JP2006276173A - Photopolymerizable resin layered body and glass substrate with black matrix - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable resin layered body for a black matrix having high sensitivity to light and high adhesiveness to a glass substrate. <P>SOLUTION: The photopolymerizable resin layered body comprises a photopolymerizable resin composition containing a compound expressed by formula (I) as a photopolymerization initiator by 0.1 to 20 mass% layered on a transparent supporting film. In formula (I), each of R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>independently represents CH<SB>3</SB>or C<SB>2</SB>H<SB>5</SB>; R<SB>4</SB>represents one selected from a group consisting of H, CH<SB>3</SB>, C<SB>2</SB>H<SB>5</SB>, n-C<SB>3</SB>H<SB>7</SB>, CH(CH<SB>3</SB>)<SB>2</SB>, n-C<SB>4</SB>H<SB>9</SB>, CH(CH<SB>3</SB>)C<SB>2</SB>H<SB>5</SB>, CH<SB>2</SB>CH(CH<SB>3</SB>)<SB>2</SB>and C(CH<SB>3</SB>)<SB>3</SB>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter used for a liquid crystal display or the like, a glass substrate with a black matrix which is a part thereof, a photopolymerizable resin laminate useful for producing a glass substrate with a black matrix, and the like.

A color filter, which is an important component in a color liquid crystal display, has hundreds to thousands of vertical, red, green, and blue dot images as pixels (hereinafter also referred to as “color pixels”) on a glass substrate or the like. They are arranged in a matrix of horizontal hundreds to thousands of pixels. Further, in order to improve the performance of the color filter, it is known that a light-shielding portion called a black matrix is arranged between each pixel arranged in a red, green, and blue matrix. A glass substrate with a black matrix on which each pixel is arranged is called a color filter.
The black matrix is formed for the purpose of increasing display contrast by preventing light from leaking from the gaps between pixels. The black matrix includes a metal thin film such as chromium and chromium oxide, and a black resin. Recently, a black matrix using a black resin has been actively developed. In forming the black matrix with the black resin, a method using a black and photopolymerizable resin is a method for patterning, for example, a black resin with another photopolymerizable resin from the viewpoint of cost and process. It is superior compared.

  As a method of forming a color filter including a black matrix made of a black resin, a method of forming a color matrix after forming a black matrix on a glass substrate or the like, and then forming a color pixel on a glass substrate, There is a method of forming a black matrix after forming the film. In recent years, development of color filters by printing color ink on a glass substrate using an ink jet method for forming color pixels has been extensive. When forming color pixels by the ink jet method, it is necessary to accurately apply ink to a predetermined minute region. A black matrix is formed on a glass substrate first, and the formed black matrix is used as a weir. Use is a better technique from the viewpoint of preventing mixing of inks of different pixels.

As a method of forming a black matrix on a glass substrate using a black resin having photopolymerizability, a method in which a liquid photosensitive resin is directly applied to a glass substrate is used (Patent Documents 1 to 3). reference). Further, a method is known in which a resin laminate is prepared in advance on a temporary support and then transferred to a glass substrate and used (see Patent Document 4).
In patent document 1, it is a composition containing a colorant, a binder polymer, a polymerizable compound, a photopolymerization initiator, and a photopolymerization initiation assistant, and the photopolymerization initiator is 2-methyl-2-morpholino-1- ( A colored photopolymerizable resin composition using 4- (methylthiophenyl) -propan-1-one and 4,4′-bis (dimethylamino) benzophenone as a photopolymerization initiator is described. The resin composition does not have sufficient sensitivity to light, particularly when it is a black photopolymerizable resin composition, photocuring is insufficient, and satisfactory adhesion when used as a black matrix on a glass substrate is satisfactory. It was not a thing.

Patent Document 2 describes a radiation-sensitive composition comprising a colorant, an alkali-soluble resin, a polyfunctional monomer, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Patent Document 3 describes a photopolymerizable composition containing bisacylphosphine oxide, at least one monomer capable of ethylenically unsaturated bond, an alkali-soluble dispersion resin, and a colorant. However, these resin compositions do not have sufficient sensitivity to light, particularly when they are made into a black photopolymerizable resin composition, photocuring is insufficient, and adhesion when used as a black matrix on a glass substrate Was not satisfactory.
Patent Document 4 describes a method of forming a light-shielding pixel on a glass substrate using a transfer material in which an alkali-soluble thermoplastic support layer, an intermediate layer, and a black photosensitive resin layer are provided on a temporary support. Has been. However, it is necessary to peel off the temporary support before exposure, and the three-layer transfer material is not satisfactory in terms of process and cost, and in terms of adhesion and light shielding when used as a black matrix on a glass substrate Was not satisfactory.

  Patent Document 5 describes a photopolymerizable resin composition for a color filter containing a specific aminoacetophenone-based initiator. Furthermore, Patent Document 6 proposes that a photosensitive composition containing a specific aminoacetophenone-based initiator is used for the color filter resist. However, when the black photopolymerizable resin composition for a color filter described in Patent Document 5 is applied as it is to a black matrix as a liquid resist, the sensitivity to light and the adhesion to a glass substrate are insufficient. It was. In addition, there is no disclosure of a specific black matrix production method in Patent Document 6, and as shown in a comparative example described later, the inventors of the present application set the conditions that seemed appropriate, and made a retrial. The sensitivity to light and the adhesion to the glass substrate were insufficient.

JP 2002-287348 A JP-A-11-211911 JP-A-11-184093 Japanese Patent No. 3409925 Japanese Patent No. 2678684 JP-T-2004-536352 (Claims 16 and 17)

  An object of the present invention is to obtain a photopolymerizable resin laminate for a black matrix that has high sensitivity to light and high adhesion to a glass substrate despite the use of a colored substance. Also, a method for producing a glass substrate with a black matrix having a high light-shielding property and a high resolution using the photopolymerizable resin laminate for black matrix, and a method for producing a color filter using the glass substrate with a black matrix The purpose is to provide.

  As a result of intensive studies to solve the previous problems, the present inventor has simply used a photoinitiator that is highly sensitive to light in a black photopolymerizable resin composition. It has been found that the sensitivity and the adhesion to the glass substrate when forming the film are not satisfactory. Then, using a specific photopolymerization initiator, blending this with a specific linear polymer, a photopolymerizable compound and a coloring substance at a specific ratio, and further using a specific support film, a photopolymerizable resin laminate For the first time, the inventors have found that sufficient sensitivity and adhesion to a glass substrate when forming a black matrix can be obtained, and the present invention has been made.

（式中、Ｒ_１、Ｒ_２、及びＲ_３は、各々独立にＣＨ_３またはＣ_２Ｈ_５を表し、Ｒ_４は、Ｈ、ＣＨ_３、Ｃ_２Ｈ_５、ｎ−Ｃ_３Ｈ_７、ＣＨ（ＣＨ_３）_２、ｎ−Ｃ_４Ｈ_９、ＣＨ（ＣＨ_３）Ｃ_２Ｈ_５、ＣＨ_２ＣＨ（ＣＨ_３）_２、及びＣ（ＣＨ_３）_３からなる群から選択されるいずれかを表す） That is, the present invention
(1) (a) 1 to 70% by mass of a linear polymer having a weight average molecular weight of 3000 to 50000 and an acid equivalent of 100 to 600, and (b) light having at least one ethylenically unsaturated double bond. 5 to 50% by mass of the polymerizable compound, (c) 0.1 to 20% by mass of the photopolymerization initiator, (d) 5 to 70% by mass of the coloring substance, and (c) the following formula: A black layer obtained by laminating a layer made of a photopolymerizable resin composition containing 0.1 to 20% by mass of the compound represented by (I) on a transparent support film having a thickness of 5 to 40 μm. Photopolymerizable resin laminate for matrix.

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent CH ₃ or C ₂ H ₅ , and R ₄ represents H, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , CH Represents any one selected from the group consisting of (CH ₃ ) ₂ , nC ₄ H ₉ , CH (CH ₃ ) C ₂ H ₅ , CH ₂ CH (CH ₃ ) ₂ , and C (CH ₃ ) _3. )

(2) A layer made of a photopolymerizable resin composition in which the content of the linear polymer (a) is 1.0 to 3.0 times the content of the photopolymerizable compound (b) is laminated on the support film. (1) The photopolymerizable resin laminate for black matrix according to (1).
(3) The content of the linear polymer (a) is 2.0 to 3.0 times the content of the photopolymerizable compound (b), and the compound represented by the above formula (I) is 5 to The photopolymerizable resin laminate for black matrix according to (1) or (2), wherein a layer made of a photopolymerizable resin composition containing 20% by mass is laminated on a support film.

（式中、Ｒ_５、Ｒ_６およびＲ_７は、各々独立にＨまたはＣＨ_３を表す。） (4) A layer made of a photopolymerizable resin composition containing 0.05 to 10% by mass of at least one of the compounds represented by the following formula (II) or formula (III) was laminated on the support film. The photopolymerizable resin laminate for black matrix according to any one of (1) to (3).

(In the formula, R ₅ , R ₆ and R ₇ each independently represent H or CH _3. )

（式中、Ｒ_８は、ＨまたはＣＨ_３を表す。ＸはＣ_２Ｈ_４またはＣＨ（ＣＨ_３）ＣＨ_２またはＣＨ_２ＣＨ（ＣＨ_３）を表し、ｎは１〜６の正の整数である。また、Ｙは炭素数が１〜６の２価の鎖状飽和炭化水素基、若しくは炭素数が５〜７の２価の環状飽和炭化水素基、または２価の芳香族基を表す。）

(Wherein R ₈ represents H or CH ₃ , X represents C ₂ H ₄ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), and n represents a positive integer of 1 to 6. Y represents a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent cyclic saturated hydrocarbon group having 5 to 7 carbon atoms, or a divalent aromatic group. )

(5) Lamination for laminating the photopolymerizable resin laminate for black matrix according to any one of (1) to (4) on the glass substrate so that the layer made of the photopolymerizable resin composition is in contact with the glass substrate A photomask having a matrix pattern from the support film side, an exposure step of irradiating the layer comprising the photopolymerizable resin composition through the support film with an actinic ray, and a photopolymerizable resin composition not cured in the exposure step The manufacturing method of the glass substrate with a black matrix characterized by including the image development process which forms the black matrix which consists of a photopolymerizable resin composition which removed and hardened | cured with the developing solution on this glass substrate.
(6) A heating step of heating a glass substrate on which a layer made of a photopolymerizable resin composition is laminated at 60 to 130 ° C. for 1 to 6 minutes between the exposure step and the development step (5) ) A method for producing a glass substrate with a black matrix.
(7) A glass substrate with a black matrix produced by the method according to (5) or (6).
(8) A step of producing a glass substrate with a black matrix by the method according to (4) or (5), and at least a part of the glass substrate with a black matrix not covered with the black matrix is heat sensitive or photosensitive. A method for producing a color filter, comprising a printing step of printing a color ink having a color characteristic by an ink jet method.
(9) A color filter produced by the method according to (8).

  The photopolymerizable resin laminate for black matrix of the present invention is highly sensitive to light and has high adhesion to the glass substrate of the cured black matrix. In addition, by using the method for producing a glass substrate with a black matrix of the present invention, a high performance glass substrate with a black matrix having excellent light-shielding properties and resolution can be provided. Furthermore, a high-performance color filter can be provided by using the method for producing a color filter of the present invention.

Hereinafter, the present invention will be specifically described. In addition, the compounding quantity of each component in this invention is described in the mass% at the time of making the reference | standard the whole photopolymerizable resin composition.
It is essential that the photopolymerizable resin composition used in the photopolymerizable resin laminate for black matrix of the present invention contains 0.1 to 20% by mass of a compound represented by the following formula (I). From the point of sensitivity, it is necessary to be 0.1% by mass or more. Moreover, it is necessary to be 20% by mass or less from the viewpoint of reducing fogging due to light diffraction through a photomask during exposure and obtaining sufficient resolution. More preferably, it is 0.5% or more and 10% or less. By using the compound represented by the formula (I), high sensitivity and high resolution and high adhesion can be exhibited while maintaining high light shielding properties.

  Examples of the compound represented by the formula (I) include 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-ethyl Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-isopropylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butane- 1-one, 2- (4-n-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- [4- (2-methylprop-1-yl) -Benzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-n-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -Bu 1-one, 2- (4-benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like, particularly 2- (4-methylbenzyl)- 2-Dimethylamino-1- (4-morpholinophenyl) -butan-1-one is preferred.

The photopolymerizable resin composition in the present invention may contain a photopolymerization initiator other than the compound represented by the formula (I). The photopolymerization initiator here is a compound that is activated by various actinic rays, such as ultraviolet rays, and initiates polymerization.
Examples of the photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole. 2,4,5-triarylimidazole dimers such as dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer.
In addition, p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino) benzophenone, p, p′-bis (dimethylamino) benzophenone [Michler's ketone] ], P, p'-bis (diethylamino) benzophenone, and p-aminophenyl ketones such as p, p'-bis (dibutylamino) benzophenone.

Further, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and acridine such as 9-phenylacridine And benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal.
In addition, 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9. H. And oxime esters such as -carbazol-3-yl] -ethane-1-one oxime-O-acetate.
Further, N-aryl-α-amino acid compounds can also be used, and among these, N-phenylglycine is preferable.
Further, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-2-morpholino-1- (4- (methylthiophenyl) -propan-1-one, and the like can be given.

In the present invention, the proportion of all (c) photopolymerization initiators including the compound represented by formula (I) in the photopolymerizable resin composition is 0.1% by mass to 20% by mass. It is preferable. From the viewpoint of sensitivity, 0.1% by mass or more is preferable. Further, it is preferably 20% by mass or less from the viewpoint of reducing fogging due to light diffraction through a photomask during exposure and obtaining sufficient resolution.
The weight average molecular weight of the linear polymer (hereinafter also referred to as “binder resin”) used in the present invention needs to be 3000 to 50000. The molecular weight is preferably 50000 or less from the viewpoint of developability, and 3000 or more is preferable from the viewpoint of edge fuse. The edge fuse here is a phenomenon in which a part of the photopolymerizable resin composition oozes out from the roll end face when the photopolymerizable resin composition of the present invention is laminated at least with a support and wound into a roll. It shows that. In order to further exhibit the effects of the present invention, the molecular weight is particularly preferably 10,000 to 40,000. The molecular weight was measured by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, KF manufactured by Showa Denko KK). -806M, KF-806M, KF-802.5) It is calculated | required as a weight average molecular weight (polystyrene conversion) by 4 in-line, moving bed solvent: Tetrahydrofuran, using a calibration curve by a polystyrene standard sample).

The amount of the carboxyl group contained in the linear polymer (a) used in the present invention needs to be 100 to 600 in terms of acid equivalent. An acid equivalent shows the mass of the polymer which has a 1 equivalent carboxyl group. (A) The carboxyl group in the linear polymer is necessary for imparting developability to an aqueous alkali solution to a layer made of an uncured photopolymerizable resin composition. The acid equivalent needs to be 600 or less from the viewpoint of developability, and the acid equivalent needs to be 100 or more from the viewpoint of adhesion to the glass substrate and resolution. From a practical viewpoint, it is preferably 250 to 500. In addition, the measurement of an acid equivalent is performed by the potentiometric titration method using Hiranuma Sangyo Co., Ltd. product and Hiranuma automatic titrator (COM-555) using 0.1 mol / L sodium hydroxide.
Examples of the (a) linear polymer used in the present invention include acrylic polymers, epoxy polymers, phenoxy polymers, polyester polymers, polyether polymers, and urethane polymers. Among them, acrylic polymers and urethane polymers are preferable, and acrylic polymers are particularly preferable.

The acrylic polymer used in the present invention can be obtained by copolymerizing one or more monomers from the following two types of monomers.
The first monomer is a carboxylic acid or acid anhydride having one ethylenically unsaturated double bond in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, and maleic acid half ester.
The second monomer is non-acidic, has one ethylenically unsaturated double bond in the molecule, and retains various characteristics such as developability of the photopolymerizable resin layer and flexibility of the cured film. So chosen. Examples of such compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, vinyl compounds having a phenyl group (for example, styrene), benzyl (meth) acrylate, and the like. In addition, it is a preferred embodiment of the present invention to use benzyl (meth) acrylate in terms of heat resistance as a black matrix.

The ratio of the acrylic polymer used in the present invention to the photopolymerizable resin composition is preferably in the range of 1 to 70% by mass, and in the range of 10 to 50% by mass from the viewpoint of resistance in the development process of the black matrix. Particularly preferred.
The acrylic polymer used in the present invention is a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile in a solution obtained by diluting a mixture of the above monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to synthesize by adding an appropriate amount of and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization and emulsion polymerization may be used in addition to solution polymerization.
Various known compounds can be used as the photopolymerizable compound (b) having at least one ethylenically unsaturated double bond in the present invention.

  For example, dimethacrylate of polyalkylene glycol in which an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide are added to both ends of bisphenol A, or a polyethylene glycol dimethacrylate in which an average of 5 mol of ethylene oxide is added to both ends of bisphenol A, respectively. Methacrylate (NK Nakamura Chemical Co., Ltd. NK ester BPE-500), 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, or polypropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) ) Acrylate, bisphenol A diglycidyl ether di (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxy Examples include polyalkylene glycol (meth) acrylate and polypropylene glycol mono (meth) acrylate. .

（式中、Ｒ_５、Ｒ_６およびＲ_７は、ＨまたはＣＨ_３を表す。） As the component (b) in the present invention, it is possible to include a compound having at least one carboxyl group and an ethylenically unsaturated double bond in the same molecule, and having a molecular weight of 100 to 1000, to adhere to a glass substrate. It is preferable for improving. The compound having at least one carboxyl group and at least one ethylenically unsaturated double bond in the same molecule and having a molecular weight of 100 to 1000 is represented by the compound represented by formula (II) or formula (III). And the like.

(In the formula, R ₅ , R ₆ and R ₇ represent H or CH _3. )

（式中、Ｒ_８は、ＨまたはＣＨ_３を表す。ＸはＣ_２Ｈ_４またはＣＨ（ＣＨ_３）ＣＨ_２またはＣＨ_２ＣＨ（ＣＨ_３）を表し、ｎは１〜６の正の整数である。また、Ｙは炭素数が１〜６の２価の鎖状飽和炭化水素基、若しくは炭素数が５〜７の２価の環状飽和炭化水素基、または２価の芳香族基を表す。）

(Wherein R ₈ represents H or CH ₃ , X represents C ₂ H ₄ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), and n represents a positive integer of 1 to 6. Y represents a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent cyclic saturated hydrocarbon group having 5 to 7 carbon atoms, or a divalent aromatic group. )

Examples of the compound represented by the formula (II) include succinic acid-modified pentaerythritol tri (meth) acrylate, phthalic acid-modified pentaerythritol tri (meth) acrylate, isophthalic acid-modified pentaerythritol tri (meth) acrylate, and terephthalic acid-modified pentaerythritol. And tri (meth) acrylate.
Moreover, as a compound mentioned by Formula (III), the half ester compound of the compound which added 1-3 mol of ethylene oxide to 2-hydroxyethyl (meth) acrylate, and hexahydrophthalic acid, 2-hydroxyethyl (meth) A half ester compound of succinic acid and a compound obtained by adding 1 to 3 moles of ethylene oxide to an acrylate, a half ester compound of a compound obtained by adding 1 to 3 moles of ethylene oxide to 2-hydroxyethyl (meth) acrylate and isophthalic acid, and Examples thereof include a half ester compound of terephthalic acid and a compound obtained by adding 1 to 3 moles of ethylene oxide to 2-hydroxyethyl (meth) acrylate.
These compounds are preferably 0.1% by mass or more from the viewpoint of adhesion to the substrate, and preferably 30% by mass or less from the viewpoint of developability. It is more preferable to contain 1-30 mass%.

The photopolymerizable resin composition in the present invention may contain a urethane compound having an ethylenically unsaturated double bond. Examples of the urethane compound include a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (meth) acryl group in one molecule (2 -Hydroxypropyl acrylate, oligopropylene glycol monomethacrylate and the like) and urethane compounds. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremer PP1000).
(B) The ratio of the photopolymerizable compound having at least one ethylenically unsaturated double bond (hereinafter also referred to as “photopolymerizable monomer”) to the entire photopolymerizable resin composition is 5 to 50 mass. % Range is preferred. If this ratio is less than 5% by mass, the sensitivity is not sufficient, and 50% by mass or less is preferable from the viewpoint of edge fuse. Preferably it is 10-50 mass%, More preferably, it is 10-40 mass%.

As for the compounding ratio of (a) and (b) in the present invention, the value of (a) / (b) is preferably 1.0 to 3.0. When the value of (a) / (b) is 3.0 or less, development is possible even with a low-concentration alkaline developer, and the time required for development is preferably moderate. When the value of (a) / (b) is 1.0 or more, it is preferable because the adhesiveness to the glass substrate is high under conditions where the development time is long. When the support film is peeled off after being laminated on the glass substrate Since the transfer of the photosensitive resin layer becomes easy, it is preferable.
In the present invention, the value of (a) / (b) and the amount of the compound represented by the formula (I) have an important relationship with the sensitivity of the photopolymerizable resin composition to light. (A) / (b) is preferably a larger value from the viewpoint of over-development adhesion, but if (a) / (b) is increased, the amount of exposure necessary to sufficiently cure the pattern increases, and the sensitivity Tends to be relatively low. The case where the value of (a) / (b) is 2.0 to 3.0 is preferable from the viewpoint of over-development adhesion, but in this case, from the viewpoint of maintaining sufficient sensitivity, it is simultaneously represented by the formula (I). It is preferable to contain 5-20 mass% of compounds made. It is more preferable that (a) / (b) is 2.0 to 3.0 and 8 to 20% by mass of the compound represented by the formula (I) is contained.

Examples of the coloring material (d) in the present invention include pigments and dyes, and these may be used simultaneously. Examples of pigments include organic pigments such as phthalocyanine, anthraquinone, bisanthraquinone, quinacridone, dioxazine, methine / azomethine, and isoindolinone, carbon blacks, titanium black, titanium oxynitride, black lower order There are inorganic pigments such as titanium oxide, graphite powder, iron black, and copper oxide, and a plurality of pigments may be included. These pigments may be subjected to a surface treatment for enhancing the dispersibility in the photopolymerizable resin composition or for increasing the electric resistance value. Examples of the dye include azo series, acridine series, alizanin series, anthraquinone series, indigo series, and perylene series.
Examples of the pigment include compounds divided into pigments in the color index (CI; issued by The Society of Dyers and Colorists), and specifically, the following color index (C.I. I.) Numbers can be mentioned.

C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 105, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment Red 264, and C.I. I. And red pigments such as CI Pigment Red 265.
Furthermore, C.I. I. Pigment orange 13, C.I. I. Pigment orange 31, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 42, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 65, C.I. I. Pigment orange 71, and C.I. I. And orange pigments such as CI Pigment Orange 73.

  Furthermore, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, and C.I. I. And yellow pigments such as CI Pigment Yellow 173.

Furthermore, C.I. I. Pigment green 7, and C.I. I. Green pigments such as C.I. Pigment Green 36, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and C.I. I. Blue pigments such as C.I. Pigment Blue 60, C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, and C.I. I. Purple pigments such as CI Pigment Violet 38, and C.I. I. Pigment brown 23, and C.I. I. And brown pigments such as CI Pigment Brown 25.
Examples of the dye include fuchsin, phthalocyanine green, chalcoxide green S, paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic Blue 20 and diamond green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) and the like.

As the coloring substance (d) in the present invention, carbon black and titanium black are preferable from the viewpoints of light shielding properties, sensitivity, resolution, and adhesion as a black matrix.
In the photopolymerizable resin composition of the present invention, it is a preferable embodiment that a coloring dye that develops color by light irradiation is also included from the viewpoint of achieving both photosensitivity before curing and light-shielding property after curing. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound.
Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet].

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like.
Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
Among such coloring dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.
(D) The ratio with respect to the whole photopolymerizable resin composition of a coloring material needs to be the range of 5-70 mass%. 5 mass% or more is required from the light-shielding property of a black matrix, and it is 70 mass% or less from the curability of a photopolymerizable composition and the formation property of a black matrix pattern.

In the present invention, in order to improve the thermal stability and storage stability of the photopolymerizable resin composition, it is preferable to include a radical polymerization inhibitor in the photopolymerizable resin composition. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine, triethyleneglycol-bis- [3- (3-tertiary Butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] and the like. The ratio of the radical polymerization inhibitor to the entire photopolymerizable resin composition is preferably 0.01% to 3%.
Moreover, additives, such as a plasticizer, can also be contained in the photopolymerizable resin composition in this invention as needed. Examples of such additives include phthalic acid esters such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, and polyethylene glycol monoalkyl ether.

The photopolymerizable resin laminate in the present invention is preferably prepared by coating the above-described photopolymerizable resin composition on a transparent support film having a thickness of 5 to 40 μm. The support film used here needs to be transparent to transmit actinic rays. Support films that transmit actinic rays include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film. , Polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, triacetyl cellulose film, and polypropylene film. As these films, those stretched as necessary can be used.
The haze of the support film is preferably 5.0 or less. The haze here is a value representing turbidity, and the haze value H = the total transmittance T that is irradiated by the lamp and transmitted through the sample and the transmittance D of the light diffused and scattered in the sample. It is calculated as D / T × 100. These are defined by JIS-K-7105 and can be easily measured by a commercially available turbidimeter. A more preferable haze value is 2.5% or less, and further preferably 1.0% or less.

In the photopolymerizable resin laminate of the present invention, a protective film can be laminated on the surface of the layer made of the photopolymerizable resin opposite to the support film, if necessary. It is preferable that the adhesive force between the protective film and the photopolymerizable resin layer is sufficiently smaller than the adhesive force between the support film and the photopolymerizable resin layer and can be easily peeled off.
Examples of such a protective film include a polyethylene film, a polyethylene terephthalate film, and a polypropylene film. Furthermore, it is preferable to use a protective film having a smooth surface from the viewpoint of suppressing unevenness on the protective film from being transferred to the photosensitive resin layer. When the unevenness on the protective film is transferred to the photosensitive resin layer, micro air voids may be generated between the substrate and the photosensitive resin layer when this is laminated on the substrate. Transfer as described above tends to be prominent when the layer made of a photopolymerizable resin is thin. For example, it is preferable to use a stretched polypropylene film (OPP). Specific examples include E-200A and E-200C manufactured by Oji Paper Co., Ltd.

The photopolymerizable resin laminate for black matrix of the present invention can be produced, for example, by the following method. As a photopolymerizable resin composition, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, a pigment dispersant, a radical polymerization inhibitor, and a solvent are mixed to prepare a photopolymerizable resin dope solution. The photopolymerizable resin dope solution is applied onto a 20 μm thick transparent polyester film to be a support film and dried to form a layer made of the photopolymerizable resin. The thickness of the layer made of the photopolymerizable resin at this time is preferably in the range of 0.5 μm to 4.5 μm. From the light shielding property of the black matrix and the film thickness accuracy at the time of coating, the thickness is preferably 0.5 μm or more. Moreover, it is preferable that it is 4.5 micrometers or less from flatness when it uses for a color filter. Thereafter, a polyethylene film to be a protective film is laminated and laminated.
As the solvent, any known solvent can be used as long as it is a liquid that dissolves the binder resin, the photopolymerizable monomer, the photopolymerization initiator, the pigment, the pigment dispersant, and the radical polymerization inhibitor. Examples thereof include organic solvents such as alcohols, ethers, aromatic hydrocarbons, ketones, and hydrocarbon compounds having one or more ether bonds or ester bonds in the molecule. Of these, methyl ethyl ketone, cyclohexanone, and propylene glycol monomethyl ether acetate are preferable.

The pigment dispersant is used as necessary to prevent the pigment from aggregating in the dope solution. In some cases, the pigment and the pigment dispersant may be mixed in advance in the solvent to prepare a pigment dispersion separately, and then mixed with the photopolymerizable resin dope solution. At this time, if necessary, a dispersion aid may be used to improve the dispersion stability by electrically and chemically adsorbing the pigment surface and the pigment dispersant.
Examples of the pigment dispersant include known compounds that are dispersed in the solvent. For example, carboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acid (partial) amine salts, and ammonium polycarboxylates. Salts, polycarboxylic acid alkylamine salts, polysiloxanes, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxylic acid groups, and the like (A) A linear polymer having a molecular weight of 20000 or less can also be used as a pigment dispersant. Examples of the dispersion aid include anionic activators such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic activators such as polyoxyethylene and polyoxylene block polymers. Can be mentioned.

The glass substrate with a black matrix of the present invention can be formed, for example, by the following method using the above photopolymerizable resin laminate. First, after the protective film is peeled from the photopolymerizable resin laminate, a lamination step is performed in which the photopolymerizable resin laminate for black matrix is laminated (thermocompression bonding) on a glass substrate. As the glass substrate, an alkali-free glass substrate or the like is preferably used.
Next, an exposure step of irradiating with actinic rays from the support film side through a photomask (mask film or glass mask) having a matrix pattern is performed. At this time, it is preferable to perform exposure without peeling off the support film because of high sensitivity. Moreover, it is preferable from the point of sensitivity or the adhesiveness to a glass substrate to perform the heating process which heats a glass substrate during exposure after exposure as needed. The heating temperature is preferably 60 to 130 ° C., and the heating time is preferably 1 to 6 minutes. The heating step is preferably performed within 10 minutes after the exposure is completed immediately after the start of exposure, and more preferably within 1 to 5 minutes after the exposure is completed.

Next, the supporting film on the photopolymerizable resin layer is removed, and a developing process is performed in which the unexposed photopolymerizable resin layer is dissolved and removed with a developer. As a removal method, there is so-called alkali development using a difference in solubility in an alkaline aqueous solution between an exposed portion and an unexposed portion. An aqueous solution of sodium carbonate, potassium carbonate or the like is used as the alkaline aqueous solution. These alkaline aqueous solutions are selected in accordance with the characteristics of the photopolymerizable resin layer, but generally 0.1 to 3% by mass of sodium carbonate aqueous solution is used. In order to remove the photopolymerizable resin layer remaining undeveloped as necessary, further development may be performed in another developer. Another developer is an aqueous alkali solution having a different alkalinity from the developer used for developing the photopolymerizable resin layer first, an acid developer, or a developer containing an organic solvent. The composition of the photopolymerizable resin layer can be appropriately selected according to the developer.
These developing solutions are used as bath solutions or spray solutions. Examples of developing methods using these developing solutions include dip development, shower development, spray development, and paddle development.

Moreover, it is preferable to perform the washing process using distilled water, ion-exchange water, and an ultrapure water as needed after image development. Examples of water washing methods include dip water washing, shower water washing, spray water washing and paddle water washing, but shower water washing and spray water washing are effective because it is easy to remove the unexposed photopolymerizable resin layer remaining without being developed. preferable. The unexposed photopolymerizable resin layer remaining undeveloped can be physically removed by a method such as dry desmear or sandblast using plasma.
In addition, as a method for removing the unexposed portion of the photopolymerizable resin layer, the unexposed portion of the photopolymerizable resin layer is swollen or modified with an alkaline aqueous solution, and then washed with dip water, shower water, spray water or paddle. The photopolymerizable resin layer in the unexposed area can also be removed by a water washing technique such as water washing. In this case, since the photopolymerizable resin layer of the unexposed part remains on the glass substrate, the penetration from the resist side by the alkaline aqueous solution is small, and the adhesiveness to the glass substrate is high, which is a preferable method.

The color filter of the present invention, after forming the glass substrate with a black matrix described above, is formed on at least a part of the glass substrate with a black matrix that is not covered with the black matrix by a heat-sensitive or photosensitive color ink. -It can be produced by forming a blue / green pixel pattern.
The shape of the black matrix is generally a lattice shape surrounding pixels. Further, the pattern width of each side of the lattice is generally 5 μm to 50 μm, and the lattice point interval is generally 30 μm to 500 μm.
The pixel pattern of red, blue, and green can be produced by photolithography using a color resist such as a liquid resist or a dry film resist, or can be produced by an ink jet method using a color ink, and various methods can be used. . In particular, the inkjet method is inexpensive and simple because it does not require an exposure process that requires an expensive mask, does not require a development process, can form a pixel pattern regardless of unevenness, and improves yield. It is preferable because a pixel pattern can be formed. Known heat-sensitive or photosensitive color inks can be used. In the present invention, a composition having a pigment and a dye exemplified as a coloring substance, a monomer having an ethylenically unsaturated double bond, a heat or photopolymerization initiator, and having a viscosity adjusted appropriately with a solvent is used. I can do it. For example, the color ink described in Example 1 of JP-A-2004-213033 can be used.

In the manufacturing method of the glass substrate with a black matrix of this invention, it is necessary to use the photopolymerizable resin laminated body laminated | stacked on the transparent support film whose thickness is 5 micrometers-40 micrometers. The manufacturing method of the black matrix using the photopolymerizable resin laminate of the present invention is compared with the manufacturing method in which the photopolymerizable resin composition is directly applied to a glass substrate, dried, and then exposed and developed through a photomask. , Without using a drying process, no film thickness unevenness when applied to glass, and the transparent support film prevents the photopolymerizable resin composition from contacting the photomask, so the photomask is less likely to get dirty, etc. This is a preferable method.
A glass substrate with a black matrix prepared using the photopolymerizable resin laminate of the present invention is prepared by directly applying a photopolymerizable resin composition to a glass substrate, drying, and then exposing and developing through a photomask. Compared to a glass substrate with a black matrix, the photopolymerizable resin composition is located between the transparent support film and the glass substrate at the time of exposure, and is not susceptible to oxygen inhibition because it is not in contact with air. Even if the coloring substance is contained in a high concentration, it is preferable because the sensitivity to light is high and the adhesion to the glass substrate and the resolution are excellent.

  In general, when a color filter is formed using a photopolymerizable resin laminate, a color pixel having a thickness of about 2 μm is formed on a glass substrate, and then the photopolymerizable resin laminate is laminated on a glass substrate with pixels. Exposure is performed from the substrate side (see Patent Document 4). This is because when the black matrix is formed in this order, the black matrix is originally formed only between the pixels, so that the alignment between the pixels and the black matrix can be omitted. At the same time, in order to embed the photopolymerizable resin between the pixels, a support film having a thickness of 70 to 100 μm or more must be used. When exposure is performed through such a thick support film, it is difficult to cope with from the viewpoint of resolution and pattern reproducibility, and a process of peeling and exposing the support film is necessary. At this time, in order to prevent the curing of the photopolymerizable resin from being blocked by oxygen at the time of exposure, an intermediate layer or the like must be provided between the photopolymerizable resin layer and the support film. The structure of the resin laminate is complicated.

On the other hand, in the color filter manufacturing method of the present invention, by adopting a method of forming a black matrix on a glass substrate in advance of the pixels, preferably forming a weir with a black matrix and then filling the pixels by an ink jet method. The support film can be designed to be thin. Since the thickness of the support film is as thin as 40 μm or less, even in exposure through the support film during exposure, the amount of diffracted light from the mask is small, and the pattern width becomes thicker than the mask design width, so-called It is thought that image fatness is difficult to occur. As a result, a photopolymerizable resin laminate having high sensitivity and high adhesion, and a glass substrate with a black matrix having high resolution and excellent pattern reproducibility can be obtained.
The thickness of the support film is 40 μm or less for the above reason, and 5 μm or more from the viewpoint of maintaining strength. More preferably, they are 10 micrometers or more and 25 micrometers or less.

The present invention will be described based on examples.
[Examples 1-7]
Preparation of Photopolymerizable Resin Composition Solution A binder solution, a monomer, a photopolymerization initiator, and an additive are mixed at a ratio shown in Table 1, and a photopolymerizable resin composition solution 1-7 having a solid content of 20% by mass. Get. In Table 1, components constituting the photopolymerizable resin composition represented by abbreviations (P-1 to B-3) are as follows.
P-1: Copolymer of benzyl methacrylate / methacrylic acid = 8/2 (mass ratio) and a methyl ethyl ketone solution of a binder having a weight average molecular weight of 20,000, an acid equivalent of 430, and a solid content of 40% M-1: triethoxymethylolpropane tri Acrylate M-2: Nonaethylene glycol diacrylate M-3: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756 manufactured by Toa Gosei Co., Ltd.)
M-4: Half-ester compound of a compound obtained by adding 1 mol of ethylene oxide to 2-hydroxyethyl methacrylate and hexahydrophthalic acid A-1: 2- (4-methylbenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one (IRGACURE 379 manufactured by Ciba Specialty Chemicals)
A-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907 manufactured by Ciba Specialty Chemicals)
A-3: 2-mercaptobenzotriazole A-4: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819 manufactured by Ciba Specialty Chemicals)
I-1: Triethylene glycol-bis- [3- (3-tertiarybutyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245 manufactured by Ciba Specialty Chemicals)
B-1: Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.)
B-2: leuco crystal violet B-3: carbon black MEK: methyl ethyl ketone

○ Preparation of photopolymerizable resin laminate The photopolymerizable resin composition solutions 1 to 7 were uniformly applied to a 20 μm-thick polyethylene terephthalate support film (AT301 manufactured by Teijin DuPont Films Co., Ltd.) using a bar coater. And dried in a dryer at 95 ° C. for 3 minutes. Next, a 25 μm-thick polyethylene protective film (GF85 manufactured by Tamapoly Co., Ltd.) is bonded to the resulting photopolymerizable resin composition laminate, and the photopolymerizable resin laminates of Examples 1 to 7 are obtained. it can. In addition, the photopolymerizable resin laminate of Example 8 is obtained in the same manner as in Example 1 except that the protective film is replaced with a 20 μm thick stretched polypropylene protective film (E-200A manufactured by Oji Paper Co., Ltd.). I can do it.

Formation of glass substrate with black matrix After peeling off the protective film of the photopolymerizable resin laminate of Examples 1 to 7 above and laminating it on a non-alkali glass substrate having a thickness of 0.7 mm at 95 ° C., the line width / space width Is exposed through a glass photomask having a pattern of 5 μm / 45 μm, 10 μm / 90 μm with an ultrahigh pressure mercury lamp (HMW-801, manufactured by Oak Manufacturing Co., Ltd.). At this time, exposure is performed from the support film side without peeling off the support film. The exposure amount is 100 mJ / cm ² as a standard exposure amount, and is adjusted in the range of 25 to 200 mJ / cm ² according to the sensitivity of the photopolymerizable resin laminate. After peeling off the support film, a 0.2% by mass aqueous sodium carbonate solution is sprayed at 30 ° C. to dissolve and remove the unexposed photopolymerizable resin layer and develop. The standard development time at this time is 1.5 times the time (defined as a break point) when the unexposed portion of the photopolymerizable resin layer is just removed from the glass substrate. Thereafter, post baking is performed at 240 ° C. for 60 minutes to form a glass substrate with a black matrix.

○ Evaluation of Glass Substrate with Black Matrix (1) Film Thickness About the black matrix on the above glass substrate, the height of the pattern formed on the glass substrate was measured using Alpha Step (AS200) manufactured by Tencor Instruments, This is the film thickness.
(2) Light shielding properties (optical density)
A glass substrate with a solid pattern is prepared in the same manner as the above glass substrate with a black matrix, and the optical density is measured using an optical densitometer D200-II manufactured by Gretag Macbeth as an evaluation of light shielding properties. The optical density is expressed by the relationship of optical density = log ₁₀ (I ₀ / I), where the incident light intensity is I ₀ and the transmitted light intensity is I with respect to light from a certain light source.
(3) Adhesion As an evaluation of adhesion, whether or not a matrix pattern of line width / space width = 5 μm / 45 μm, 10 μm / 90 μm is formed is visually observed with an optical microscope.

(4) Over-development adhesion As an evaluation of over-development adhesion, line width / space width = 5 μm / 45 μm, 10 μm / 90 μm when the above-mentioned black matrix was produced with development time 1.5 times the standard development time. Whether the matrix pattern is formed is visually observed with an optical microscope.
(5) Line width reproducibility The line width of the matrix pattern of line width / space width = 10 μm / 90 μm formed on the glass substrate is measured using a length measuring microscope. If the measured line width of the pattern is 2 μm or more thicker than the mask line width, the line width is thickened. If it is thinner than 2 μm, the line width is thinned.
(6) ST sensitivity As an evaluation of sensitivity to light, after laminating a photopolymerizable resin laminate on a separately prepared glass substrate in the same manner as described above, it was passed through a mask film of a stove 21-step tablet in the same manner as described above. The glass substrate subjected to exposure / development and post-baking is evaluated by visually reading how many step tablet patterns remain.
The evaluation results of the above (1) to (6) are shown in Table 2. The evaluation result of Example 8 is the same as the evaluation result of Example 1.

[Comparative Examples 1 and 2]
The binder solution, the monomer, the photopolymerization initiator, and the additive used in the examples are mixed in the ratio shown in Table 1 to obtain photopolymerizable resin composition solutions 8 and 9 having a solid content of 20% by weight. The photopolymerizable resin composition solutions 8 and 9 were formed on a polyethylene terephthalate support film having a thickness of 20 μm in the same manner as in the Examples, and a protective film made of polyethylene was laminated. A photopolymerizable resin laminate is prepared. Using these photopolymerizable resin laminates of Comparative Examples 1 and 2, a glass substrate with a black matrix is formed in the same manner as in Example 1. For the evaluation of Comparative Examples 1 and 2, the same items as in the Examples were evaluated, and the results are shown in Table 2.

[Comparative Example 3]
The photopolymerizable resin composition solution 1 used in Example 1 was dropped on a non-alkali glass substrate having a thickness of 0.7 mm, and then applied using a spin coater so that the dry film thickness was 1.2 μm. For 2 minutes at 95 ° C. It exposes at 200 mJ / cm < ² > with a super-high pressure mercury lamp (HMW-801 by Corporation | KK Oak Manufacturing Co., Ltd.) through the glass mask of the pattern whose line width / space width is 5 micrometers / 45 micrometers and 10 micrometers / 90 micrometers. At this time, the gap is fixed so that the distance between the mask and the glass substrate is 50 μm. A 0.2% by mass aqueous sodium carbonate solution is sprayed at 30 ° C. for a standard development time, and the unexposed photopolymerizable resin layer is dissolved and removed for development. Thereafter, post baking is performed at 240 ° C. for 60 minutes to form a glass substrate with a black matrix. About evaluation, it evaluates like Example 1 and a result is shown in Table 2.
[Comparative Example 4]
The photopolymerizable resin composition solution 1 used in Example 1 was formed on a polyethylene terephthalate support film having a thickness of 75 μm in the same manner as in Example 1, and a protective film made of polyethylene was laminated thereon. 4 photopolymerizable resin laminate is prepared. Using the photopolymerizable resin laminate of Comparative Example 4, a glass substrate with a black matrix is formed in the same manner as in Example 1. About evaluation, it evaluates like Example 1 and a result is shown in Table 2.

[Comparative Example 5]
The photopolymerizable resin composition solution 1 used in Example 1 was formed on a polyethylene terephthalate support film having a thickness of 20 μm in the same manner as in Example 1, and a protective film made of polyethylene was bonded thereto. 5 is produced. The protective film of the photopolymerizable resin laminate is peeled off and laminated on a non-alkali glass substrate having a thickness of 0.7 mm at 95 ° C., and then the support film is peeled off, and then the line width / space width is 5 μm / 45 μm, 10 μm / It exposes at 200 mJ / cm < ² > with a super high pressure mercury lamp (HMW-801 by Oak Manufacturing Co., Ltd.) through a glass photomask having a 90 [mu] m pattern. At this time, the gap is fixed so that the distance between the mask and the glass substrate is 50 μm. Moreover, it exposes from the photopolymerizable resin laminated body side. A 0.2% by mass aqueous sodium carbonate solution is sprayed at 30 ° C. for a standard development time, and the unexposed photopolymerizable resin layer is dissolved and removed for development. Thereafter, post baking is performed at 240 ° C. for 60 minutes to form a glass substrate with a black matrix. About evaluation, it evaluates like Example 1 and a result is shown in Table 2.

本発明のブラックマトリックス用光重合性樹脂積層体は高い光感度を有し、ガラス基板への密着性が高く、高い光学濃度を有しながら高解像度でパターンを形成できる。

The photopolymerizable resin laminate for black matrix of the present invention has high photosensitivity, high adhesion to a glass substrate, and can form a pattern with high resolution while having high optical density.

  With the photopolymerizable resin laminate for black matrix of the present invention, a glass substrate with a black matrix, a color filter and the like can be produced. The glass substrate with a black matrix and the color filter of the present invention can be used in the field of flat panel displays such as liquid crystal displays, organic EL displays, and plasma displays, and are particularly preferably used in the field of liquid crystal displays.

Claims (9)

(A) 1 to 70% by mass of a linear polymer having a weight average molecular weight of 3000 to 50000 and an acid equivalent of 100 to 600, and (b) a photopolymerizable compound having at least one ethylenically unsaturated double bond. 5 to 50% by mass, (c) 0.1 to 20% by mass of a photopolymerization initiator, (d) 5 to 70% by mass of a colored substance, and (c) as a component represented by the following formula (I) Light for black matrix, characterized in that a layer made of a photopolymerizable resin composition containing 0.1 to 20% by mass of a compound represented by the formula (1) is laminated on a transparent support film having a thickness of 5 to 40 μm. Polymeric resin laminate.

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent CH ₃ or C ₂ H ₅ , and R ₄ represents H, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , CH Represents any one selected from the group consisting of (CH ₃ ) ₂ , nC ₄ H ₉ , CH (CH ₃ ) C ₂ H ₅ , CH ₂ CH (CH ₃ ) ₂ , and C (CH ₃ ) _3. )   That the layer which consists of a photopolymerizable resin composition whose content of a linear polymer (a) is 1.0-3.0 times of content of a photopolymerizable compound (b) was laminated | stacked on the support film. The photopolymerizable resin laminate for a black matrix according to claim 1.   The content of the linear polymer (a) is 2.0 to 3.0 times the content of the photopolymerizable compound (b), and 5 to 20% by mass of the compound represented by the above formula (I). 3. The photopolymerizable resin laminate for a black matrix according to claim 1 or 2, wherein a layer made of the photopolymerizable resin composition is laminated on a support film. A layer comprising a photopolymerizable resin composition containing 0.05 to 10% by mass of at least one of the compounds represented by the following formula (II) or formula (III) is laminated on a support film. The photopolymerizable resin laminate for black matrix according to any one of claims 1 to 3.

(In the formula, R ₅ , R ₆ and R ₇ each independently represent H or CH _3. )

(Wherein R ₈ represents H or CH ₃ , X represents C ₂ H ₄ or CH (CH ₃ ) CH ₂ or CH ₂ CH (CH ₃ ), and n represents a positive integer of 1 to 6. Y represents a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent cyclic saturated hydrocarbon group having 5 to 7 carbon atoms, or a divalent aromatic group. )   A lamination step of laminating the photopolymerizable resin laminate for a black matrix according to any one of claims 1 to 4 on the glass substrate so that the layer made of the photopolymerizable resin composition is in contact with the glass substrate, the support film side An exposure step of irradiating the photopolymerizable resin composition layer with actinic rays through a photomask having a matrix pattern and a support film, and a photopolymerizable resin composition not cured in the exposure step with a developer A method for producing a glass substrate with a black matrix, comprising a development step of forming a black matrix comprising a photopolymerizable resin composition removed and cured on the glass substrate.   6. The method according to claim 5, further comprising a heating step of heating the glass substrate on which the layer made of the photopolymerizable resin composition is laminated at 60 to 130 ° C. for 1 to 6 minutes between the exposure step and the development step. Manufacturing method of glass substrate with black matrix.   A glass substrate with a black matrix produced by the method according to claim 5 or 6.   6. A step of producing a glass substrate with a black matrix by the method according to claim 4 or 5, and at least a part of the glass substrate with a black matrix not covered with a black matrix is coated with a heat-sensitive or photosensitive color ink. A method for producing a color filter, comprising a printing step of printing by an inkjet method.   A color filter manufactured by the method according to claim 8.