 CH 2} -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 _{COO -, - CH 2 CH 2} OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or preferably a single bond, -COO -, - OCO -, - OCH 2 -, - CH 2 O _{-, - CH 2 CH 2 O} -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or more preferably a single bond, r1 is 0, 1, 2 or 3 When a plurality of A1 and Z1 are present, they may be the same or different. Of these, it is preferable that A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.

Examples of the general formula (I-1-1) include compounds represented by the following general formulas (I-1-1-1) to (I-1-1-4). It is not limited to the formula.

^{Wherein, P 11, Sp 11, X} 11, q1, X 12, Sp 12, q2, P 12 , respectively, represent the same as defined in formula (I-1-1),
A11, A12, A13, A2, and A3 represent the same definitions as A1 to A3 in the general formula (I-1-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 and Z2 in the general formula (I-1-b), and may be the same or different.

Among the compounds represented by the above general formulas (I-1-1-1) to (I-1-1-4), general formulas (I-1-1-2) to (I-1-1-4). ), a compound having three or more ring structures in the compound is preferably used because the resulting optically anisotropic substance has good orientation, and a compound represented by the general formula (3) having three ring structures in the compound ( It is particularly preferable to use the compound represented by I-1-1-2).

The compounds represented by the general formulas (I-1-1-1) to (I-1-1-4) include the following general formulas (I-1-1-1-1) to (I-1). Examples of the compound represented by (1-1-21)) are not limited thereto.

In the formula, R ^d and R ^e each independently represent a hydrogen atom or a methyl group,
The cyclic group may include one or more F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, 1 to carbon atoms 8 alkanoyl group, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, carbon atom It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms,
m1 and m2 each independently represent an integer of 0 to 18, and n1, n2, n3 and n4 each independently represent 0 or 1.

The liquid crystal compound having two polymerizable functional groups may be used alone or in combination of two or more, but is preferably 1 to 5 types, more preferably 2 to 5 types.

The total content of the polymerizable liquid crystal compounds having two polymerizable functional groups in the molecule is the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound represented by the general formula (II-1). The total amount of liquid crystal compounds is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and particularly preferably 20 to 80% by mass. When the curability of the resulting coating film is emphasized, the lower limit value is preferably 30% by mass or more, more preferably 50% by mass or more, and the adhesion of the resulting coating film to the substrate is emphasized. In that case, the upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.
(Trifunctional polymerizable liquid crystal compound)
The polymerizable liquid crystal compound represented by the above general formula (I-1) having two or more polymerizable functional groups in the molecule is represented by the following general formula (I- It is preferable to use the trifunctional polymerizable liquid crystal compound represented by 1-2).

(In the formula, P ^{12 to} P ¹³ each independently represent a polymerizable functional group, and Sp ^{11 to} Sp ¹³ each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond. Even if one —CH ₂ — in the group or two or more —CH ₂ — which are not adjacent to each other are independently substituted by —O—, —COO—, —OCO— or —OCO—O—. Well, one or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ^{11 to} X ¹³ are each _{independently, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O- _{CO-O -, - CO-} NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond and represents ^{(where, P 11 -Sp 11, P 12} -Sp 12, Sp ^{11 -X 11, Sp 12 -X 12} , Sp 13 -X 13, and the ^Sp 13 ^{-X 13,} does not include a direct bond between heteroatom.), q1, q2, q4 , and q5 are each independently , 0 or 1, and MG ¹² represents a mesogenic group.)
Here, it is preferable that P ^{12 to} P ¹³ each independently represent a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20). ..

Of these polymerizable functional groups, from the viewpoint of enhancing the polymerizability, formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1), (P-2-2) and (P-2-7) are particularly preferable.

Further, Sp ^{11 to} Sp ¹³ each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more — which are not adjacent to each other. Each CH ₂ — may be independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or two or more hydrogen atoms contained in the alkylene group are halogen atoms. (Fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group may be substituted, and it is more preferable that Sp ^{11 to} Sp ¹³ each independently represent an alkylene group having 1 to 12 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - substituted OCO- or by --OCO-O- May be. X ¹¹ to X ¹³ are each _{independently, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- _{, -COO-CH 2 CH 2 -} , - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 - _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single Preferably, it represents a bond, and X ^{11 to} X ¹³ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—. _{O -, - CF 2 O -} , - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH _{2 CH 2 -, - OCO-} CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 - _{COO -, - CH 2 -OCO -} , - CH = CH -, - CF = CF -, - C≡C- or more preferably a single bond.
MG ¹² represents a mesogen group and has the general formula (I-2-b).

In the formula, A1, A2 and A3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3 -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 ,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene- group 2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b:4,5- b′]diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2,7 - represents a diyl group, or a fluorene-2,7-diyl group, one or more _F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, carbon atoms 1 ~8 alkoxy group, alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, carbon atom It may have an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and/or an alkenoyloxy group having 2 to 8 carbon atoms, but it is present A1, A2 and A3. any of ^- having an _{(Sp ¹³⁾} q4 ^-P ₁₃ group ^- _(X 13) ^q5. Z1 and Z2 are each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH - , - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C- , -CONH -, - NHCO -, - C (CF 3) 2 -, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) of good C2-10 also have an alkyl group or a single It represents a bond, the Z1 and Z2 each independently -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C-, -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or preferably a single bond, r1 represents 0, 1, 2 or 3, and when plural A1 and Z1 are present, they may be the same or different. ). Of these, it is preferable that A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.

Examples of the general formula (I-1-2) include compounds represented by the following general formulas (I-1-2-1) to (I-1-2-9). It is not limited to the formula.

^{Wherein, P 11, Sp 11, X} 11, q1, X 12, Sp 12, q2, P 12, X 13, q5, Sp 13, q4, P 13 , respectively, the general formula (I-1-2 ) Represents the same definition as
A11, A12, A13, A2, and A3 each represent the same definition as A1 to A3 in the general formula (I-2-b), and may be the same or different.
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 and Z2 in the general formula (I-2-b), and may be the same or different.

The compounds represented by the general formulas (I-1-2-1) to (I-1-2-9) include the following general formulas (I-1-2-1-1) to (I-1). Examples of the compound represented by 2-1-8) are not limited thereto.

In the formula, R ^f , R ^g and R ^h each independently represent a hydrogen atom or a methyl group, and R ^l is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a carbon number of 1 To a C6 alkyl group, a C1-6 alkoxy group, and a cyano group, and when these groups are a C1-6 alkyl group or a C1-6 alkoxy group, all are unsubstituted. Or may be substituted by one or two or more halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), and the cyclic group is one or more F, Cl, or CF ₃ , OCF ₃ , CN group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, Alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, alkenoyl group having 2 to 8 carbon atoms, alkene group having 2 to 8 carbon atoms It may have a noyloxy group.
m4 to m9 each independently represent an integer of 0 to 18, and n4 to n10 each independently represent 0 or 1.

The polyfunctional polymerizable liquid crystal compound having three polymerizable functional groups can be used alone or in combination of two or more.
(Tetrafunctional polymerizable liquid crystal compound)
The polymerizable liquid crystal compound represented by the above general formula (I-1) having two or more polymerizable functional groups in the molecule is represented by the following general formula (I- It is preferable to use a trifunctional polymerizable liquid crystal compound represented by 1-3).

(In the formula, P ^{11 to} P ¹⁴ each independently represent a polymerizable functional group, and Sp ^{11 to} S ¹⁴ each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond; Even if one —CH ₂ — or two or more non-adjacent —CH ₂ — in the group are independently substituted by —O—, —COO—, —OCO— or —OCO—O—. Well, the one or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ^{11 to} X ¹⁴ are respectively _{independently, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O- _{CO-O -, - CO-} NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond and represents ^{(where, P 11 -Sp 11, P 12} -Sp 12, Sp ^{11 -X 11, Sp 12 -X 12} , Sp 13 -X 13, and the ^{Sp 13 -X 13, Sp 14 -X} 14, does not include a direct bond between heteroatom.), q1, q2, q4, and, q5 each independently represents 0 or 1, and MG ¹² represents a mesogen group.)
Here, it is preferable that P ^{11 to} P ¹⁴ each independently represent a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20). ..

Of these polymerizable functional groups, from the viewpoint of enhancing the polymerizability, formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1), (P-2-2) and (P-2-7) are particularly preferable.

Further, Sp ^{11 to} Sp ¹⁴ each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more — which are not adjacent to each other. Each CH ₂ — may be independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or two or more hydrogen atoms contained in the alkylene group are halogen atoms. (Fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group may be substituted, and it is more preferable that Sp ^{11 to} Sp ¹⁴ each independently represent an alkylene group having 1 to 12 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - substituted OCO- or by --OCO-O- May be. X ¹¹ to X ¹⁴ are each _{independently, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- _{, -COO-CH 2 CH 2 -} , - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 - _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single Preferably, it represents a bond, and X ^{11 to} X ¹⁴ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—. _{O -, - CF 2 O -} , - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH _{2 CH 2 -, - OCO-} CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 - _{COO -, - CH 2 -OCO -} , - CH = CH -, - CF = CF -, - C≡C- or more preferably a single bond.
MG ¹² represents a mesogen group and has the general formula (I-2-b).

In the formula, A1, A2 and A3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3 -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 ,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene- group 2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b:4,5- b′]diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2,7 - represents a diyl group, or a fluorene-2,7-diyl group, one or more _F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, carbon atoms 1 ~8 alkoxy group, alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, carbon atom It may have an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and/or an alkenoyloxy group having 2 to 8 carbon atoms, but it is present A1, A2 and A3. any of ^- having an _{(Sp ¹⁴⁾} q4 ^-P ₁₄ group ^{_{- (X 13) q5 - (}} Sp 13) q4 -P 13 group and ^- _(X 14) ^q5. Z1 and Z2 are each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH - , - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C- , -CONH -, - NHCO -, - C (CF 3) 2 -, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) of good C2-10 also have an alkyl group or a single It represents a bond, the Z1 and Z2 each independently -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C-, -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or preferably a single bond, r1 represents 0, 1, 2 or 3, and when plural A1 and Z1 are present, they may be the same or different. ). Of these, it is preferable that A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.

Examples of the general formula (I-1-3) include compounds represented by the following general formulas (I-1-3-1) to (I-1-3-3). It is not limited to the formula.

In the formula, P ¹¹ , Sp ¹¹ , X ¹¹ , q1, X ¹² , Sp ¹² , q2, P ¹² , X ¹³ , q5, Sp ¹³ , q4, P ¹³ , X ¹⁴ , Sp ¹⁴ , P ^14, respectively, the above general ones. Represents the same definition as in formula (I-1-3), A11, A12, A2, and A3 represent the same definitions as A1 to A3 in the above general formula (I-2-b), respectively. , May be the same or different, and Z11, Z12, and Z2 represent the same definitions as Z1 and Z2 in the general formula (I-2-b), and are the same. Can also be different.

The compounds represented by the general formulas (I-1-3-1) to (I-1-3-3) include the following general formulas (I-1-2-1-1) to (I-1). Examples of the compound represented by 2-1-8) are not limited thereto.

In the formula, R ^f , R ^g , R ^h and R ⁱ each independently represent a hydrogen atom or a methyl group, and R ^l is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), It represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, all are It may be unsubstituted or substituted by one or more halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), and the cyclic group may be one or more F as a substituent. , Cl, CF ₃ , OCF ₃ , CN group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkanoyl group having 1 to 8 carbon atoms, alkanoyl having 1 to 8 carbon atoms An oxy group, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and 2 to 2 carbon atoms It may have 8 alkenoyloxy groups. m4 to m7 each independently represent an integer of 0 to 18, and n4 to n7 each independently represent 0 or 1.
(6-functional polymerizable liquid crystal compound)
The polymerizable liquid crystal compound represented by the above general formula (I-1) having two or more polymerizable functional groups in the molecule is represented by the following general formula (I- It is preferable to use a hexafunctional polymerizable liquid crystal compound represented by 1-4).

(In the formula, P ^{11 to} P ¹⁶ each independently represent a polymerizable functional group, and Sp ^{11 to} S ¹⁶ each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond; Even if one —CH ₂ — in the group or two or more —CH ₂ — which are not adjacent to each other are independently substituted by —O—, —COO—, —OCO— or —OCO—O—. Well, one or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ^{11 to} X ¹⁶ are each _{independently, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O- _{CO-O -, - CO-} NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, _{-CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond and represents ^{(where, P 11 -Sp 11, P 12} -Sp 12, Sp in ^{11 -X 11, Sp 12 -X 12} , Sp 13 -X 13, and ^{Sp 13 -X 13, Sp 14 -X} 14, Sp 15 -X 15, Sp 16 -X 16, a direct bond between heteroatom (Not included), q1, q2, q4, q5, q6 and q7 each independently represent 0 or 1, and MG ¹² represents a mesogen group.)
Here, it is preferable that P ^{11 to} P ¹⁶ each independently represent a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20). ..
Here, it is preferable that P ^{11 to} P ¹⁶ each independently represent a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20). ..

Of these polymerizable functional groups, from the viewpoint of enhancing the polymerizability, formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1), (P-2-2) and (P-2-7) are particularly preferable.

Further, Sp ^{11 to} Sp ¹⁶ each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more — which are not adjacent to each other. Each CH ₂ — may be independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or two or more hydrogen atoms contained in the alkylene group are halogen atoms. (Fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group may be substituted, and it is more preferable that Sp ^{11 to} Sp ¹⁴ each independently represent an alkylene group having 1 to 12 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - substituted OCO- or by --OCO-O- May be. X ¹¹ to X ¹⁶ are each _{independently, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- _{, -COO-CH 2 CH 2 -} , - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 - _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single It is preferred that they represent a bond, and X ^{11 to} X ¹⁴ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—. _{O -, - CF 2 O -} , - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH _{2 CH 2 -, - OCO-} CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 - _{COO -, - CH 2 -OCO -} , - CH = CH -, - CF = CF -, - C≡C- or more preferably a single bond.
MG ¹² represents a mesogen group and has the general formula (I-2-b).

In the formula, A1, A2 and A3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3 -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 ,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a-octahydrophenanthrene- group 2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b:4,5- b′]diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2,7 - represents a diyl group, or a fluorene-2,7-diyl group, one or more _F as _{substituents, Cl, CF 3, OCF 3} , CN group, an alkyl group having 1 to 8 carbon atoms, carbon atoms 1 To alkoxy group, alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, carbon atom It may have an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and/or an alkenoyloxy group having 2 to 8 carbon atoms, but it is present A1, A2 and A3. to any one of ^{_{- (X 13) q5 - (}} Sp 13) q4 -P 13 ^{_{group, (X 14) q5 - (}} Sp 14) q4 -P 14, (X 15) q7 - (Sp 15) q6 -P 15 and ^- having a _{(Sp ¹⁶⁾} q6 ^-P ₁₆ group ^- _(X 16) ^q7. Z1 and Z2 are each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = CH - , - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C- , -CONH -, - NHCO -, - C (CF 3) 2 -, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) of good C2-10 also have an alkyl group or a single It represents a bond, the Z1 and Z2 each independently -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C-, -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - or preferably a single bond, r1 represents 0, 1, 2 or 3, and when plural A1 and Z1 are present, they may be the same or different. ). Of these, it is preferable that A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.

Examples of the general formula (I-1-4) include compounds represented by the following general formulas (I-1-4-1) to (I-1-4-3). It is not limited to the formula.

^{Wherein, P 11, Sp 11, X} 11, q1, X 12, Sp 12, q2, P 12, X 13, q5, Sp 13, q4, P 13, X 14, Sp 14, P 14, X 15, Sp ¹⁵ , P ¹⁵ , X ¹⁶ , Sp ¹⁶ , and P ¹⁶ each represent the same definition as in the general formula (I-1-4), and A 11, A 12, A 2, and A 3 respectively represent the general formula (I -2-b) represents the same definition as A1 to A3, and may be the same or different, and Z11, Z12 and Z2 are each represented by the above general formula (I-2-b). Z1 and Z2 are the same as those defined above, and they may be the same or different.

The compounds represented by the general formulas (I-1-4-1) to (I-1-4-3) include the following general formulas (I-1-2-1-1) to (I-1). Examples of the compound represented by 2-1-8) are not limited thereto.

In the formula, R ^f , R ^g , R ^h , R ⁱ , R ^j and R ^k each independently represent a hydrogen atom or a methyl group, and R ^l is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom). Atom, iodine atom), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group, and these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. In the case of a group, all may be unsubstituted or may be substituted with one or two or more halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), and the above cyclic group is a substituent group. as one or more _{F, Cl, CF 3, OCF} 3, CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, alkanoyl group having 1 to 8 carbon atoms, carbon atoms Alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, alkenoyl group having 2 to 8 carbon atoms , May have an alkenoyloxy group having 2 to 8 carbon atoms. m4 to m9 each independently represent an integer of 0 to 18, and n4 to n9 each independently represent 0 or 1.

Further, the total content of the polyfunctional compounds having 3 or more polymerizable functional groups in the molecule may be 40% by mass or less based on the content of the entire polymerizable composition (solid content). Preferably, the content is 1 to 30% by mass.

These polymerizable compounds (B) can be used alone or in combination of two or more kinds.

The total content of the polymerizable compound (B) is preferably 0 to 90 mass% from the viewpoint of excellent effect of improving the response speed when used as a photospacer, and 10 to 80 mass% provides high contrast. It is preferable in that it can be obtained, and if both are taken into consideration, it is particularly preferably 10 to 80 mass %. When the total content of the polymerizable compound (B) is within the above range, the sensitivity, the strength and smoothness of the cured film, and the reliability tend to be good. The photopolymerization initiator (C) used in the present invention Is not particularly limited as long as it is a compound that generates an active radical and an acid by the action of light and initiates the polymerization of the polymerizable compound (B) having at least one polymerizable functional group in the molecular structure. Various polymerization initiators can be used.

The photopolymerization initiator (C) is preferably, for example, a biimidazole compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound or an oxime compound. Moreover, you may use the photocationic polymerization initiator (for example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Among them, the oxime compound is preferable in terms of sensitivity.

Examples of the above-mentioned biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl). -4,4',5,5'-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-Tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra( Trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.); And imidazole compounds (see, for example, JP-A-7-10913). Preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5. Examples thereof include 5'-tetraphenylbiimidazole and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.
Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)- 2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl Examples thereof include oligomers of -1-(4-isopropenylphenyl)propan-1-one, preferably 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethyl. Amino-1-(4-morpholinophenyl)-2-benzylbutan-1-one and the like can be mentioned. Commercially available products such as Irgacure 369 and 907 (all manufactured by BASF Japan Ltd.) may be used.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-Methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Are listed.

Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by Ciba Japan) may be used.

Examples of the oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-. On-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl -6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine and the like can be mentioned. Commercially available products such as Irgacure OXE-01, OXE-02 (all manufactured by BASF Japan) and N-1919 (manufactured by ADEKA) may be used.
Further, as a polymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 may be used. Examples of the polymerization initiator having a group capable of causing chain transfer include compounds of the following formulas (C1) to (C6).

Further, as the polymerization initiator (C), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with (G) a polymerization initiation auxiliary agent (particularly amines) described below.
The polymerizable composition of the present invention may further contain a polymerization initiation aid (G). The polymerization initiation aid (G) is a compound or a sensitizer used in combination with the photopolymerization initiator (C) and used for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. is there.

Examples of the polymerization initiation aid (G) include amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-dimethylhexyl dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly called Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis Examples thereof include (ethylmethylamino)benzophenone, and among them, 4,4′-bis(diethylamino)benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the thiazoline compound include compounds represented by formula (G1) to formula (G3).

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10. -Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid. Examples thereof include acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the photopolymerization initiator (C) is preferably 0.1 to 40 parts by mass, more preferably 1 with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the polymerizable compound (B). ˜30 parts by mass. When the total amount of the photopolymerization initiator (C) is in this range, the obtained product tends to have good chemical resistance, mechanical strength and surface smoothness.

When the polymerization initiation aid (G) is used in the present invention, the amount thereof is preferably 0.01 to 50 with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the polymerizable compound (B). Parts by mass, more preferably 0.1 to 40 parts by mass. Further, it is preferably 0.01 to 10 mol, and more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (C). When the amount of the polymerization initiation aid (G) is in this range, the pattern can be formed with higher sensitivity, and the pattern productivity tends to be improved.

Further, the alkali developable polymerizable composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having two or more sulfanyl groups in the molecule. Among them, it is preferable to use a compound having two or more sulfanyl groups adjacent to an aliphatic hydrocarbon group because a pattern can be formed with high sensitivity.

The (D) organic solvent used in the present invention is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO-), ether solvent other than ester solvent (solvent containing -O-), ether ester solvent (solvent containing -COO- and -O-), ketone other than ester solvent A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used. These solvents may be used alone or in combination of two or more.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate. Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol. Monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Examples thereof include diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate. Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropione Methyl acid, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Examples thereof include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, Examples thereof include cyclohexanone and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like.

Among the above solvents, an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.

The content of the organic solvent (D) is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass, based on the alkali developable polymerizable composition. In other words, the solid content of the alkali developable polymerizable composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. When the content of the organic solvent (D) is within the above range, the flatness during coating tends to be good.

For the purpose of imparting leveling property to the polymerizable composition of the present invention, a surfactant (H) having a surface active effect may be contained within a range not impairing the effect of the present invention. Examples of the surfactant (H) include a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and a surfactant having a fluorine atom and an ethylenically unsaturated bond. ..

When the surfactant (H) is used, the amount thereof is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0%, based on the alkali developable polymerizable composition. 0.1 mass% or less, more preferably 0.01 mass% or more and 0.05 mass% or less.

The alkali developable polymerizable composition of the present invention may contain various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anticoagulant, an organic amine compound, and a curing agent, if necessary. Good.

Examples of the filler include fine particles such as glass and alumina.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2- Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Examples thereof include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

Examples of the antioxidant include 4,4′-thio-bis(6-tert-butyl-3-methylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-methyl-). 4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis[3-(3,3. 5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4. 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol , 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3- Methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(4-hydroxybenzyl)benzene and tetrakis. [Methylene-3-(3,5′-di-tert-butyl-4′-hydroxyphenylpropionate)]methane and the like.

Examples of the ultraviolet absorber include benzotriazoles such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4-octyloxybenzophenone and the like. Benzophenone series; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and other benzoate series; 2-(4,6-diphenyl-1,3,5-triazine Examples include triazine-based compounds such as 2-yl)-5-hexyloxyphenol.

Examples of the aggregation preventing agent include sodium polyacrylate.

By adding the organic amine compound, it is possible to provide a pixel which does not cause a residue on the unexposed portion of the substrate during development and has excellent adhesion to the substrate. Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octyl. Monoalkylamines such as amine, n-nonylamine, n-decylamine, n-undecylamine and n-dodecylamine; monocyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine and the like Cycloalkylamines; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di -Tert-butylamine, di-n-pentylamine, di-n-hexylamine and other dialkylamines; methylcyclohexylamine, ethylcyclohexylamine and other monoalkylmonocycloalkylamines; dicyclohexylamine and other dicycloalkylamines Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri- Trialkylamines such as n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine and tri-n-hexylamine; dialkyls such as dimethylcyclohexylamine and diethylcyclohexylamine Monocycloalkylamines; monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine; 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4- Mono-alkanolamines such as amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol; monocycloalkanolamines such as 4-amino-1-cyclohexanol; diethanolamine, di-n -Propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n -Dialkanolamines such as pentanolamine, di-n-hexanolamine; dicycloalkanolamines such as di(4-cyclohexanol)amine; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri Trialkanolamines such as n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine; tricycloalkanolamines such as tri(4-cyclohexanol)amine; 3-amino -1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2- Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol; 4-amino-1,2 Aminocycloalkanediols such as cyclohexanediol and 4-amino-1,3-cyclohexanediol; amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol; 1- Amino group-containing cycloalkanemethanols such as aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol; β-alanine , 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid , Aminocarboxylic acids such as 1-aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid; aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p -Isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline Aromatic amines such as; o-aminoben Aminobenzyl alcohols such as diyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p -Aminophenols such as dimethylaminophenol and p-diethylaminophenol; and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

As the curing agent, for example, when (A) a resin having a carboxyl group is used as an alkali-soluble resin, a compound capable of reacting with the carboxyl group to crosslink the (A) alkali-soluble resin when heated. Etc. Further, a compound which can be polymerized alone to cure the coating film of the alkali developable polymerizable composition of the present invention to form a cured film is also included. Examples of the compounds include epoxy compounds and oxetane compounds.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac type epoxy resin, other aromatic epoxy resin, and fat. Epoxy resins such as cyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils, brominated derivatives of these epoxy resins, epoxy resins and fats other than their brominated derivatives Group, alicyclic or aromatic epoxy compound, epoxide of butadiene (co)polymer, epoxide of isoprene (co)polymer, (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanurate And so on.

Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

When the alkali developable polymerizable composition of the present invention contains an epoxy compound as a curing agent, an oxetane compound, etc., it contains an epoxy group of the epoxy compound, a compound capable of ring-opening polymerization of the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polycarboxylic acid anhydrides, acid generators, and the like.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid and 3 ,3',4,4'-benzophenonetetracarboxylic acid and other aromatic polycarboxylic acids; succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, Aliphatic polycarboxylic acids such as itaconic acid; hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2, Examples thereof include alicyclic polycarboxylic acids such as 4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic anhydrides include aromatic polyvalents such as phthalic anhydride, pyromellitic dianhydride, trimellitic dianhydride, and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride. Carboxylic anhydrides; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride and other aliphatic compounds Polyvalent carboxylic acid anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride, Alicyclic polyvalent carboxylic acid anhydrides such as cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic acid anhydride, and nadic acid anhydride; ethylene glycol bistrimellitate Examples thereof include acid and ester group-containing carboxylic acid anhydrides such as glycerin tris trimellitate anhydride.

As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents may be used. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Co., Ltd.), RIKACID HH, MH-700 (both manufactured by Shin Nihon Rika Co., Ltd.), etc. under the trade name. To be

The above curing agents may be used alone or in combination of two or more.

Further, the alkali developable polymerizable composition of the present invention may contain an organic acid having a molecular weight of 1,000 or less. Examples of the organic acid include the organic acids disclosed in JP-A-5-343631. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, Methacrylic acid may be mentioned, preferably malonic acid, oxalic acid, fumaric acid and phthalic acid.

The polymerizable composition of the present invention may contain a polymerization inhibitor. The polymerization inhibitor to be used is not particularly limited and known ones can be used.

For example, p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 2.2. '-Methylenebis(4-ethyl-6-t-butylphenol), 4.4'-thiobis(3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2 , 2′-bi-1-naphthol, and other phenolic compounds, hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone , 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone, and the like.
(Method for preparing polymerizable composition)
The polymerizable composition of the present invention contains (A) an alkali-soluble resin, (B) a polymerizable compound having at least one polymerizable functional group in the molecular structure, and (C) a photopolymerization initiator, ) A compound having a mesogenic skeleton is contained as an essential component in the alkali-soluble resin and/or as the (B) polymerizable compound, but it is prepared by mixing other optional components in a predetermined ratio, if necessary. It The polymerizable composition is preferably dissolved in a suitable solvent and used in a solution state. When the polymerizable composition is prepared in a solution state, the solid content concentration (a component other than the solvent in the composition solution) may be, for example, 5% by mass to 50% depending on the purpose of use or the desired film thickness value. It can be set to any concentration such as mass%. The more preferable solid content concentration depends on the method of forming a coating film on a substrate. The composition solution thus prepared can be used, if necessary, after being filtered using a Millipore filter or the like having a pore size of about 0.5 μm.

Also, the carbon black dispersion and the colorant dispersion can be prepared by the same method as the method for preparing the polymerizable composition.

Furthermore, in the polymerizable composition for a liquid crystal-polymer complex, when the component (A) contains a solvent, the solvent is removed (A) component, the (C) component, and the (B). The components and the liquid crystal composition are contained as essential components, but they are prepared by mixing other optional components in predetermined ratios as needed. The polymerizable composition is preferably used in a liquid state containing no solvent. In the polymerizable composition, the ratio of the component (A), the component (B), the component (C), etc. to the liquid crystal composition can be arbitrarily set according to the purpose of use and the desired thickness. A more preferable ratio of the liquid crystal composition varies depending on the kind of the liquid crystal composition, but can be set to 30% by mass to 95% by mass. The polymerizable composition thus prepared can be used, if necessary, after being filtered using a membrane filter having a pore size of about 0.5 to 5.0 μm.
(Cured film manufacturing method)
The polymerizable composition of the present invention is a spacer material such as a columnar spacer, a material for forming an overcoat layer for protecting the substrate of a display element, a cured film as an interlayer insulating material for a display element used in a flexible display or the like, Alternatively, it is preferably used for forming a liquid crystal-polymer composite used for a light control element, a display element, an optical element, or the like. Further, the present invention preferably includes a spacer material formed using the polymerizable composition, an overcoat layer (protective film) for a display element, a cured film as an interlayer insulating film, and a liquid crystal-polymer composite. Be done.

As one of the methods for producing a cured film of the present invention, (I) a step of forming a coating film using the polymerizable composition, (II) a step of irradiating at least a part of the coating film with radiation, (III) ) A so-called photolithography method having a step of developing the coating film irradiated with the radiation and (IV) a step of baking the developed coating film can be mentioned. In the method for producing a cured film of the present invention, the steps (I) to (IV) may be partially omitted. Hereinafter, each step will be described.
[Step (I)]
In the step, a coating film of the polymerizable composition is formed on a substrate or the like. Examples of the substrate include a glass substrate, a resin substrate made of a polymer such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and polyimide. A transparent electrode such as ITO, IZO, IGZO, graphene, carbon nanotube, and silver wire may be formed on one surface of the substrate. When a coating film is formed by coating, the coating film can be formed by coating the polymerizable composition or the solution of the polymerizable resin composition, and then preferably heating (prebaking) the coated surface. .. When the solution of the polymerizable resin composition is applied, the solid content concentration of the composition solution used in the application method is 2% by mass to 60% by mass, and 5% by mass to 50% by mass is Preferably, 10% by mass to 40% by mass is more preferable, and 15% by mass to 35% by mass is further preferable. As a method for applying the polymerizable composition, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, an inkjet coating method, or the like. Can be adopted. Of these, the spin coating method or the slit coating method is preferable. When prebaking is carried out, the prebaking conditions are preferably 70° C. to 120° C., and preferably about 1 minute to 15 minutes, although the conditions vary depending on the type of each component, the blending ratio and the like. The film thickness of the coating film after prebaking is preferably 0.5 μm to 10 μm, more preferably 1.0 μm to 7.0 μm.
[Step (II)]
In the step, radiation is applied to at least a part of the formed coating film. When irradiating only a part of the coating film, a method of irradiating through a photomask can be adopted. Examples of the radiation used for irradiation include visible light, ultraviolet rays, far ultraviolet rays and the like. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable. Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of radiation irradiated ^is preferably ^{100J / m 2 ~5,000J / m 2} , 200J / m 2 ~3,000J / m ² is more preferable.

In addition, in the liquid crystal-polymer composite, the upper surface of the coating film can be covered with a substrate before irradiation with radiation.
[Step (III)]
In this step, the coating film after irradiation with radiation is developed to remove unnecessary portions and form a desired pattern. Examples of the developer used for development include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide and sodium carbonate, and alkaline compounds such as quaternary ammonium salts such as tetramethylammonium hydroxide. A water-soluble organic solvent such as methanol or ethanol may be appropriately added to the aqueous solution of the alkaline compound. As the developing method, a method such as a puddle method, a dipping method or a shower method can be adopted, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Following the development treatment, for example, washing with running water is performed, and then air drying is performed to obtain a desired pattern.
[Step (IV)]
In the step, a cured film is obtained by baking (post-baking) the obtained patterned coating film with an appropriate heating device such as an oven. The firing temperature is preferably 60°C to 200°C, more preferably 80°C to 190°C, and further preferably 100°C to 180°C. The firing time is preferably 2 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven, for example.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
(Adjustment of alkali-soluble resin "A-1")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of methacrylic acid, and glycidyl methacrylate. In addition to 20 parts by mass, 10 parts by mass of styrene, 20 parts by mass of vinylbiphenyl, and 10 parts by mass of methyl methacrylate, and after substituting with nitrogen, the temperature of the solution was raised to 70° C. with slow stirring, and the above temperature was maintained. The polymerization reaction was carried out for 4 hours. The weight average molecular weight Mw of the obtained copolymer was 8000.
(Adjustment of alkali-soluble resin "A-2")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of methacrylic acid, and glycidyl methacrylate. 20 parts by mass, 10 parts by mass of styrene, 20 parts by mass of acrylic acid=6-(4′-cyanobiphenyl-4-yloxy)hexyl, and 10 parts by mass of methyl methacrylate, and after nitrogen substitution, the solution was slowly stirred. The temperature was raised to 80° C., and the polymerization reaction was carried out for 4 hours while maintaining the above temperature. The weight average molecular weight Mw of the obtained copolymer was 9000.
(Adjustment of alkali-soluble resin "A-3")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of methacrylic acid, and glycidyl methacrylate. 20 parts by mass, 10 parts by mass of vinylbiphenyl, 20 parts by mass of 4-[6-(acryloyloxy)hexyloxy]benzoic acid 4-(4-propylcyclohexyl)phenyl, 10 parts by mass of methyl methacrylate, and nitrogen substitution was performed. Then, the temperature of the solution was raised to 80° C. with slow stirring, and the polymerization reaction was carried out for 4 hours while maintaining the temperature. The weight average molecular weight Mw of the obtained copolymer was 8500.
(Adjustment of alkali-soluble resin "A-4")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of methacrylic acid, and glycidyl methacrylate. 20 parts by mass, 10 parts by mass of vinyl biphenyl, 20 parts by mass of 4-[6-(acryloyloxy)hexyloxy]benzoic acid=4-(2,4-dimethylphenyloxycarbonyl)phenyl, 10 parts by mass of methyl methacrylate After purging with nitrogen, the temperature of the solution was raised to 80° C. with slow stirring, and the polymerization reaction was carried out for 4 hours while maintaining the temperature. The weight average molecular weight Mw of the obtained copolymer was 9,500.
(Adjustment of alkali-soluble resin "A-5")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of methacrylic acid, and glycidyl methacrylate. 20 parts by mass, 1,3-butadiene 5 parts by mass, bis{4-[3-(acryloyloxy)propoxy]benzoic acid}=2-methyl-1,4-phenylene 25 parts by mass, methyl methacrylate 10 parts by mass After replacement with nitrogen, the temperature of the solution was raised to 70° C. with slow stirring, and the polymerization reaction was carried out for 4 hours while maintaining the temperature. The weight average molecular weight Mw of the obtained copolymer was 10500.
(Adjustment of alkali-soluble resin "A-6")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of methacrylic acid, glycidyl methacrylate. 20 parts by mass, 1,3-butadiene 5 parts by mass, 4-(6-acryloyloxyhexyloxy)benzoic acid=4-[2-[4-(6-(acryloyloxyhexyloxy)benzoyloxy]ethyl]phenyl 25 parts by mass Parts, and 10 parts by mass of methyl methacrylate, and after substituting with nitrogen, the temperature of the solution was raised to 70° C. with slow stirring, and a polymerization reaction was carried out for 4 hours while maintaining the temperature. The weight average molecular weight Mw of the obtained copolymer was 7,500.
(Adjustment of alkali-soluble resin "C1")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, glycidyl methacrylate. 25 parts by mass, 10 parts by mass of styrene, 15 parts by mass of methyl methacrylate, 20 parts by mass of tricyclo[5.2.1.2.6]decane-8-yl methacrylate, and after substituting with nitrogen, slowly stirring. The temperature of the solution was raised to 70° C., and the polymerization reaction was carried out for 4 hours while maintaining the temperature. The weight average molecular weight Mw of the obtained copolymer was 8000.
(Adjustment of alkali-soluble resin "C2")
In a four-necked flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), 200 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, glycidyl methacrylate. 30 parts by mass, 5 parts by mass of styrene, 5 parts by mass of 1,3-butadiene, 30 parts by mass of tricyclo[5.2.1.2.6]decane-8-yl methacrylate, and after nitrogen substitution, slowly stirred. While raising the temperature of the solution to 70° C., the polymerization reaction was carried out for 4 hours while maintaining the temperature. The weight average molecular weight Mw of the obtained copolymer was 7,500.
(Example 1)
(Polymerizable composition 1)
As the alkali-soluble resin, 150 parts by mass of the alkali-soluble resin solution A-1 obtained in Synthesis Example 1, 45 parts by mass of Aronix M-400 (manufactured by Toagosei Co., Ltd.) as a polymerizable compound having an ethylenically unsaturated bond, 7 parts by mass of Irgacure OXE02 (manufactured by BASF) as a polymerization initiator, 0.1 parts by mass of Megafac R-40 (manufactured by DIC Corporation) as a leveling agent, and 0.2 parts by mass of p-methoxyphenol as a polymerization inhibitor propylene. It was dissolved in 100 parts by mass of glycol monomethyl ether acetate and 22 parts by mass of 3-methoxybutyl acetate, and then filtered through a membrane filter having a pore size of 0.2 μm to obtain a polymerizable composition of Example 1.
(Column spacer: liquid crystal is vertically aligned)
The obtained polymerizable composition 1 was applied using a spin coater to the ITO electrode side of a non-alkali glass substrate on which ITO was sputtered as a transparent electrode, and dried at 90° C. for 2 minutes to give a film having a thickness of 3.0 μm. A coating film was formed.

Then, the obtained coating film was irradiated with ultraviolet light having a light intensity of 365 nm of 30 mW/cm 2 for 3.3 seconds through a chrome photomask made of quartz glass having a circular pattern opening having a diameter of 10 μm. The chrome photomask used had a circular pattern having an aperture having a transmittance of 90% or more, a light-shielding portion (chrome portion) having a transmittance of 436 nm of 11%, and an aperture-to-aperture spacing of 200 μm. .. The distance between the obtained coating film and the photomask was 150 μm.

Next, it was developed with a 0.1% potassium hydroxide aqueous solution at 25° C., and rinsed with ultrapure water to form a pattern on the glass substrate. Furthermore, it heated at 230 degreeC for 30 minutes, and obtained the columnar spacer of the Example.

A polyimide for vertical alignment was applied to a spin coater on the columnar spacers of the obtained glass substrate with columnar spacers, dried at 80° C. for 5 minutes, and further baked at 230° C. for 30 minutes. On the other hand, polyimide for vertical alignment was similarly applied to the ITO electrode side of the glass substrate on which ITO was formed by a spin coater, dried at 80° C. for 5 minutes, and further baked at 230° C. for 30 minutes.

Both glass substrates thus obtained were subjected to rubbing orientation treatment so that the pretilt was 1 to 2° with respect to the normal direction to the substrate surface, and an epoxy resin-based resin was placed on the polyimide film by using a dispenser on the outer periphery of one of the glass substrates. After applying the sealant, both glass substrates were bonded together so that the pretilt angle of the liquid crystal composition after bonding was about 1°. Then, the sealing agent was cured at 90° C. for 5 minutes and 150° C. for 30 minutes to obtain a cell for evaluation.

An N-type liquid crystal composition (LCN-1, Δn: 0.102, viscosity: 16.8, Δε: -3.8 described in JP-A-2017-95712) was added to the obtained evaluation cell at 60°C. It was heated and injected into the glass cell by the vacuum injection method.
After the injection, the glass cell was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by ThreeBond Co., Ltd.). As a result, a VA mode liquid crystal display device was obtained. Placing the cell between two orthogonal polarizers makes it black, and the dark field does not change even if the cell is rotated in the azimuth direction, and there is no in-plane phase difference in the column spacer, or It was confirmed that the optical axis direction of the spacer and the liquid crystal alignment easy axis direction were the same direction.
(response speed)
A rectangular wave of 60 Hz/20 V was applied to the obtained liquid crystal display element, and the response time was measured. The response time was confirmed to be faster when the rise time τon was 3.0 msec and the fall time τoff was 3.2 msec.
(contrast)
A white LED, a polarizing plate, a liquid crystal display element, a polarizing plate, and a spectroradiometer (SR-LEDW: manufactured by Topcon Technohouse Co., Ltd.) were arranged in that order. The two polarizing plates were arranged so as to be crossed Nicols.
The brightness (OFF brightness) when no voltage was applied to the obtained liquid crystal display element and the brightness (ON brightness) when the maximum brightness was reached by applying a voltage were measured, and the ratio (ON brightness/ON brightness/ OFF luminance) was used as the contrast.
Liquid crystal display device ⊚: 2500 or more O: 2000 or more and less than 2500 Δ: 1500 or more and less than 2000 x: less than 1500 The obtained liquid crystal display device had a good contrast of 2650. In particular, the OFF luminance was significantly reduced.
(Examples 2-4, Examples 7-8, Examples 11-12, Examples 14-15, Comparative Examples 1-2)
For the columnar spacers and liquid crystal display devices of Examples 2 to 4, Examples 7 to 8, Examples 11 to 12, Examples 14 to 15, and Comparative Examples 1 to 2, the polymerizable composition used was as shown in Table 1. It was produced in the same manner as in Example 1 except that the polymerizable composition shown in 1 was used.
For the columnar spacers and liquid crystal display elements of Examples 14 to 15, the polymerizable composition used was the polymerizable composition shown in Table 1, and the columnar spacer was irradiated under conditions of 365 nm light intensity of 30 mW/cm 2. It was produced in the same manner as in Example 1 except that it was irradiated with ultraviolet light for 10 seconds.

Aronix M-400: dipentaerythritol penta and hexaacrylate (manufactured by Toagosei Co., Ltd.)
A-DPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Light acrylate DPE-6A: dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
Irgacure OXE02: oxime ester-based photopolymerization agent (manufactured by BASF Corporation)
Irgacure OXE04: Oxime ester photopolymerization agent (manufactured by BASF Corporation)
ADEKA ARKUL'S NCI-831: Oxime ester photopolymerizer (made by ADEKA Corporation)
Irganox 1076: hindered phenolic antioxidant (manufactured by BASF Corporation)
MEHQ: p-methoxyphenol (polymerization inhibitor)
LSN: hydroxynaphthoquinone (polymerization inhibitor)
Megafac R-40: Fluorine-containing/hydrophilic group/lipophilic group-containing oligomer (manufactured by DIC Corporation)
Megafac F-554: Fluorine-containing/lipophilic group-containing oligomer (manufactured by DIC Corporation)
(Example 5)
As the alkali-soluble resin, 150 parts by mass of the alkali-soluble resin solution A-5 obtained in Synthesis Example 5, 45 parts by mass of Aronix M-400 (manufactured by Toagosei Co., Ltd.) as a polymerizable compound having an ethylenically unsaturated bond, 7 parts by mass of Irgacure OXE02 (manufactured by BASF) as a polymerization initiator, 0.2 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a leveling agent, and 0.2 parts by mass of p-methoxyphenol as a polymerization inhibitor propylene. It was dissolved in 100 parts by mass of glycol monomethyl ether acetate and 22 parts by mass of 3-methoxybutyl acetate, and then filtered through a membrane filter having a pore size of 0.2 μm to obtain a polymerizable composition of Example 5.
(Column spacer: Liquid crystal is horizontally aligned)
The obtained polymerizable composition 5 was applied using a spin coater to the ITO electrode side of a non-alkali glass substrate on which ITO was sputtered as a transparent electrode, and dried at 90° C. for 2 minutes to give a film having a thickness of 3.0 μm. A coating film was formed.

Then, the obtained coating film was irradiated with ultraviolet light having a light intensity of 365 nm of 30 mW/cm 2 for 3.3 seconds through a chrome photomask made of quartz glass having a circular pattern opening having a diameter of 10 μm. The chrome photomask used had a circular pattern having an aperture having a transmittance of 90% or more, a light-shielding portion (chrome portion) having a transmittance of 436 nm of 11%, and an aperture-to-aperture spacing of 200 μm. .. The distance between the obtained coating film and the photomask was 150 μm.

Next, it was developed with a 0.5 wt% tetramethylammonium hydroxide aqueous solution at 25° C., and rinsed with ultrapure water to form a pattern on the glass substrate. Furthermore, it heated at 230 degreeC for 30 minutes, and obtained the columnar spacer of the Example.
A polyimide for horizontal alignment was applied to a spin coater on the columnar spacer of the obtained glass substrate with the columnar spacer, dried at 80° C. for 5 minutes, and further baked at 230° C. for 30 minutes. On the other hand, polyimide for orientation was similarly applied to the ITO electrode side of the glass substrate on which ITO was formed by a spin coater, dried at 80° C. for 5 minutes, and further baked at 230° C. for 30 minutes.

Rubbing alignment treatment is performed on the obtained both glass substrates so that the pretilt is 1 to 2° with respect to the substrate surface, and an epoxy resin-based sealant is applied on the polyimide film using a dispenser on the outer periphery of one of the glass substrates. After coating, both glass substrates were bonded so that the pretilt angle of the liquid crystal composition after bonding was about 1 degree. Then, the sealing agent was cured at 90° C. for 5 minutes and 150° C. for 30 minutes to obtain a cell for evaluation.

A P-type liquid crystal composition (LCP-1, Δn0.103, viscosity η20 mPa·s described in JP-A-2017-95712) was heated to 60° C. in the obtained evaluation cell, and a glass cell was formed by a vacuum injection method. Injected inside.

A parallel rubbing alignment cell with ITO coated with a polyimide alignment film having a cell gap of 3 μm was used so that uniaxial alignment (homogeneous alignment) of liquid crystal was obtained. The polymerizable liquid crystal composition (LCM-1) was injected into the glass cell by a vacuum injection method.

After the injection, the glass cell was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by ThreeBond Co., Ltd.). Ultraviolet rays with an irradiation intensity of 15 mW/cm 2 through an ultraviolet ray cut filter L-37 (manufactured by Hoya Candeo Optronics) were irradiated at 25° C. for 300 seconds. As a result, the polymerizable compound in the polymerizable liquid crystal composition was polymerized to obtain an ECB mode liquid crystal display device. It was confirmed that when the cell prepared between two orthogonal polarizing plates was placed so that the rubbing treatment direction coincided with the polarization axis direction, a dark field was obtained and uniaxial orientation was obtained.
(response speed)
A rectangular wave of 60 Hz/10 V was applied and the response time in the ECB mode was examined.
The response speed τon when voltage was applied tended to be slightly slower than 0.2 msec, but the response speed τoff when the voltage was turned off was confirmed to be faster from 5 msec to 3 msec, and the overall response of τon+τoff was faster. It has been found.
(contrast)
A white LED, a polarizing plate, a liquid crystal display element, a polarizing plate, and a spectroradiometer (SR-LEDW: manufactured by Topcon Technohouse Co., Ltd.) were arranged in that order. The two polarizing plates were arranged so as to be crossed Nicols.
The brightness (OFF brightness) when no voltage was applied to the obtained liquid crystal display element and the brightness (ON brightness) when the maximum brightness was reached by applying a voltage were measured, and the ratio (ON brightness/ON brightness/ OFF luminance) was used as the contrast.
Liquid crystal display device A: 2000 or more O: 1500 or more and less than 2000 B: 1000 or more and less than 1500 X: less than 1000 The obtained liquid crystal display device had a good contrast of 2020. In particular, the OFF luminance was significantly reduced.
(Example 6, Example 9-10, Example 13, Example 16)
For the columnar spacers and liquid crystal display devices of Examples 6, 9 to 10, 13 and 16, except that the polymerizable composition used was the polymerizable composition shown in Tables 1 to 3. It was produced in the same manner as in Example 1.
For the columnar spacers and liquid crystal display elements of Examples 14 to 15, the polymerizable composition used was the polymerizable composition shown in Table 1, and the columnar spacer was irradiated under conditions of 365 nm light intensity of 30 mW/cm 2. It was produced in the same manner as in Example 1 except that it was irradiated with ultraviolet light for 10 seconds. As shown in Tables 1 to 3, the response speeds of the obtained liquid crystal display elements were all confirmed to be high, and the contrasts of the obtained liquid crystal display elements were all good.
(Example 17) Preparation of overcoat layer and evaluation of smoothness (surface roughness)
As the alkali-soluble resin, 100 parts by mass of the alkali-soluble resin solution A-1 obtained in Synthesis Example 1, and as the polymerizable compound having an ethylenically unsaturated bond, the polymerizable compound represented by the formula (B-4-1) 15 parts by mass of the compound, 5 parts of the polymerizable compound represented by the formula (B-4-2), 25 parts by mass of Aronix M-400 (manufactured by Toagosei Co., Ltd.), and Irgacure OXE02 (manufactured by BASF Corporation) as a polymerization initiator. 7 parts by mass, 0.2 parts by mass of Megafac R-40 (manufactured by DIC Corporation) as a leveling agent, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor, 50 parts by mass of propylene glycol monomethyl ether acetate, and 3 parts of acetic acid. -Dissolved in 22 parts by mass of methoxybutyl and 50 parts by mass of cyclopentanone, and filtered through a membrane filter having a pore size of 0.2 µm to obtain a polymerizable composition of Example 17.

A glass substrate was spin-coated with the obtained polymerizable composition on the color filter substrate described in the example of JP-A-2016-157118, dried at 90° C. for 2 minutes, and then at 230° C. for 30 minutes. Minute heating was performed to obtain an overcoat layer.

A part of the obtained color filter coating film with an overcoat layer was scraped off with a cutter until the glass surface was visible, and a substrate with steps was obtained. The coating film portion 2 mm near the substrate step and the glass portion 1 mm were measured using a stylus type surface profile measuring device Dektak XT (manufactured by Bruker), and the difference between the maximum value and the minimum value of the film thickness of the coating film portion. Was calculated to be 30 nm.
(Example 18) Preparation of overcoat layer and evaluation of smoothness (surface roughness)
The overcoat layer of Example 18 was produced in the same manner as in Example 17, except that the polymerizable composition used was the polymerizable composition shown in Table 3.

(Example 19) Preparation of liquid crystal-polymer composite (1)
Liquid crystal composition (1) (transition temperature T _NI from liquid crystal to isotropic phase: 90.5° C., melting point: −27° C., dielectric anisotropy Δε at 25° C.: 11.0, refractive index anisotropy Δn Is 0.201, the rotational viscosity coefficient γ ₁ is 54 mPa·s), 70 parts by mass, the solvent is distilled from the alkali-soluble resin “A-1”, 7.5 parts by mass, and isostearyl acrylate (trade name “S”). -1800A" manufactured by Shin-Nakamura Chemical Co., Ltd.), 12.5 parts by mass, polypropylene glycol diacrylate (trade name "APG-400" manufactured by Shin-Nakamura Chemical Co., Ltd.), 10.0 parts by mass, Omnirad651 (IGM Resins Co., Ltd.) 0.3 part by mass of (1) was mixed at room temperature, and the mixture was heated and stirred at 50° C. for 30 minutes to prepare a polymerizable composition (19).

A PET film with a thickness of 188 μm and a 10 cm×10 cm ITO transparent electrode was coated with an ethanol dispersion of spherical spacer particles having a thickness of 15 μm on the transparent electrode side, dried, and then the polymerizable composition 19 was dropped using an applicator to form the electrode. It was laminated on the polymerizable composition 19 so as to be in contact with the electrode side of the base material. At that time, the base materials were each offset by 5 mm so that the electro-optical characteristics could be evaluated.

Then, pressure is applied to the bonding base material to make the entire thickness almost constant, and then ultraviolet light is irradiated while maintaining the bonding base material at 25±1° C. to adjust light including the liquid crystal-polymer composite. A device was produced. At this time, a metal halide lamp was used as an ultraviolet light source, and ultraviolet rays were irradiated for 300 seconds at an illuminance of 5 mW/cm ² (total 1.5 J/cm ² ). The illuminance was measured using a unimeter UIT-101 with a UVD-365PD light receiver manufactured by Ushio Inc.

It was confirmed that the obtained light control device was in a scattering state when no voltage was applied.

The electro-optical characteristics were measured by measuring the haze (Hz) of the liquid crystal element when measuring light was incident on the obtained dimming element in the normal direction, using a haze meter (NDH-7000 manufactured by Nippon Denshoku Industries Co., Ltd.). It was performed by measuring with. The haze value was calculated from the total light transmittance (TT) and the parallel light transmittance (PT) by the following formula.

Hz=[{TT-PT}/TT]×100 (%)
The haze of the obtained liquid crystal element before applying a voltage was 97.5%. When the haze was measured with a voltage of AC 30 V (60 Hz, rectangular wave) applied to the liquid crystal element, the haze was 7.0%.
Haze OFF: Ratio of diffused light transmittance to total light transmittance when no voltage is applied
Haze ON: Ratio of diffused light transmittance to total light transmittance when voltage is applied (Example 20) Preparation of liquid crystal-polymer composite (2)
Liquid crystal composition (2) (transition temperature T _NI from liquid crystal to isotropic phase: 105.5° C., melting point: −37° C., dielectric anisotropy Δε at −25° C.: −3.4, refractive index anisotropy Δn is 0.156, rotational viscosity coefficient γ ₁ is 90 parts by mass of 282 mPa·s, 1.0 part by mass of the resin obtained by distilling the solvent from the alkali-soluble resin “A-3”, and the formula (B-2-4). ), a compound represented by formula (B-2-5), and an isostearyl acrylate (trade name "S-1800A" manufactured by Shin-Nakamura Chemical Co., Ltd.). 5.0 parts by mass and 0.1 parts by mass of Omnirad 651 (IGM Resins Co., Ltd.) were mixed at room temperature, and the mixture was heated with stirring at 60° C. for 30 minutes to prepare a polymerizable composition (20). The resulting polymerizable composition (20) showed a nematic phase at room temperature.

10 μm on the vertical alignment film side of the electrode substrate obtained by applying a polyimide solution for a vertical alignment film to a PET film with an ITO transparent electrode having a thickness of 188 μm and a thickness of 10 cm×10 cm to about 0.1 μm, and drying and baking the solution. After coating the ethanol dispersion of spherical spacer particles, and drying the polymerizable composition 1 with an applicator, the polymerizable composition (20) is contacted with the vertical alignment film side of the electrode substrate. Pasted on top. At that time, the base materials were each offset by 5 mm so that the electro-optical characteristics could be evaluated.

Then, pressure is applied to the bonding base material to make the entire thickness almost constant, and then ultraviolet light is irradiated while maintaining the bonding base material at 25±1° C. to adjust light including the liquid crystal-polymer composite. A device was produced. At this time, a metal halide lamp was used as an ultraviolet light source, and ultraviolet rays were irradiated for 200 seconds at an illuminance of 15 mW/cm ² (total 3.0 J/cm ² ). The illuminance was measured using a unimeter UIT-101 with a UVD-365PD light receiver manufactured by Ushio Inc.

In the obtained light control device, when no voltage was applied, no scattering was observed in the transparent state, and it was confirmed that the liquid crystal was vertically aligned.

The haze of the obtained light control device before applying a voltage was 2.1%. When the haze was measured with a voltage of AC 60 V (60 Hz, rectangular wave) applied to the liquid crystal element, the haze was 93.3%.

Claims (12)

(A) Alkali-soluble resin, and
(B) A polymerizable composition comprising a polymerizable compound having at least one polymerizable functional group in the molecular structure as an essential component,
The compound (B) has a mesogenic structure in its molecular structure and has the following general formula (1)

(In the formula,
P represents a polymerizable functional group,
Sp represents an alkylene group having 0 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms or CN, and one CH ₂ group present in this group or not adjacent to it) Two or more CH ₂ groups are each independently of the other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N(CH ₃ )—, —CO—, It may be replaced by -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-),
m represents 0 or 1,
MG represents a mesogenic group,
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an isocyano group, a thioisocyano group, a hydroxy group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group is one or more halogen atoms or It may be substituted by CN, and one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other. _{, -O -, - S -,} - NH -, - N (CH 3) -, - CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or -C≡C- Or R ¹ is represented by the general formula (1-a)

(In the formula,
P represents a polymerizable functional group,
Sp represents a spacer group having 0 to 18 carbon atoms,
m represents 0 or 1. ) Represents a structure represented by. )
Using a compound represented by
In the polymerizable compound (B) the total content of the alkali-soluble resin (A), and the total amount of the polymerizable compound (B), the polymerizable composition comprising 10 to 80 wt% There
A polymerizable composition containing a photopolymerization initiator (C) in addition to the components (A) and (B) . The addition to the (A) ~ (C) component, further, the polymerizable composition according to claim 1 containing (D) an organic solvent. The alkali-soluble resin (A), polymerizable composition according to any one of claims 1-2 and has a mesogenic skeleton in the resin structure. The alkali-soluble resin (A) has a mesogenic skeleton in its resin structure and has the following structural formula (1)

(In the formula,
P represents a polymerizable functional group,
Sp represents an alkylene group having 0 to 18 carbon atoms (the alkylene group may be substituted with one or more halogen atoms or CN, and one CH ₂ group present in this group or not adjacent to it) Two or more CH ₂ groups are each independently of the other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N(CH ₃ )—, —CO—, It may be replaced by -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-),
m represents 0 or 1,
MG represents a mesogenic group,
R ¹ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. One existing CH ₂ group or two or more non-adjacent CH ₂ groups are each independently of the other, —O—, —S—, —NH—, in a form in which oxygen atoms are not directly bonded to each other. _{-N (CH 3) -, -} CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or may be replaced by -C≡C- or R ¹ in general, Formula (1-a)

(In the formula,
P represents a reactive functional group,
Sp represents a spacer group having 0 to 18 carbon atoms,
m represents 0 or 1. )
Represents a structure represented by. )
The polymerizable composition according to claim 3 , which is obtained by copolymerizing the polymerizable liquid crystal compound represented by the formula (3) and an acid group-containing polymerizable monomer. Cured product using the polymerizable composition according to any one of claims 1-4. A photo spacer composed of the cured product according to claim 5 . Display device overcoat using the polymerizable composition according to any one of claims 1-4. Display element for an interlayer insulating material comprising a polymerizable composition according to any one of claims 1-4. The polymerizable composition according to any one of claims 1-4, and a liquid crystal comprising the liquid crystal composition - polymer composite-body composition. A liquid crystal display device comprising the photo spacer according to claim 6 . A liquid crystal-polymer composite using the composition for liquid crystal-polymer composite according to claim 9 . A light control device comprising the liquid crystal-polymer composite according to claim 11 .