JP2009145436A - Resin composition for forming projection for controlling liquid crystal alignment, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition for forming projections for controlling liquid crystal alignment, the resin composition reducing failure in driving a liquid crystal panel due to projections for controlling liquid crystal alignment, using a negative resist and achieving formation of projections for controlling liquid crystal alignment for improving the display qualities, and to provide a color filter having projections for controlling liquid crystal alignment by using the resin composition. <P>SOLUTION: The negative photosensitive resin composition for forming projections for controlling liquid crystal alignment contains an acrylic acid 2-(tricyclo[5. 2. 1. 0<SP>2, 6</SP>]-3-en-9-yloxy)alkyl (A), having a specified structure and exhibiting a relative dielectric constant of from 1.0 to 4.0 at 1 kHz, after being cured. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid crystal alignment control protrusion-forming resin composition used when forming a liquid crystal alignment control protrusion of a vertical alignment liquid crystal display type color filter, and a liquid crystal alignment using the liquid crystal alignment control protrusion formation resin composition The present invention relates to a color filter having a control protrusion.

  In a liquid crystal display device, a transparent substrate on the color filter side and a liquid crystal driving side substrate are opposed to each other, and a liquid crystal compound is sealed between the two to form a thin liquid crystal layer, and the liquid crystal driving side substrate forms a liquid crystal array in the liquid crystal layer. Display is performed by selectively changing the amount of transmitted or reflected light of the color filter under electrical control.

  In recent years, there has been proposed a vertical alignment liquid crystal display device in which liquid crystal molecules are arranged perpendicular to a substrate surface in a state where no voltage is applied, and the liquid crystal molecules are tilted in various directions when a voltage is applied. As such a vertically aligned liquid crystal display device in which the liquid crystal molecules are tilted in many directions, the transparent electrode layer (ITO (indium tin oxide) layer) and the second electrode layer formed on the opposite liquid crystal driving side substrate are used. A method using a method of forming liquid crystal alignment control protrusions on the surface and controlling the alignment direction of liquid crystal when a voltage is applied (hereinafter also referred to as an MVA method) has been proposed (Patent Document 1). This MVA method is superior in terms of contrast ratio, response speed, and the like as compared with the twisted nematic method used conventionally. In addition, since the liquid crystal molecules are tilted in many directions, there is an advantage that a high viewing angle can be effectively realized.

  In the vertical alignment liquid crystal display device, black display is performed in a state where liquid crystal molecules are aligned vertically, that is, a state where no voltage is applied. Here, when the liquid crystal alignment control protrusion is formed using a negative resist as the photosensitive resist, the liquid crystal alignment control protrusion has a high relative dielectric constant, and therefore, after the voltage is applied to the liquid crystal display device, the voltage is removed. In this case, the charging is not eliminated, and the liquid crystal panel is not driven properly by the liquid crystal alignment control projection, that is, burn-in occurs. Further, even when switching to a new display in a state where the liquid crystal alignment control protrusion remains charged, there is a problem in that an image cannot be displayed accurately because burn-in remains and an afterimage is generated.

  On the other hand, by lowering the relative dielectric constant of the liquid crystal alignment control projection using a negative resist, the charging when the voltage is removed is eliminated, and the drive failure of the liquid crystal panel is improved. Therefore, it is considered that display quality can be improved by using a liquid crystal alignment control protrusion having a low relative dielectric constant.

  As a method for reducing the dielectric constant of the composition, (1) a method in which an atom having a small molar polarizability such as a fluorine atom is introduced into a component of the composition to reduce the relative dielectric constant of the entire composition, (2 ) A method of introducing bulky groups into the constituents of the composition to reduce the density of polar groups per unit volume and lowering the relative dielectric constant of the entire composition. Thus, the use of a bulky and low-polarity liquid crystal alignment control protrusion-forming resin composition is effective in reducing the dielectric constant of the liquid crystal alignment control protrusion. However, since the solubility of the negative resist in the developer decreases when the polarity of the resin composition decreases, the resin composition is applied onto the transparent electrode layer, dried, exposed, and developed to obtain a liquid crystal. It is difficult to form alignment control protrusions in a pattern.

JP 2003-75839 A

  In view of the above situation, the present invention reduces negative liquid crystal panel drive failure due to liquid crystal alignment control protrusions using a negative resist, and can form a liquid crystal alignment control protrusion capable of improving display quality. An object of the present invention is to provide a liquid crystal alignment control protrusion-forming resin composition and a color filter having a liquid crystal alignment control protrusion using the resin composition.

As a result of intensive studies, the inventors of the present invention include a compound (A) represented by the following chemical formula (1) having a specific structure in the negative photosensitive liquid crystal alignment control protrusion-forming resin composition. As a result, the inventors have found that a liquid crystal alignment control protrusion having a low dielectric constant can be obtained, and have completed the present invention.
That is, the present invention contains 2- (tricyclo [5.2.1.0 ^2,6 ] -3-en-9-yloxy) alkyl acrylate (A) represented by the following chemical formula (1): Provided is a negative photosensitive liquid crystal alignment controlling protrusion forming resin composition having a relative dielectric constant after curing of 1.0 or more and 4.0 or less at 1 kHz.

（化学式（１）中、Ｒは、炭素数が１〜４のアルキレン基を表す。）

(In chemical formula (1), R represents an alkylene group having 1 to 4 carbon atoms.)

  According to the present invention, by incorporating the compound (A) represented by the above chemical formula (1) having a specific structure into the negative photosensitive liquid crystal alignment control protrusion-forming resin composition, a low dielectric constant is obtained. The liquid crystal alignment control protrusion can be obtained.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, a compound (B) having at least one alicyclic structure having 7 to 20 carbon atoms and a light or thermosetting reactive group. ) Is further preferable from the viewpoint of improving the heat resistance and residual film ratio of the cured film.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, the heat resistance of the cured film is such that the light or thermosetting reactive group is an ethylenically unsaturated group or a glycidyl group. And from the point which improves a remaining-film rate, it is preferable.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, the ethylenically unsaturated group is preferably a methacryl group or an acryloyl group from the viewpoint of improving the hardness of the cured film.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, the alicyclic structure is adamantane or diamantane, and the curability is not increased significantly. It is preferable from the point of improving.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, the content of the compound (B) is preferably 5 to 25% by weight based on the total solid content.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, it is hardened to further contain a silicon-based compound (C) having a linear or network structure of —Si—O— or Si. This is preferable from the viewpoint of lowering the relative dielectric constant later.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, the silicon compound (C) is at least one compound selected from the following compound group after curing. This is preferable from the viewpoint of reducing the relative dielectric constant.

（化学式（Ｃ−１）中、Ｒはメチル基、又はメトキシ基である。）

(In the chemical formula (C-1), R is a methyl group or a methoxy group.)

（Ａ_{Ｓｉ‐Ｎｅｔｗｏｒｋ}は、Ｓｉが架橋結合してなる編目構造を表す。Ｌは、当該Ｓｉが架橋結合してなる編目構造の末端に結合した炭素数が１〜４のアルキル基、又はフェニル基を表す。ＯＨは、当該Ｓｉが架橋結合してなる編目構造の末端に結合したヒドロキシ基を表す。）

(A _Si-Network represents a stitch structure formed by cross-linking Si. L represents an alkyl group having 1 to 4 carbon atoms or a phenyl group bonded to the end of the stitch structure formed by cross-linking Si. OH represents a hydroxy group bonded to the end of the stitch structure formed by cross-linking of the Si.)

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to the present invention, the content of the silicon compound (C) is preferably 5 to 20% by weight based on the total solid content. .

  Further, in order to solve the above-mentioned problems, the present invention is characterized in that it has a liquid crystal alignment control protrusion comprising a cured product of the negative photosensitive liquid crystal alignment control protrusion forming resin composition according to the present invention. Provide a filter. According to the present invention, since the liquid crystal alignment control protrusion is formed using the resin composition according to the present invention, it causes burn-in when the color filter of the present invention is used in a liquid crystal display device. It is possible to improve the drive failure of the liquid crystal panel and to obtain good display characteristics.

  According to the present invention, a liquid crystal alignment control protrusion having a low dielectric constant is obtained by incorporating the compound (A) having a specific structure into the negative photosensitive liquid crystal alignment control protrusion forming resin composition. be able to. Therefore, in the vertical alignment liquid crystal display device, by using the liquid crystal alignment control protrusion having a low relative dielectric constant, the charging when the voltage is removed is eliminated, and the drive failure of the liquid crystal panel that causes image sticking can be improved. And good display characteristics can be obtained.

  Hereinafter, the negative photosensitive liquid crystal alignment control protrusion-forming resin composition and the color filter of the present invention will be described in order.

I. Negative photosensitive liquid crystal alignment control protrusion forming resin composition The negative photosensitive liquid crystal alignment control protrusion forming resin composition of the present invention is acrylic acid 2- (tricyclo [5] represented by the following chemical formula (1). 2.1.0 ^2,6 ] -3-en-9-yloxy) alkyl (A), and the specific dielectric constant after curing is 1.0 or more and 4.0 or less at 1 kHz. And

（化学式（１）中、Ｒは、炭素数が１〜４のアルキレン基を表す。）

(In chemical formula (1), R represents an alkylene group having 1 to 4 carbon atoms.)

  Here, the “alicyclic structure” refers to a structure in which an aromatic ring is excluded from a structure in which carbon atoms are bonded in a ring shape. The “bulky structure” means a structure having a steric hindrance that can reduce the density of polar groups per unit volume in the molecular structure of the compound (A).

Hereinafter, each configuration of the negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention will be described in detail in order.
In the present specification, (meth) acryloyl represents acryloyl and / or methacryloyl, and (meth) acryl represents acryl and / or methacryl. The light in this specification includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.

The reactive group in this specification includes a photocurable reactive group and a thermosetting reactive group. The photocurable reactive group means a reactive group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation. For example, photoradical polymerization, photocationic polymerization, photoanionic polymerization Examples of the polymerization reaction include those in which the reaction proceeds by a reaction mode such as addition polymerization or condensation polymerization that proceeds through photodimerization. In addition, the thermosetting reactive group in this specification is a reaction that can cure a coating film by causing a polymerization reaction or a crosslinking reaction to proceed between the same reactive groups or other reactive groups by heating. Means a group, and examples thereof include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and an isocyanate group.
As the reactive group used in the present invention, in particular, from the viewpoint of improving the hardness of the cured film, a polymerizable unsaturated group is preferably used, preferably a photocurable unsaturated group, and specific examples thereof include: Examples thereof include ethylenically unsaturated groups such as (meth) acryloyl group, vinyl group and allyl group.

The negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention has a non-reactive functional group or a thermosetting functional group in addition to a photocurable functional group-containing monomer, oligomer, and polymer. Monomers, oligomers, and polymers having groups may be included.
Examples of the photocurable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group. Among them, a (meth) acryloyl group is preferable.

Examples of the compound having a photocurable functional group include compounds having a radical polymerizable functional group such as a (meth) acrylate group. Specifically, ethyl (meth) acrylate, ethylhexyl (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) Examples include (meth) acrylate monomers such as acrylate, neopentyl glycol di (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. In addition, polymers having a polymer skeleton such as a polyester resin, a polyether resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin, and a polyhydric alcohol, and a polymer introduced with a (meth) acrylate group are listed. It is done. In addition, (meth) acrylate means an acrylate or / and a methacrylate.
Examples other than the above compounds include monofunctional or polyfunctional monomers such as styrene, methylstyrene and N-vinylpyrrolidone, or compounds having a cationic polymerizable functional group such as aromatic vinyl ether and aliphatic vinyl ether.

  The monomer, oligomer, and polymer are preferably contained in an amount of 20 to 75% by mass in the solid content of the negative photosensitive liquid crystal alignment control protrusion-forming resin composition.

<2- (Tricyclo [5.2.1.0 ^2,6 ] -3-en-9-yloxy) alkyl acrylate (A) represented by chemical formula (1)>
The acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] -3-en-9-yloxy) alkyl (A) used in the present invention is a compound represented by the following chemical formula (1). .

（化学式（１）中、Ｒは、炭素数が１〜４のアルキレン基を表す。）

(In chemical formula (1), R represents an alkylene group having 1 to 4 carbon atoms.)

  In the above chemical formula (1), R represents an alkylene group having 1 to 4 carbon atoms, and is preferably an ethylene group. Specific examples of the compound (A) include dicyclopentenyloxyethyl acrylate and dicyclopentenyloxypropyl acrylate.

  Since the compound (A) has a sterically bulky alicyclic structure, the density of polar groups per unit volume in the compound (A) is small. Accordingly, since the compound (A) has low polarity, the relative permittivity of the liquid crystal alignment control protrusions made of the negative photosensitive liquid crystal alignment control protrusion forming resin composition containing the compound (A) is lowered. Can be made. In addition, since the compound (A) has an acryloyloxyalkyl group and is highly polar and water-soluble, the compound (A) is soluble in a developer and has a negative photosensitive liquid crystal alignment containing the compound (A). The developability of the control protrusion-forming resin composition can be improved.

The content of the compound (A) is preferably 10 to 40% by weight, more preferably 20 to 35% by weight, based on the total solid content. However, when not using either the compound (B) which has an alicyclic structure mentioned later, or a silicon-type compound (C) together, the said compound (B) and the said compound ( When both of C) are not used in combination, the compound (A) can be added up to 50% by weight. When the content of the compound (A) is less than 10% by weight, the relative dielectric constant after curing may be increased, and when it exceeds 50% by weight, the remaining film ratio after curing may be decreased. There is.
In addition, in this invention, solid content means things other than a solvent among the components contained in a resin composition.

<Compound (B) having an alicyclic structure having 7 to 20 carbon atoms and at least one light or thermosetting reactive group>
The compound (B) having an alicyclic structure having 7 to 20 carbon atoms and at least one light or thermosetting reactive group used in the present invention does not significantly increase the relative dielectric constant of the cured film. For the purpose of improving the remaining film ratio, it is a preferable compound to be contained in the negative photosensitive liquid crystal alignment control protrusion-forming resin composition.

The number of carbon atoms constituting the alicyclic structure is preferably 7 to 20, and more preferably 10 to 15. The carbon atom here does not include a linking group substituted with an alicyclic structure or a carbon atom of the substituent. For example, 1-methyladamantane is composed of 10 carbon atoms.
The alicyclic structure is preferably a saturated aliphatic hydrocarbon, and adamantane and diamantane are particularly preferred from the viewpoint of improving curability without significantly increasing the relative dielectric constant.

The compound (B) according to the present invention preferably has at least one reactive group that is light or thermosetting, and further has two or more from the viewpoint of improving the remaining film ratio of the cured film. The reactive group is preferably an ethylenically unsaturated group or a glycidyl group.
The number of ethylenically unsaturated groups for one alicyclic structure is preferably 1 to 4, more preferably 2 to 3. Examples of the ethylenically unsaturated group include a methacryl group, an acryloyl group, a vinyl group, and an allyl group. Among these, a methacryl group or an acryloyl group is particularly preferable from the viewpoint of improving curability.
The number of glycidyl groups in the compound (B) is preferably 1 to 4 and more preferably 2 to 3 from the viewpoint of improving the remaining film ratio of the cured film.

The compound (B) is a nonpolymer containing about 1 to 2 alicyclic structures.
Moreover, it is preferable that content of the said compound (B) is 5 to 25 weight% with respect to the total solid, More preferably, it is 10 to 20 weight%. When content of the said compound (B) is less than 5 weight%, there exists a possibility that the heat resistance of a cured film and a remaining film rate may fall. On the other hand, if it exceeds 25% by weight, the developability may be lowered.
In addition, it is preferable that content of the said compound (B) with respect to total solid content is less than content of the said compound (A) from the point which improves developability.

  Specific examples are shown below, but the compound (B) used in the present invention is not limited thereto.

  Among them, preferred as the compound (B) is 1,3-adamantane dimethanol diacrylate represented by the above chemical formula (x-1), 2,4-di (glycidyloxy) represented by the above chemical formula (x-2). ) Phenyl-1-adamantane and the like.

<Silicon compound (C) having a linear or network structure of -Si-O- or Si>
The silicon-based compound (C) having a linear or network structure of —Si—O— or Si used in the present invention is a negative photosensitive liquid crystal alignment control for the purpose of reducing the relative dielectric constant after curing. It is a preferable compound to be contained in the projection forming resin composition.

  The silicon-based compound (C) used in the present invention is preferably at least one compound selected from the following compound group from the viewpoint of reducing the relative dielectric constant after curing. However, it is not limited to these.

（化学式（Ｃ−１）中、Ｒはメチル基、又はメトキシ基である。）

(In the chemical formula (C-1), R is a methyl group or a methoxy group.)

Moreover, it is preferable that the mass mean molecular weight (Mw) of the compound (C) represented by the said Chemical formula (C-1) is 800-3200 from a point of sclerosis | hardenability improvement, More preferably, it is 1100-2900. .
In addition, the mass average molecular weight of the compound (C) represented by the chemical formula (C-1) was measured using lithium bromide and phosphorus using HLC-8220 column, TSK gel α-2500, α-3000 manufactured by Tosoh Corporation. It is a value measured with a DMF solution to which an acid is added at 0.1%.

  The compound (C) represented by the chemical formula (C-2) has a repeating unit of Si—Si bond as a main chain, both ends thereof have a hydroxy group, and side chains have a methyl group or a phenyl group. ing.

  Moreover, it is preferable that the mass mean molecular weight (Mw) of the compound (C) represented by the said Chemical formula (C-2) is 1000-2200 from the point of sclerosis | hardenability improvement, More preferably, it is 1300-1900. .

（Ａ_{Ｓｉ‐Ｎｅｔｗｏｒｋ}は、Ｓｉが架橋結合してなる編目構造を表す。Ｌは、当該Ｓｉが架橋結合してなる編目構造の末端に結合した炭素数が１〜４のアルキル基、又はフェニル基を表す。ＯＨは、当該Ｓｉが架橋結合してなる編目構造の末端に結合したヒドロキシ基を表す。）

(A _Si-Network represents a stitch structure formed by cross-linking Si. L represents an alkyl group having 1 to 4 carbon atoms or a phenyl group bonded to the end of the stitch structure formed by cross-linking Si. OH represents a hydroxy group bonded to the end of the stitch structure formed by cross-linking of the Si.)

  In the compound (C) represented by the chemical formula (C-3), a predetermined amount of an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a hydroxy group bonded to the end of the stitch structure formed by cross-linking of Si. Have.

  Moreover, it is preferable that the mass average molecular weight (Mw) of the compound (C) represented by the said Chemical formula (C-3) is 500-2100 from the point of sclerosis | hardenability improvement, More preferably, it is 900-1700. .

In addition, the mass average molecular weight of the compound (C) represented by the chemical formulas (C-2) and (C-3) is a THF solution using Tosoh Co., Ltd. HLC-8220 column, TSK gel GMH _HR- L. It is the value measured by.

  Moreover, it is preferable that content of the said compound (C) is 5 to 20 weight% with respect to the total solid, More preferably, it is 10 to 20 weight%. When content of the said compound (C) is less than 5 weight%, there exists a possibility that the dielectric constant after hardening may not fully fall. Moreover, when it exceeds 25 weight%, there exists a possibility that compatibility may deteriorate.

<Other ingredients>
The negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention comprises the monomer, oligomer, polymer, and acrylic acid 2- (tricyclo [5.2.1.5] represented by the chemical formula (1). It is not particularly limited as long as it contains 0 ^2,6 ] -3-en-9-yloxy) alkyl (A), and may contain other materials as needed. Usually, a photopolymerization initiator, a surfactant, an adhesion assistant, a solvent and the like are used together with the above components.

(Photopolymerization initiator)
As the photopolymerization initiator used in the present invention, general ones can be used. For example, radical photopolymerization initiators such as Michler's ketone, and cationic photopolymerizations such as triarylsulfonium salts and diaryliodonium salts. An initiator etc. can be mentioned. These may be used alone or in combination of two or more.

  Moreover, such a photoinitiator can be used in combination with a photosensitizer. As the photosensitizer, a general one can be used, and examples thereof include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, and triethylamine. . These photosensitizers may be used alone or in combination of two or more.

  The photopolymerization initiator is contained within the range of 1% by mass to 30% by mass, and particularly within the range of 5% by mass to 15% by mass, in the solid content of the negative photosensitive resin composition for controlling protrusions for controlling liquid crystal alignment. It is preferred that This is because the curability of the resin composition can be made sufficient.

(Surfactant)
Moreover, the negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention may contain a surfactant, if necessary. The surfactant is used for improving the coating property of the negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention or for improving the developability of the coating film.

  Examples of the surfactant used in the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Polyoxyethylene aryl ethers such as ethers; nonionic surfactants such as polyoxyethylene dialkyl esters (for example, polyoxyethylene dilaurate and polyoxyethylene distearate); Ftop EF301, Ftop 303, Ftop 352 (Manufactured by Shin-Akita Kasei Co., Ltd.); Megafuck F171, Megafuck F172, Megafuck F173, Megafuck F475, (Megafuck R-08MH) (Daihin Manufactured by Ink Chemical Co., Ltd.); Fluorad FC-430, Fluorad FC-431 (manufactured by Sumitomo 3M); Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103 Fluorosurfactants commercially available under trade names such as Surflon SC-104, Surflon SC-105, Surflon SC-106 (Asahi Glass Co., Ltd.); Organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) ; (Meth) acrylic acid copolymer polyflow No .; 57, 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.); These may be used alone or in combination of two or more.

  The content of the surfactant is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the solid content in the negative photosensitive liquid crystal alignment control protrusion-forming resin composition. is there.

(Adhesion aid)
The negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention may contain an adhesion assistant, if necessary. The adhesion assistant is used to improve the adhesion between the coating film and the transparent electrode layer when the negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention is applied on the transparent electrode layer or the like. Used. Examples of such adhesion assistants include silane coupling agents.

  The content of the adhesion assistant is preferably 10% by mass or less, more preferably 5% by mass or less, based on the solid content in the negative photosensitive liquid crystal alignment control protrusion-forming resin composition.

(solvent)
The negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention may contain a solvent, if necessary. The solvent is used for uniformly dissolving each component in the negative photosensitive liquid crystal alignment control protrusion-forming resin composition and facilitating coating on, for example, the transparent electrode layer.

  The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the negative photosensitive liquid crystal alignment control protrusion-forming resin composition and can dissolve or disperse them. It is not something. Specifically, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl Ethylene glycol alkyl ether acetates such as cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol methyl ether Propylene glycol alkyl ether acetates such as cetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, Estes such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate S; dimethyl diglycol, 3-methoxybutanol, 3-methoxybutyl acetate, cyclohexanol acetate. These solvents may be used alone or in combination of two or more.

  Of these, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, and diethylene glycols are preferable as the solvent. In particular, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methyl amyl ketone, dimethyl diglycol, 3-methoxybutanol, 3-methoxybutyl acetate, cyclohexanol acetate and diethylene glycol ethyl Methyl ether is preferred.

  In the negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention, the component excluding the solvent is preferably 5% by mass to 40% by mass, more preferably in the range of 10% by mass to 30% by mass. A solvent is blended so as to be inside. Thereby, it can be set as the viscosity suitable for application | coating.

(Additive)
The negative photosensitive liquid crystal alignment control protrusion-forming resin composition of the present invention may contain an additive as necessary. Examples of the additive include an antistatic agent, a storage stabilizer, an antifoaming agent, a polymerization inhibitor, a plasticizer, and a leveling agent.

<Protrusions for controlling liquid crystal alignment>
Next, the liquid crystal alignment control protrusion formed using the negative photosensitive liquid crystal alignment control protrusion forming resin composition of the present invention will be described.

The relative dielectric constant at 1 kHz of the liquid crystal alignment control protrusion used in the present invention can be 1.0 or more and 4.0 or less, and in a particularly preferred embodiment, it is 2.5 or more and 4.0 or less. Can do. By setting the relative dielectric constant of the liquid crystal alignment control protrusion within the above range, in the vertical alignment liquid crystal display device using the liquid crystal alignment control protrusion, charging when the voltage is removed is eliminated. Thereby, the afterimage due to the drive failure of the liquid crystal panel is eliminated, and the display quality can be improved.
The relative dielectric constant of the liquid crystal alignment control protrusions was measured by INPEDANCE / GAIN-PHASE ANALYZER SI 1260, DIETRACERIC INTERFACE 1296 (manufactured by Solartron).

II. Next, the color filter of the present invention will be described. The color filter of the present invention is characterized by having a liquid crystal alignment control protrusion formed using the negative photosensitive liquid crystal alignment control protrusion forming resin composition described above.

  The color filter of the present invention corresponds to, for example, a transparent substrate, a colored layer formed on the transparent substrate, a transparent electrode layer formed on the colored layer, and the colored layer on the transparent electrode layer. And a liquid crystal alignment control protrusion formed in the region. The liquid crystal alignment control protrusions are formed in the region corresponding to the colored layer on the transparent electrode layer so that the colored layer and the liquid crystal alignment control protrusions correspond to each other with the transparent electrode layer interposed therebetween. It means that it is formed.

  According to the present invention, since the liquid crystal alignment control protrusion is formed using the negative photosensitive liquid crystal alignment control protrusion-forming resin composition described above, the color filter of the present invention is applied to a liquid crystal display device. When used, the drive failure of the liquid crystal panel is improved, and good display characteristics can be obtained.

  The color filter of the present invention is usually formed on a transparent substrate, a light shielding portion formed on the transparent substrate, a colored layer formed on the transparent substrate and the light shielding portion, and the colored layer. It has a transparent electrode layer and a projection for controlling liquid crystal alignment formed on the transparent electrode layer. Since the transparent substrate, the light-shielding portion, the colored layer, and the transparent electrode layer can be the same as those used in general color filters, description thereof is omitted here. Hereinafter, the liquid crystal alignment control protrusion in the present invention will be described.

(Protrusion for liquid crystal alignment control)
The liquid crystal alignment control protrusion used in the color filter of the present invention is formed using the negative photosensitive liquid crystal alignment control protrusion forming resin composition described above, and is usually a colored layer on the transparent electrode layer. Is formed in a region corresponding to.

  In the present invention, the negative photosensitive liquid crystal alignment control protrusion-forming resin composition is applied on the transparent electrode layer, dried, exposed and developed to form the liquid crystal alignment control protrusions in a pattern. Can be formed.

The application method of the negative photosensitive liquid crystal alignment control protrusion-forming resin composition is not particularly limited, and examples thereof include spray coating, dip coating, bar coating, roll coating, spin coating, and the like. Can be mentioned.
The thickness of the coating film is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the liquid crystal alignment control protrusion-forming resin composition.
After the negative photosensitive liquid crystal alignment control protrusion-forming resin composition is applied, the coating film is dried to remove the solvent. For example, the solvent can be evaporated and dried using a vacuum dryer, the coating film can be dried using a hot plate or an oven, or a combination thereof can be used.

Next, the coating film is exposed through a mask having a predetermined pattern to cause a polymerization reaction (curing reaction).
Examples of radiation used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, and electron beams. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.

After the exposure, development is performed using a developer, and unexposed portions are dissolved and removed, whereby liquid crystal alignment control protrusions are formed in a desired pattern.
As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution.
Further, a general method can be adopted as the developing method. The development conditions may be general conditions. In addition, after development, the developer is usually washed and dried.

  Further, after the development, a heat treatment may be performed so that the liquid crystal alignment control protrusions are sufficiently cured. The heating conditions are not particularly limited, and may be the same as the conditions for forming a general liquid crystal alignment control protrusion.

  The negative photosensitive liquid crystal alignment control protrusion-forming resin composition used in the present invention has been described in detail in the above section "I. Negative photosensitive liquid crystal alignment control protrusion forming resin composition". The description in is omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described more specifically with reference to examples.

<Example 1>
(Formation of liquid crystal alignment control protrusions)
A negative photosensitive liquid crystal alignment control protrusion-forming resin composition having the following composition was prepared.
<Negative photosensitive liquid crystal alignment control protrusion forming resin composition>
Acrylic resin (I6805: trade name, manufactured by Negami Kogyo Co., Ltd., molecular weight 59000): 43.1 parts by weight (in terms of solid content)
Dicyclopentenyloxyethyl acrylate (FA512AS: trade name, manufactured by Hitachi Chemical Co., Ltd.): 48.5 parts by weight (in terms of solid content)
Photopolymerization initiator (N-1919: trade name, manufactured by ADEKA Corporation) 8.4 parts by weight Diethylene glycol ethyl methyl ether (EDM): added so that the solid content of the formulation is 20% by mass

The negative photosensitive liquid crystal alignment control protrusion-forming resin composition is applied onto a base material indium tin oxide (ITO) vapor-deposited glass substrate by spin coating, dried under reduced pressure, and then at 80 ° C. for 3 minutes. And pre-baked. Next, the applied coating film was exposed through a photomask so that the integrated exposure amount was 60 mJ / cm ² . Thereafter, development is performed with a potassium hydroxide aqueous solution at a temperature of 25 ° C. and 0.05%, followed by heating in an oven at 230 ° C. for 30 minutes, post-baking, and liquid crystal alignment control with a film thickness of 0.9 μm and a line width of 20 μm. A protrusion was formed.

<Example 2>
In Example 1, 39.1 parts by weight of the compound (A) and 2,4-di (glycidyloxy) phenyl-1-adamantane (A-ARS-EPO: trade name, Idemitsu Kosan Co., Ltd.) as the compound (B) The liquid crystal alignment control projections were formed in the same manner as in Example 1 except that 9.4 parts by weight of (made) was used.

<Example 3>
In Example 2, liquid crystal alignment control protrusions were formed in the same manner as in Example 2 except that 29.7 parts by weight of compound (A) and 18.8 parts by weight of compound (B) were used.

<Example 4>
In Example 1, the compound (A) is 39.1 parts by weight, and the compound (B) is 1,3-adamantane dimethanol diacrylate (A-DMODA: trade name, manufactured by Idemitsu Kosan Co., Ltd.) 9.4. A protrusion for controlling liquid crystal alignment was formed in the same manner as in Example 1 except that the weight part was used.

<Example 5>
In Example 4, protrusions for controlling liquid crystal alignment were formed in the same manner as in Example 4 except that 29.7 parts by weight of compound (A) and 18.8 parts by weight of compound (B) were used.

<Example 6>
In Example 1, except that the compound (A) was 38.5 parts by weight, and the composite compound C103 was 10.0 parts by weight of Composelan E103A (trade name, manufactured by Arakawa Chemical Industries, Ltd.). Protrusions for controlling liquid crystal alignment were formed in the same manner as in Example 1.

<Example 7>
In Example 6, 28.5 parts by weight of the compound (A) and 20.0 parts by weight of the silicon compound (C) were used to form liquid crystal alignment control protrusions in the same manner as in Example 6. .

<Example 8>
In Example 1, except that the compound (A) was 43.5 parts by weight, and 5.0 parts by weight of Ogsol SI10-20 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.) was used as the silicon compound (C). In the same manner as in Example 1, liquid crystal alignment control protrusions were formed.

<Example 9>
In Example 8, liquid crystal alignment control protrusions were formed in the same manner as in Example 8 except that 38.5 parts by weight of compound (A) and 10.0 parts by weight of silicon-based compound (C) were used. .

<Example 10>
In Example 1, except that the compound (A) was 43.5 parts by weight, and 5.0 parts by weight of Ogsol SI20-12 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.) was used as the silicon compound (C). In the same manner as in Example 1, liquid crystal alignment control protrusions were formed.

<Example 11>
In Example 10, a liquid crystal alignment control protrusion was formed in the same manner as in Example 10 except that 38.5 parts by weight of compound (A) and 10.0 parts by weight of silicon compound (C) were used. .

<Example 12>
In Example 1, 23.6 parts by weight of the compound (A), 1,4.9 parts by weight of 1,3-adamantane dimethanol diacrylate (A-DMODA) as the compound (B), and silicon compound (C) Protrusions for controlling liquid crystal alignment were formed in the same manner as in Example 1 except that 10.0 parts by weight of Composelane E103A was used.

<Example 13>
In Example 12, liquid crystal alignment control protrusions were formed in the same manner as in Example 12 except that 10.0 parts by weight of Ogsol SI10-20 was used as the silicon compound (C).

<Example 14>
In Example 12, liquid crystal alignment control protrusions were formed in the same manner as in Example 12 except that 10.0 parts by weight of Ogsol SI20-12 was used as the silicon compound (C).

<Example 15>
In Example 1, 31.0 parts by weight of the compound (A), 7.5 parts by weight of 2,4-di (glycidyloxy) phenyl-1-adamantane (A-ARS-EPO) as the compound (B), Protrusions for controlling liquid crystal alignment were formed in the same manner as in Example 1 except that 10.0 parts by weight of Composeran E103A was used as the silicon compound (C).

<Example 16>
In Example 15, liquid crystal alignment control protrusions were formed in the same manner as in Example 15 except that 10.0 parts by weight of Ogsol SI10-20 was used as the silicon compound (C).

<Example 17>
In Example 15, liquid crystal alignment control protrusions were formed in the same manner as in Example 15 except that 10.0 parts by weight of Ogsol SI20-12 was used as the silicon compound (C).

<Comparative Example 1>
In Example 1, 48.5 parts by weight of dipentaerythritol hexaacrylate ethylene oxide modified product (DPEA-12: trade name, manufactured by Nippon Kayaku Co., Ltd.) instead of compound (A), and dipentaerythritol hexaacrylate Protrusions for controlling liquid crystal alignment were formed in the same manner as in Example 1 except that 9.4 parts by weight of an acid-modified product (TO2371: trade name, manufactured by Toa Gosei Co., Ltd.) was used.

<Comparative example 2>
In Example 3, compound (A) was not used and 2,4-di (glycidyloxy) phenyl-1-adamantane (A-ARS-EPO: trade name, manufactured by Idemitsu Kosan Co., Ltd.) was used as compound (B). A liquid crystal alignment control protrusion was formed in the same manner as in Example 3 except that 48.5 parts by weight were used.

<Comparative Example 3>
In Example 3, instead of compound (A), dipentaerythritol hexaacrylate acid-modified product (TO2335: trade name, manufactured by Toagosei Co., Ltd.) 18.8 parts by weight, compound (B) as 2,4-di For controlling liquid crystal alignment in the same manner as in Example 3 except that 29.7 parts by weight of (glycidyloxy) phenyl-1-adamantane (A-ARS-EPO: trade name, manufactured by Idemitsu Kosan Co., Ltd.) was used. A protrusion was formed.

<Comparative example 4>
In Example 1, instead of the compound (A), 29.7 parts by weight of dicyclopentenyl acrylate (FA-511AS: trade name, manufactured by Hitachi Chemical Co., Ltd.) and dipentaerythritol hexaacrylate acid-modified product (TO2335) : Product name, manufactured by Toagosei Co., Ltd.) 18.8 parts by weight was used in the same manner as in Example 1 to form a liquid crystal alignment control protrusion.

<Comparative Example 5>
In Example 1, instead of the compound (A), 29.7 parts by weight of dicyclopentanyl acrylate (FA-513AS: trade name, manufactured by Hitachi Chemical Co., Ltd.) and dipentaerythritol hexaacrylate acid-modified product ( A projection for controlling liquid crystal alignment was formed in the same manner as in Example 1 except that 18.8 parts by weight of TO2335: trade name, manufactured by Toa Gosei Co., Ltd. was used.

<Comparative Example 6>
In Example 1, instead of the compound (A), 29.7 parts by weight of dicyclopentanyl methacrylate (FA-513M: trade name, manufactured by Hitachi Chemical Co., Ltd.) and dipentaerythritol hexaacrylate acid-modified product ( A projection for controlling liquid crystal alignment was formed in the same manner as in Example 1 except that 18.8 parts by weight of TO2335: trade name, manufactured by Toa Gosei Co., Ltd. was used.

〔Evaluation methods〕
The following points were evaluated with respect to the above examples and comparative examples. The results are shown in Tables 1 and 2.
(1) Relative permittivity The relative permittivity at 1 kHz of each liquid crystal alignment control protrusion created in the above examples and comparative examples was measured by using INPEDANCE / GAIN-PHASE ANALYZER SI 1260, DELECTRIC INTERFACE 1296 (manufactured by Solarton). .

(2) Developability In the above examples and comparative examples, pattern formation with a photomask after the development process was evaluated. The evaluation criteria are shown below.
<Evaluation criteria>
Evaluation (circle): The unexposed part is removed completely by the image development process, and the pattern by the photomask is formed.
Evaluation x: The unexposed portion remains partly or entirely after the development step, and the pattern is not completely formed.

(3) Residual film ratio The film thickness after post-baking (230 ° C., heating for 30 minutes) is divided by the film thickness of the exposed portion after exposure, and the ratio of the film remaining after the post-baking process from the exposure process Asked.
In Comparative Examples 2 to 6, since the pattern formation could not be performed in the development process, the remaining film ratio could not be obtained.

Claims (10)

It contains 2- (tricyclo [5.2.1.0 ^2,6 ] -3-en-9-yloxy) alkyl (A) acrylate represented by the following chemical formula (1), and has a relative dielectric constant after curing. Is a negative photosensitive liquid crystal alignment control protrusion-forming resin composition, wherein the composition is 1.0 or more and 4.0 or less at 1 kHz.

(In the chemical formula (1), R represents an alkylene group having 1 to 4 carbon atoms.)   The negative photosensitive liquid crystal alignment control according to claim 1, further comprising a compound (B) having an alicyclic structure having 7 to 20 carbon atoms and at least one light or thermosetting reactive group. Protrusion-forming resin composition.   The negative photosensitive liquid crystal alignment controlling protrusion-forming resin composition according to claim 2, wherein the light or thermosetting reactive group is an ethylenically unsaturated group or a glycidyl group.   4. The negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to claim 3, wherein the ethylenically unsaturated group is a methacryl group or an acryloyl group.   The negative photosensitive liquid crystal alignment controlling protrusion-forming resin composition according to claim 2, wherein the alicyclic structure is adamantane or diamantane.   The negative photosensitive liquid crystal alignment controlling protrusion forming resin according to any one of claims 2 to 5, wherein the content of the compound (B) is 5 to 25% by weight based on the total solid content. Composition.   2. The negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to claim 1, further comprising a silicon compound (C) having a linear or network structure of -Si-O- or Si. The negative photosensitive liquid crystal alignment controlling protrusion-forming resin composition according to claim 7, wherein the silicon-based compound (C) is at least one compound selected from the following compound group.

(In the chemical formula (C-1), R is a methyl group or a methoxy group.)

(A _Si-Network represents a stitch structure formed by cross-linking Si. L represents an alkyl group having 1 to 4 carbon atoms or a phenyl group bonded to the end of the stitch structure formed by cross-linking Si. OH represents a hydroxy group bonded to the end of the stitch structure formed by cross-linking of the Si.)   The negative photosensitive liquid crystal alignment control protrusion-forming resin composition according to claim 7 or 8, wherein the content of the silicon-based compound (C) is 5 to 20% by weight based on the total solid content.   A color filter comprising a liquid crystal alignment control protrusion formed using the negative photosensitive liquid crystal alignment control protrusion forming resin composition according to claim 1.