JP2005189720A - Photosensitive resin composition, photosensitive transfer material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of achieving photosetting up to a deep portion of a film even with a small light exposure, a photosensitive transfer material capable of forming a black matrix having a high optical density and little disarray, and an image forming method. <P>SOLUTION: The photosensitive resin composition contains at least an alkali-soluble binder, a photopolymerization initiator, a polyfunctional monomer and a light shielding agent, wherein the polyfunctional monomer is a dipentaerythritol polyacrylate compound having a viscosity of ≤4,000 mPa s. The photosensitive transfer material and the image forming method use the same. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition that can be sufficiently photocured to a deep part of a film, and a photosensitive transfer material and an image forming method using the same. In particular, the photosensitive resin composition, the photosensitive transfer material, and the image forming method of the present invention are suitably used for producing a color filter by a self-alignment exposure method.

  Conventionally, when a color filter is manufactured, a black matrix is formed at intervals of pixels for the purpose of improving display contrast and the like at intervals of pixels of R (red), G (green), and B (blue). ing. As a method for forming a black matrix, a method using a metal film such as chromium as a black matrix, a method using a photosensitive resin composition in which a light-shielding pigment or the like is dispersed, and the like are known.

  Among the methods for forming the black matrix, a method using a photosensitive resin composition is considered to be advantageous in terms of manufacturing cost and the like as compared with a method using a metal thin film. According to a method using a photosensitive resin in which a light-shielding pigment or the like is dispersed, a photosensitive resin layer in which the light-shielding pigment or the like is dispersed is formed on a substrate by a method such as coating or printing, and pattern exposure and development steps. Through this process, a black matrix is formed.

  As a method for forming a black matrix using the above photosensitive resin composition, photocurability mainly composed of a color pigment, an acrylic monomer, a pigment dispersant, a photopolymerization initiator, a dilution solvent, and an adhesion improver. A method using an acrylic coloring composition has been proposed (see, for example, Patent Document 1). According to such a method, it is said that by using dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate as the acrylic monomer, it is possible to form a uniform color pattern having excellent adhesion and no stains. .

One of the functions of the black matrix is to prevent light leakage from the wiring portion of the TFT substrate or the like, which is intended to improve contrast. In order to achieve such an object, the higher the optical density of the black matrix, the better. However, the light-shielding agent contained in the photosensitive resin layer absorbs not only visible light but also ultraviolet rays that are the exposure wavelength when the photosensitive resin layer is exposed. Therefore, in the method using the photosensitive resin composition described above, even if the light shielding agent (pigment, carbon black) or the like of the photosensitive resin composition is adjusted to increase the optical density of the black matrix, for example, the glass substrate When light (for example, ultraviolet rays) is irradiated from the back surface (surface where no pixel is provided: non-pixel formation surface), it becomes difficult to sufficiently cure the photosensitive resin layer. As described above, when the photosensitive resin layer is developed without being sufficiently cured, even the incompletely cured portion is removed, and when the black matrix is formed, a desired film thickness cannot be obtained, and the optical density is reduced. Will also decline.
Japanese Patent No. 2768137

In order to solve the above-mentioned problems, a first object of the present invention is to provide a photosensitive resin composition that can be photo-cured to a film deep portion even with a low exposure amount.
A second object of the present invention is to provide a photosensitive transfer material and an image forming method capable of forming a black matrix having a high optical density and little alignment disorder.

The above problem is solved by the following means.
<1> A photosensitive resin composition containing at least an alkali-soluble binder, a photopolymerization initiator, a polyfunctional monomer, and a light-shielding agent, wherein the polyfunctional monomer has a viscosity of 4000 mPa · s or less. It is a photosensitive resin composition characterized by being a dipentaerythritol polyacrylate compound.

  <2> The photosensitivity according to <1>, wherein the dipentaerythritol polyacrylate compound is a compound in which at least one alcohol portion of dipentaerythritol is acrylated via a divalent linking group. It is a resin composition.

  <3> The above-mentioned <1>, wherein the dipentaerythritol polyacrylate compound is an acrylated compound after an addition reaction of at least one alcohol portion of dipentaerythritol with a lactone or alkylene oxide compound. <2> The photosensitive resin composition.

  <4> The above-mentioned <1> to <3, wherein the dipentaerythritol polyacrylate compound is a compound that is acrylated after addition reaction with ε-caprolactone in at least one alcohol portion of dipentaerythritol. > Photosensitive resin composition.

  <5> A photosensitive transfer material having a photosensitive resin layer formed by using at least the photosensitive resin composition of the above <1> to <4> on a temporary support.

  <6> An image forming method using a photosensitive transfer material having a photosensitive resin layer using at least the photosensitive resin composition of the above <1> to <4> on a temporary support, A laminating step in which the photosensitive resin layer of the photosensitive transfer material and the substrate are in intimate contact, a removing step of removing the temporary support from the photosensitive transfer material, an exposure step of pattern exposing the photosensitive resin layer, and a pattern An image forming step of developing the exposed photosensitive resin layer to form an image on the substrate.

  <7> The image according to <6>, wherein the substrate has light transparency, and the exposure step performs pattern exposure of the photosensitive resin layer by irradiating light from the substrate side. It is a forming method.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can be photocured to the film deep part even with a low exposure amount can be provided. Further, according to the present invention, it is possible to provide a photosensitive transfer material and an image forming method capable of forming a black matrix having a high optical density and excellent orientation and light shielding properties.

<< Photosensitive resin composition >>
The photosensitive resin composition of the present invention is a photosensitive resin composition containing at least an alkali-soluble binder, a photopolymerization initiator, a polyfunctional monomer, and a light-shielding agent, and the polyfunctional monomer. Is a dipentaerythritol polyacrylate compound having a viscosity of 4000 mPa · s or less. In the present invention, the “dipentaerythritol polyacrylate compound” means an acrylate compound in which at least one portion of the acrylate portion is substituted with another substituent.

The photosensitive resin composition of the present invention has a viscosity of 4000 mPa.s as the polyfunctional monomer. By using a dipentaerythritol polyacrylate compound of s or less, when a photosensitive resin layer is formed to form a black matrix, it is possible to photocure even to a film deep portion even with a low exposure amount. Thereby, when the black matrix is formed, it is possible to prevent the deterioration of the light shielding property and the disorder of the alignment due to the decrease of the optical density and the reduction of the film.
Here, the “alignment disorder” means that the upper side of the black matrix becomes lower than the upper side of the adjacent colored pixel due to the reduction in the film thickness of the black matrix, and the alignment of the liquid crystal molecules is disturbed. When the alignment is disturbed, the luminance of the pixel may be lowered, or light may leak from between the colored pixel and the black matrix.

  The photosensitive resin composition of the present invention comprises at least an alkali-soluble binder, a photopolymerization initiator, a polyfunctional monomer, and a light-shielding agent, and, if necessary, a solvent, an ultraviolet absorber, or an interface. Activators and other additives can be included. Hereinafter, each component of the photosensitive resin composition of this invention is explained in full detail.

(Alkali-soluble binder)
As the alkali-soluble binder used in the present invention, the dispersion stability of the pigment and the compatibility with the polyfunctional monomer and photopolymerization initiator described later are good, the solubility in an alkali developer and the organic solvent at the time of preparing the coating solution Those having suitable solubility, strength, softening temperature and the like are preferable.

  In the present invention, the term “alkali-soluble” means soluble in an aqueous solution of the following alkaline substance or a mixture of this with an organic solvent miscible with water. Examples of the alkaline substance and the appropriate organic solvent miscible with water include the same “alkaline substance” and “water-miscible organic solvent” as those used in the developer.

  The alkali-soluble binder may be water-insoluble or water-soluble. Specifically, the water-insoluble alkali-soluble binder includes a polymer having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, croton as described in the specifications of JP-A-25-25957, JP-A-59-53836, JP-A-59-71048, etc. Preferable examples include acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Cellulose derivatives having a carboxylic acid group in the side chain can also be used. In addition, a polymer having a hydroxyl group added to a polymer having a hydroxyl group is also useful. Particularly preferably, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in U.S. Pat. No. 4,139,391 and multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers Coalescence can be mentioned.

  Examples of the water-soluble alkali-soluble binder include polyvinyl pyrrolidone, polyethylene oxide, and polyvinyl alcohol. In addition, in order to improve various properties such as the strength of the cured film, an alkali-insoluble polymer can be used in combination as long as the development properties and the like are not impaired. Examples of such a polymer include alcohol-soluble nylon and epoxy resin.

Two or more of the alkali-soluble binders can be used in combination.
In this invention, 10-95 mass% is preferable, and, as for solid content in the photosensitive resin composition of the said alkali-soluble binder, More preferably, it is 20-90 mass%. When the content is in the range of 10% by mass to 95% by mass, it is possible to prevent the adhesiveness from becoming too high when the photosensitive resin layer is formed, and the strength of the image formed by exposure and Photosensitivity can be improved.

(Photopolymerization initiator)
As a photopolymerization initiator used in the present invention, an active species that initiates a polymerization reaction of a polymerizable monomer described later is generated by irradiation (exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. And can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.

  Examples of the photopolymerization initiator include trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, and polynuclear quinone compounds. Compounds, xanthone compounds, diazo compounds, and the like.

  Specific examples of the photopolymerization initiator described in JP-A-2001-117230 include trihalomethyloxazole derivatives or s-triazine derivatives substituted with a trihalomethyl group, as described in US Pat. No. 4,239,850. Trihalomethyl group-containing compounds such as trihalomethyl-s-triazine compounds and trihalomethyloxadiazole compounds described in US Pat. No. 4,221,976;

  9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;

  6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine; 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

  Among these, the photopolymerization initiator in the present invention is preferably at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound, and particularly a trihalomethyl group. At least one selected from a containing compound and an acridine compound is preferred. The trihalomethyl group-containing compound and the acridine compound are useful in that they are versatile and inexpensive.

  As the trihalomethyl group-containing compound, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole is preferable. The acridine compound is preferably 9-phenylacridine. More preferably, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole is mentioned.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
In this invention, 0.1-20 mass% is preferable, and solid content in the photosensitive resin composition of the said photoinitiator has more preferable 0.5-10 mass%. When the content is in the range of 0.1 to 20% by mass, the degree and strength of photocuring of the photosensitive resin composition can be sufficiently increased, and further, the formed image is prevented from being fragile and scraping downward. can do.

-Hydrogen donor-
The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. Here, the “hydrogen donor” refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator upon exposure.

  The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more mercapto groups directly bonded to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter referred to as “ It may also be referred to as a “mercaptan-based hydrogen donor”. The amine-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus ( Hereinafter, it may be referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2, 5-dimethylaminopyridine and the like can be mentioned, and 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

  Specific examples of the amine hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl- 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like can be mentioned, and 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable. 4,4′-bis (diethylamino) benzophenone is particularly preferred.

  These hydrogen donors can be used alone or in admixture of two or more. From the viewpoint of preventing the formed image (pixel) from falling off the substrate during development and improving the strength and sensitivity, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used. It is preferable to use in combination with the body.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor are 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 4,4′-bis (diethylamino) benzophenone.

When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) and the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable.
As content in the photosensitive resin composition of the said hydrogen donor, 0.1-20 mass% of the total solid (mass) of the photosensitive resin composition is preferable, and 0.5-10 mass% is especially preferable.

(Multifunctional monomer)
As the polyfunctional monomer in the present invention, a dipentaerythritol polyacrylate compound having a viscosity of 4000 mPa · s or less is used.
Here, the “viscosity” of the dipentaerythritol polyacrylate compound is a viscosity measured at a temperature of 25 ° C. The viscosity of the dipentaerythritol polyacrylate compound can be measured, for example, by the method described in JIS-K7117 (1987).

  The viscosity of the dipentaerythritol polyacrylate compound is preferably 4000 mPa · s or less, and more preferably 3000 mPa · s or less. The lower limit of the viscosity of the dipentaerythritol polyacrylate compound is not particularly limited, but is usually about 500 mPa · s or more.

As described above, in the present invention, “dipentaerythritol polyacrylate compound” means an acrylate compound in which at least one portion of the acrylate portion is substituted with another substituent. The dipentaerythritol polyacrylate compound is preferably a compound in which at least one alcohol portion of dipentaerythritol is acrylated via a divalent linking group.
Examples of the divalent linking group include an alkylene group and an arylene group.

  The dipentaerythritol polyacrylate compound is preferably a compound obtained by acrylated after at least one alcohol portion of dipentaerythritol is subjected to an addition reaction with a lactone or alkylene oxide compound. More preferably, the compound is an acrylated compound after an addition reaction with ε-caprolactone in at least one part. Specifically, the dipentaerythritol polyacrylate compound is preferably an acrylate ester of ε-caprolactone-modified dipentaerythritol.

  Specific examples of the dipentaerythritol polyacrylate compound in the present invention include compounds represented by the following general formulas (1) and (2). However, the present invention is not limited to this.

〔一般式（１）において、Ｘ¹〜Ｘ⁶は、単結合、または、下記構造式（１）〜（７）で表される連結基を表す。但し、Ｘ¹〜Ｘ⁶のうち少なくとも一つは、下記構造式（１）〜（７）で表される連結基である。〕

[In General formula (1), X < ¹ > -X < ⁶ > represents the coupling group represented by a single bond or following Structural formula (1)-(7). However, at least one of X ^{1 to} X ⁶ is a linking group represented by the following structural formulas (1) to (7). ]

〔一般式（２）において、Ｙ¹〜Ｙ⁶は、−ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂、または、下記構造式（８）で表される連結基を表す。但し、Ｙ¹〜Ｙ⁶のうち少なくとも一つは、下記構造式（８）で表される連結基である。〕

In [Formula (2), Y ¹ to Y ⁶ is, -OC (= O) CH = CH 2, or represents a linking group represented by the following structural formula (8). However, at least one of Y ^{1 to} Y ⁶ is a linking group represented by the following structural formula (8). ]

  Specifically, as the dipentaerythritol polyacrylate compound in the present invention, in addition to the acrylic acid ester of ε-caprolactone-modified dipentaerythritol, for example, an alkyl acid ester of ethylene oxide or propylene oxide adduct, or acryloyloxyethyl phosphate Etc.

  The polyfunctional monomer in the present invention can be used in combination with the dipentaerythritol polyacrylate compound and a known polymerizable monomer as long as the effects of the present invention are not impaired. Examples of the known polymerizable monomer include polymerizable monomers having an ethylenically unsaturated double bond. The polymerizable monomer having an ethylenically unsaturated double bond is a monomer compound having at least one ethylenically unsaturated bond capable of addition polymerization in the molecule, and preferably having a boiling point of 100 ° C. or higher at normal pressure. It is.

  Specific examples of the polymerizable monomer having an ethylenically unsaturated double bond include, for example, monofunctional acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Functional methacrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And (meth) acrylates after addition reaction of ethylene oxide or propylene oxide with polyfunctional alcohols such as trimethylolpropane and glycerin; Japanese Examined Patent Publication Nos. 48-41708, 50-6034, and Japanese Patent Publication No. 51-37193 Polyurethane acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, among others, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are particularly preferred examples.

Two or more kinds of polyfunctional monomers in the present invention can be mixed and used.
As for solid content in the photosensitive resin composition of the polyfunctional monomer in this invention, 5-50 mass% is preferable, More preferably, it is 10-40 mass%. When the content is in the range of 5 to 50% by mass, it is possible to prevent the photosensitivity and the strength of the image from being lowered, and the adhesiveness is hardly excessive when the photosensitive resin layer is formed. Excellent handleability.

(Light-shielding agent)
In the present invention, the “light-shielding agent” means a substance capable of adjusting the average light transmittance at a wavelength of 400 nm to 650 nm to 5% or less when the photosensitive resin layer is formed. Even if the photosensitive resin layer formed using the photosensitive composition of the present invention is a layer having such a low light transmittance, the exposed portion can be sufficiently cured.
Specific examples of the light-shielding agent in the present invention include carbon black, pigments, dyes, and metal particles.

  The light-shielding agent is preferably dispersed uniformly in the photosensitive resin layer, so that the particle size is preferably 5 μm or less, more preferably 1 μm or less, and more preferably 0.5 μm. The following particle diameters are particularly preferred.

  Specific examples of the pigment include Victoria Pure Blue BO (C.I. 42595), Auramin (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146) ), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15 Mono Light Fast Black B (C.I. Pigment Black 1), and carbon is preferably exemplified.

  Examples of yellow pigments include C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, 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 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 153, C.I. I. Pigment yellow, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 168 and the like are preferable.

  Examples of orange pigments include C.I. I. Pigment orange 36, 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 and the like are preferable.

  Examples of red pigments include C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, 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 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment Red 48: 1 and the like are preferable.

  Examples of violet pigments include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. Pigment Violet 50 and the like are preferable.

Examples of blue pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment Blue 64 and the like are preferable.
Examples of green pigments include C.I. I. Pigment green 7, C.I. I. Pigment Green 36 and the like are preferable.
Examples of the brown pigment include C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment Brown 26 and the like are preferable.
Examples of black pigments include C.I. I. Pigment black 7, C.I. I pigment black 10 or the like is preferable.

The said light-shielding agent can be used individually or in mixture of 2 or more types.
1-60 mass% is preferable and, as for solid content in the photosensitive resin composition of the light-shielding agent in this invention, 2-50 mass% is more preferable.

(Thermal polymerization inhibitor)
It is preferable to further add a thermal polymerization inhibitor to the photosensitive resin composition of the present invention. Specific examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

  Furthermore, a known additive such as a plasticizer, a surfactant, a solvent and the like can be added to the photosensitive resin composition of the present invention as required and necessary.

  As for the thickness of the light shielding film formed with the photosensitive resin composition of this invention, 1 micrometer-3 micrometers are preferable. When the thickness of the light-shielding film is 1 μm to 3 μm, the pigment concentration in the light-shielding film can be prevented from increasing and the developability can be prevented, and the developability and image formation reproducibility can be improved. it can. The film thickness of the light shielding film can be arbitrarily set within the above range. In particular, it is desirable that the finished product color filter has good flatness when producing a color filter. In this case, therefore, the thickness is set to the same thickness as other colored layers (red, blue, green colored layers, etc.). It is desirable.

  The photosensitive resin composition of this invention can be apply | coated on a board | substrate by a well-known method. Specifically, a desired light-shielding photosensitive resin layer can be provided on the substrate by applying and drying using a spinner, a winder, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder, or the like. In particular, a method of transferring onto a substrate using a photosensitive transfer material having at least a photosensitive resin layer formed using the photosensitive resin composition of the present invention on a temporary support is preferable. As specific transfer materials, transfer materials described in JP-A-4-208940, JP-A-5-72724, JP-A-5-80503 and JP-A-5-173320 are used.

  For exposure through the transparent substrate (backside exposure), the light source is selected according to the photosensitive characteristics of the light-shielding photosensitive resin layer, and known light sources such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an argon laser can be used. . As described in Japanese Patent No. 3308038, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used in combination. Further, as described in Japanese Patent No. 3308038, the red, green, and blue pixels formed on the substrate in advance may have a light transmittance of 2% or less for each pixel in the photosensitive wavelength region of the light-shielding photosensitive resin layer. preferable.

<Photosensitive transfer material>
The photosensitive transfer material of the present invention has at least a photosensitive resin layer using the photosensitive resin composition of the present invention on a temporary support, and if necessary, a thermoplastic resin layer, an intermediate layer, or the like. You may have. Moreover, it is preferable that the photosensitive transfer material of this invention has a cover sheet for protecting the photosensitive resin layer.

  Specifically, as a configuration of the photosensitive transfer material of the present invention, disclosed in JP-A-4-208940, a transfer material having a separation layer having a low adhesive force to a temporary support and a light-shielding photosensitive resin layer, JP, 5-173320, A has a thermoplastic resin layer, an intermediate layer, and a light-shielding photosensitive resin layer on a temporary support, and the adhesive force between the temporary support and the thermoplastic resin layer is It has the smallest photosensitive transfer material, the thermoplastic resin layer disclosed in JP-A-5-72724, a separation layer and a light-shielding photosensitive resin layer, and has an adhesive force between the thermoplastic resin layer and the separation layer. The smallest transfer material, having a thermoplastic resin layer, an intermediate layer and a light-shielding photosensitive resin layer on the temporary support disclosed in JP-A-5-80503, and comprising the temporary support and the thermoplastic resin layer Photosensitive transfer material with the smallest adhesive strength between Kill.

(Thermoplastic resin layer)
The thermoplastic resin layer preferably includes at least a resin component and is alkali-soluble. As said resin component, it is preferable that a substantial softening point is 80 degrees C or less. The thermoplastic resin layer is preferably provided between the temporary support and the photosensitive resin layer.
Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.

  In the thermoplastic resin layer, at least one of the thermoplastic resins can be appropriately selected and used. Further, “All-Japan Plastic Molding Industry Federation” edited by “Plastic Performance Handbook” (published by Japan Plastic Industry Federation, Industrial Research Council, 1968). Which is soluble in an aqueous alkali solution of an organic polymer having a softening point of about 80 ° C. or less, issued on October 25, 1980).

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, and the like can also be added.

  Preferable specific examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, and cresyl diphenyl phosphate biphenyl diphenyl phosphate.

  The thickness of the thermoplastic resin layer is preferably 6 μm or more. When the thickness is 6 μm or more, even if the unevenness of the base is 1 μm or more, it can be completely absorbed. The upper limit of the thickness is preferably about 100 μm or less, more preferably about 50 μm or less, from the viewpoint of developability and manufacturability when remaining on the light-shielding photosensitive resin layer side during transfer.

  When the thermoplastic resin layer is provided on the temporary support, a known coating method using a spin coater, a bar coater, or the like can be used for the coating liquid for forming the thermoplastic resin layer prepared in the form of a solution.

(Photosensitive resin layer)
The photosensitive resin layer in the present invention is formed using the photosensitive resin composition of the present invention. For this reason, it is a layer comprised by alkali solubility, and contains at least a photoinitiator, the polyfunctional monomer in this invention, and a light-shielding agent. Moreover, the other component may be included as needed. For this photosensitive resin layer, a photosensitive resin composition containing each component constituting the layer is prepared, for example, as a solution coating solution, and this is applied by a known coating method using a spin coater, a bar coater, or the like. For example, it can be formed by providing a layer on the temporary support.

  The thickness of the photosensitive resin layer in the present invention is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

In addition to the above, the photosensitive resin layer according to the present invention may further include known additives such as plasticizers, fillers, stabilizers, polymerization inhibitors, surfactants, solvents, adhesion promoters as necessary. Etc. can be contained.
In addition, the photosensitive resin composition constituting the photosensitive resin layer in the present invention is preferably softened or tacky at a temperature of 150 ° C. or less, and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

(Middle layer)
The photosensitive transfer material of the present invention can be provided with an intermediate layer.
The above intermediate layer prevents mixing when a thermoplastic resin layer or a photosensitive resin layer is applied in multiple layers, adjusts the adhesion between these layers, and remains on the light-shielding photosensitive resin layer side during transfer to block oxygen For example, those having an oxygen barrier function are known from those that are dispersed or dissolved in water or an aqueous alkali solution and exhibit low oxygen permeability. Can be applied. Polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble of carboxyalkyl starch described in JP-A Nos. 46-2121 and 56-40824 Water-soluble salts of the group consisting of salts, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches, and the like, Examples include styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof.

Particularly preferred is a combination of polyvinyl alcohol and polyvinyl pyrrolidone. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 60% by mass, based on the solid content of the intermediate layer.
The thickness of the intermediate layer is preferably about 0.1 to 5 μm, particularly preferably about 0.5 to 2 μm, from the viewpoint of oxygen permeability and development time or intermediate layer removal time.

(Temporary support)
The temporary support can be appropriately selected from those that are chemically and thermally stable and made of a flexible material. Specifically, a thin sheet or a laminate thereof such as Teflon (R), polyethylene terephthalate, polycarbonate, polyethylene, or polypropylene is preferable. As thickness of a temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers.

<Image forming method>
As a method for forming a black matrix using the photosensitive resin composition of the present invention, it is preferable to use the following image forming method of the present invention using a transfer method using the photosensitive transfer material of the present invention. The image forming method of the present invention can be suitably used as a method for forming a color filter in which multicolor pixels and a black matrix are formed on a substrate. The image forming method of the present invention is an image forming method using the above-described photosensitive transfer material of the present invention, in which the photosensitive resin layer of the photosensitive transfer material and a substrate are in close contact with each other, and the photosensitive property described above. A removal step for removing the temporary support from the transfer material, an exposure step for pattern exposure of the photosensitive resin layer, and an image formation step for developing the pattern-exposed photosensitive resin layer to form an image on the substrate. It is characterized by including these. In the image forming method of the present invention, a light-transmitting substrate (hereinafter sometimes referred to as “transparent substrate”) is used as the substrate, and the substrate side (the photosensitive of the substrate is used) in the exposure step. The photosensitive resin layer may be subjected to pattern exposure by irradiating light from the side where the photosensitive resin layer is not in close contact: hereinafter referred to as “back surface” in some cases.

  The laminating step is a step of forming a laminate by closely contacting the surface of the photosensitive resin layer of the photosensitive transfer material and the substrate while heating. In the laminating step, it is preferable to laminate the photosensitive resin layer and the substrate while applying pressure. Various conditions for the lamination are appropriately determined in consideration of the material of the photosensitive resin layer and the like.

  The said removal process is a process of peeling the temporary support body of the photosensitive transfer material from the laminated body which consists of the photosensitive transfer material of this invention, and a board | substrate. At this time, the alkali-soluble thermoplastic resin layer may be peeled off at the same time as the temporary support is peeled off.

The exposure step is a step of irradiating the photosensitive resin layer with light or radiation imagewise to form a pattern. Pattern formation on the photosensitive resin layer can be performed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, or the like.
In the present invention, for example, ultraviolet light having a wavelength of 365 nm or 405 nm can be suitably used. Moreover, as a light source, a super high pressure mercury lamp, a xenon lamp, a carbon arc lamp, an argon laser, etc. are mentioned suitably, The light transmittance of the wavelength of 400 nm or more as described in the patent No. 3308038 is 2% or less An optical filter or the like may be used in combination.

  The so-called back exposure method in which exposure is performed from the back surface of the substrate is a particularly effective method when the above-described photosensitive resin layer is laminated on a transparent substrate on which multicolor pixels are already formed. In this case, when exposed from the back surface of the transparent substrate, it was laminated to an area (non-pixel portion) where the multicolor pixels on the image forming surface side (hereinafter sometimes referred to as “front surface”) of the transparent substrate are not provided. Only the photosensitive resin layer is exposed and cured. As long as the exposure can be performed uniformly from the back surface of the substrate, the exposure may be performed on the entire surface or may be performed in a plurality of divisions.

  In the above backside exposure method, when exposed from the backside of the transparent substrate, the multicolor pixels serve as a photomask, and are provided directly on the substrate surface without interposing the multicolor pixels on the image forming surface side (front surface). Only the obtained photosensitive resin composition is exposed. At this time, the photosensitive resin layer provided via the multicolor pixels (on the multicolor pixels) is not exposed and cured because the light is absorbed by the multicolor pixels.

  As described above, when the entire surface is exposed from the back surface, each colored image functions as a light-shielding mask, so that a mask alignment step is not necessary. For this reason, anxiety such as misalignment of the mask is eliminated, and a light-shielding image (black matrix) can be formed without any gaps in all the portions where the colored pixels are not formed.

  Moreover, in the said exposure process, after laminating the photosensitive resin layer in this invention uniformly on the transparent substrate surface, imagewise exposure may be performed from the back surface of a board | substrate, and a pattern may be formed. In this case, after the black matrix is formed, a plurality of other photosensitive transfer materials having different hues (that is, photosensitive transfer materials in which pigments such as red, green, and blue, and dyes are added to the photosensitive resin layer) are used. A pattern image (color filter) composed of a plurality of colors can be formed by repeating the same image forming process as described above for the hue and forming colored pixels.

  In addition, as the photosensitive transfer material for forming each colored pixel, for example, the photosensitive resin layer containing the light shielding agent in the photosensitive transfer material of the present invention is replaced with a photosensitive resin layer containing a coloring material. A transfer material or the like is preferable. Specifically, for example, photosensitive transfer materials described in JP-A-5-80503, JP-A-10-22158, JP-A-2001-221909, and the like are preferably used.

  The image forming step is a step of developing the exposed photosensitive resin layer to form a light-shielded image (black matrix). In this step, an image (black matrix) is formed by removing the unexposed region (uncured region) of the thermal recording layer by development using a developer or the like. As the developer, a dilute aqueous solution of an alkaline substance can be used, and further a small amount of an organic solvent miscible with water may be added.

  Examples of the alkaline substance include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, sodium bicarbonate, Potassium bicarbonate), alkali metal silicates (for example, sodium silicate, potassium silicate), alkali metal metasilicates (for example, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine Tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance in the developer is preferably from 0.01 to 30% by mass, and the pH is preferably from 8 to 14.

  Examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, and benzyl. Preferable examples include alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. The concentration of the water-miscible organic solvent is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can also be added. The concentration of the surfactant with respect to the developer is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin layer, a method such as rubbing with a rotating brush or a wet sponge in a developer may be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, depending on the type of photosensitive resin composition, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If the development time is too short, the development of the non-exposed area may be insufficient, and the UV absorbance may be insufficient, and if it is too long, the exposed area may be etched. It is also possible to place a water washing step after the development processing.

  Furthermore, in the image forming process, after removing the unexposed portion of the photosensitive resin layer, a heating process for performing a heating process (baking process) as necessary may be provided. The heating step is a step of heating the substrate having each color pixel or black matrix after development in an electric furnace, a dryer or the like, or irradiating with an infrared lamp. The heating temperature and heating time in the heating step depend on the composition of the photosensitive resin composition and the thickness of the formed photosensitive resin layer, but generally have sufficient solvent resistance, alkali resistance, and a viewpoint of obtaining ultraviolet absorbance. From about 120 ° C. to about 250 ° C. for about 10 minutes to about 120 minutes.

-Board-
As said board | substrate (permanent support body), a metallic support body, a metal bonding support body, glass, a ceramic, a synthetic resin film, etc. can be used. Particularly preferred is a glass or synthetic resin film having transparency and good dimensional stability. The thickness of the substrate varies depending on the purpose, but is usually about 0.7 to 1.1 mm.

Hereinafter, a black matrix forming method using the image forming method of the present invention will be specifically described.
First, after the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer are formed in this order on the temporary support, the photosensitive transfer material of the present invention is further provided with a cover sheet on the photosensitive resin layer. Prepare.

  Next, after peeling off and removing the cover sheet, the exposed surface of the photosensitive resin layer is bonded to a transparent substrate provided with pixels of each color (red, blue, and green), and heated and pressurized through a laminator or the like for lamination. Then, a laminated body is formed. As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used to further increase the productivity.

  Next, the temporary support is removed by peeling between the thermoplastic resin layer and the temporary support or between the thermoplastic resin layer and the intermediate layer. After removing the temporary support, the entire surface is irradiated with ultraviolet rays from the back surface of the substrate to the photosensitive resin layer. In this case, since each color pixel has already been formed in the transparent pixel, the pixel group serves as a mask. After irradiation, development processing is performed using a predetermined processing solution to remove unexposed portions, and baking processing can be performed as necessary to form a black matrix between pixels.

In addition, when forming each color pixel after forming the black matrix, the above thermal recording layer is uniformly laminated on a transparent substrate, the temporary support is removed, and then the above photosensitive resin layer is image-like. Perform by exposure. In this case, after forming the black matrix, a color filter having a desired hue can be formed by repeating the same operation using a photosensitive transfer material for colored pixels.
As described above, a color filter having colored pixels and a black matrix on a substrate can be formed.

《Color filter》
The photosensitive composition of the present invention can be suitably used for forming a black matrix of a color filter. The color filter is configured by providing at least one or more colored pixels and a black matrix on a substrate.
The specific method for producing the color filter is as described above, but by producing it by the transfer method using the photosensitive transfer material of the present invention, a uniform thickness pattern can be easily formed. A color filter having a black matrix having a high density and a sufficient film thickness can be produced. .

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “%” and “part” are based on mass unless otherwise specified.

[Example 1]
<Preparation of photosensitive transfer material for black matrix formation>
(Formation of thermoplastic resin layer)
A 75 μm thick polyethylene terephthalate base film (PET base film) was prepared as a temporary support. A thermoplastic resin layer coating solution obtained by mixing the following composition on the film was applied by a spin coater, dried in an oven at 120 ° C. for 5 minutes, and a thermoplastic resin having a layer thickness of 15 μm on the PET base film. A resin layer was formed.

-Composition of coating solution for thermoplastic resin layer-
Benzyl methacrylate / 2-ethylhexyl acrylate / methyl methacrylate / methacrylic acid copolymer 4.5 parts (copolymerization ratio 4.5 / 11.7 / 55 / 28.8: weight average molecular weight 80000)
Styrene / acrylic acid copolymer 15 parts (copolymerization composition ratio 60/40: weight average molecular weight 8000)
2,2-bis [4- (methacryloxypolyethoxy) phenylpropane]
7 parts, 1.5 parts of fluorosurfactant (trade name: F-176PF, manufactured by Dainippon Ink Co., Ltd.)
・ Propylene glycol monomethyl ether 28 parts ・ Methyl ethyl ketone 27 parts

(Formation of intermediate layer)
Next, the following composition was mixed to prepare an intermediate layer coating solution, and the intermediate layer coating solution was further applied onto the thermoplastic resin layer by a spin coater. Thereafter, it was dried in an oven at 100 ° C. for 2 minutes to form an intermediate layer having a layer thickness of 1.6 μm on the thermoplastic resin layer.

-Composition of coating solution for intermediate layer-
・ Polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) 13 parts ・ Polyvinylpyrrolidone 6 parts (trade name: PVP-K30, manufactured by Gokyo Sangyo Co., Ltd.)
・ Methanol 173 parts ・ Ion-exchanged water 211 parts

(Formation of light-shielding photosensitive resin layer)
Next, the following composition was mixed and the coating liquid for light-shielding photosensitive resin layers was prepared. And the coating liquid for light-shielding photosensitive resin layers was apply | coated with the spin coater on the said intermediate | middle layer. Then, it dried for 2 minutes in 100 degreeC oven, and formed the light-shielding photosensitive resin layer of thickness 3 micrometers. Furthermore, a 12 μm-thick polypropylene film is laminated as a cover film on the photosensitive resin layer at room temperature, and a thermoplastic resin layer, an intermediate layer, a light-shielding photosensitive resin layer, and a cover film are laminated in this order on the PET base film. Thus, the photosensitive transfer material of the present invention was obtained.

-Composition of coating solution for light-shielding photosensitive resin layer-
・ C. I. PB60 dispersion 20.97 parts (trade name: SPB-10, manufactured by Fuji Photo Film Co., Ltd.)
・ C. I. 6.38 parts of PY139 dispersion (trade name: YT-20, manufactured by FUJIFILM Arch Corporation)
・ C. I. PB15: 6 dispersion 1.74 parts (trade name: RT-2-2, manufactured by FUJIFILM Arch Corporation)
・ C. I. PV23 dispersion 2.98 parts (trade name: CFP-FF-802V, manufactured by FUJIFILM Arch Corporation)
Carbon black dispersion 8.37 parts (trade name: 7270M, manufactured by Mikuni Dye Co., Ltd., alkali-soluble resin (methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylate copolymer (copolymer composition ratio (molar ratio)) ) 55 / 11.7 / 4.5 / 28.8), 10% average molecular weight 800000))
・ Propylene glycol monomethyl ether acetate 17.61 parts (MMPG-AC)
・ Methyl ethyl ketone 34.76 parts ・ Surfactant 0.07 parts (Product name: Megafac F-176PF, manufactured by Dainippon Ink Co., Ltd.)
Hydroquinone monomethyl ether 0.0021 parts Dipentaerythritol caprolactone acrylic acid ester (trade name: KAYARAD DPCA-20, Nippon Kayaku Co., Ltd., viscosity 2200 mPa · s) 4.53 parts 9-phenylacridine 0. 23 parts 2-mercapto-5-methylmercapto-1,3,4-thiadiazole
0.23 parts

  In addition, the viscosity of the acrylic ester of dipentaerythritol caprolactone was measured according to JIS-K7117 (1987).

<Preparation of photosensitive transfer material for forming colored pixels>
In the production of the black matrix-forming photosensitive transfer material, the “light-shielding photosensitive resin layer coating solution” is used as a red photosensitive resin layer coating solution, a green photosensitive resin layer coating solution, and blue Three types of photosensitive transfer materials for red pixel formation, green pixel formation, and blue pixel formation were obtained in the same manner except that each of the coating liquids for the photosensitive resin layer was changed.

-Composition of coating solution for red photosensitive resin layer-
・ C. I. 21.65 parts of PR254 dispersion (trade name: RT-107, manufactured by FUJIFILM Arch Corporation)
・ Propylene glycol monomethyl ether acetate 31.20 parts (MMPG-AC)
・ Methyl ethyl ketone 34.96 parts ・ Surfactant 0.06 parts (Brand name: Megafac F-176PF, manufactured by Dainippon Ink Co., Ltd.)
-Phenothiazine 0.0012 parts-Benzyl methacrylate / methacrylic acid copolymer 4.97 parts (copolymerization ratio = 72/28, weight average molecular weight 30000)
Dipentaerythritol hexaacrylate 4.92 parts 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole 0.31 parts 7-{[-4 (diethylamino)- 6- (3-Hydroxymethylpiperidino) -s-triazinyl (2)]-amino} -3-phenylcoumarin
1.50 parts · 2,4,6-tris [2,4bis (methoxycarbonyloxy) phenyl] -1,3,5-triazine 0.37 parts

-Composition of coating solution for green photosensitive resin layer-
・ C. I. PG36 dispersion 15.86 parts (trade name: GT-2, manufactured by FUJIFILM Arch Corporation)
・ C. I. 11.06 parts of PY138 dispersion (trade name: YT-123, manufactured by FUJIFILM Arch Corporation)
・ Propylene glycol monomethyl ether acetate 10.25 parts (MMPG-AC)
・ Methyl ethyl ketone 51.49 parts ・ Surfactant 0.19 parts (Product name: Megafac F-176PF, manufactured by Dainippon Ink, Inc.)
・ Phenothiazine 0.004 part ・ Benzyl methacrylate / methacrylic acid copolymer 4.47 parts (copolymerization ratio = 72/28, weight average molecular weight 30000)
Dipentaerythritol hexaacrylate 5.27 parts 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole 0.193 parts 7-{[-4 (diethylamino)- 6- (3-Hydroxymethylpiperidino) -s-triazinyl (2)]-amino} -3-phenylcoumarin
1.26 parts

-Composition of coating solution for blue photosensitive resin layer-
・ C. I. PB15: 6 dispersion 32.93 parts (trade name: 7075M, manufactured by Mikuni Dye Co., Ltd.)
Propylene glycol monomethyl ether acetate 0.69 parts (MMPG-AC)
・ Methyl ethyl ketone 52.50 parts ・ Surfactant 0.12 parts (Product name: Megafac F-176PF, manufactured by Dainippon Ink Co., Ltd.)
・ Phenothiazine 0.022 parts ・ Benzyl methacrylate / methacrylic acid copolymer 8.10 parts (copolymerization ratio = 78/22, molecular weight 40000)
Dipentaerythritol hexaacrylate 5.19 parts 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole 0.20 parts 2,4,6-tris (2,4 Bis (methoxycarbonyloxy) phenyl] -1,3,5-triazine 0.25 part

<Production of color filter>
The glass substrate was immersed in a silane coupling agent solution (trade name: KBM-603; 1% diluent, manufactured by Shin-Etsu Chemical Co., Ltd.) for 3 minutes. Thereafter, it was washed with water for 10 seconds, drained with an air gun, and then dried in an oven at 110 ° C. for 5 minutes to obtain a silane coupling treated glass substrate.

The cover film was removed from the red pixel photosensitive transfer material obtained as described above. Thereafter, the silane coupling treated glass substrate and the photosensitive resin layer of the photosensitive transfer material for red pixels are overlapped so that a laminator (trade name: First Laminator 8B-550-80, manufactured by Taisei Laminator Co., Ltd.) ). The pasting was performed under a pressure of ² kg / m ² , a roller temperature of 130 ° C., and a feed condition of 0.2 m / min. Subsequently, the temporary support of polyethylene terephthalate was peeled off at the interface with the thermoplastic resin layer, and the temporary support was removed. Next, using the aligner MAP-1200L (manufactured by Dainippon Screen Co., Ltd.), the photosensitive resin layer was exposed for 3 seconds from a distance of 60 cm with a super high pressure mercury lamp (2 kW) through a photomask for red pixels. (Irradiation energy: 20 mJ / cm ² ). Subsequently, the thermoplastic resin layer and the intermediate layer were removed using a predetermined treatment solution (trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd .; 10-fold diluted solution). Thereafter, the photosensitive resin layer was developed with a predetermined processing solution (trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd .; 5-fold diluted solution) to remove unexposed portions. Further, the developing residual film was removed while brushing with a predetermined processing solution (trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) to obtain a red pixel pattern on the glass substrate. In order to further cure the pixel pattern, the entire surface of the substrate was post-exposed at 500 mJ / cm ² from the front and back of the substrate with the above aligner and baked in an oven at 220 ° C. for 20 minutes.

  Next, using the green pixel photosensitive transfer material, similarly, the green photosensitive transfer material is laminated on a glass substrate with a red pixel pattern, temporary support removal, pattern exposure, thermoplastic resin layer and intermediate layer removal, development, Residual film processing was performed, post-exposure was performed, and baking was performed in an oven at 220 ° C. for 20 minutes to obtain a color filter substrate on which red pixels and green pixel patterns were provided.

  Then, using the blue pixel photosensitive transfer material, similarly, the blue photosensitive transfer material is bonded onto the glass substrate with red and green pixel patterns, temporary support removal, pattern exposure, thermoplastic resin layer and intermediate layer removal, Development, residual film treatment was performed, post-exposure was performed, and baking was performed in an oven at 220 ° C. for 20 minutes to obtain a color filter substrate provided with red pixel, green pixel, and blue pixel patterns.

Subsequently, the cover film is removed from the photosensitive transfer material for forming the black matrix, the surface of the black photosensitive resin layer of the photosensitive transfer material, and the red, green, and red of the glass substrate having red, green, and blue images, The layers were superposed so as to be in contact with the surface on which the blue image was provided, and bonded together using the laminator in the same manner as described above. Subsequently, the PET base film (temporary support) was peeled off at the interface with the light-shielding photosensitive resin layer, and the temporary support was removed. Then, using an aligner MAP-1200L (manufactured by Dainippon Screen Co., Ltd.), a super high pressure mercury lamp (2 kW) from the back side (image non-formation side) having no red, green, and blue images at 70 mJ / cm ² Perform exposure and further development and post-exposure in the same manner as in the case of a red image, etc., and baked in an oven at 240 ° C. for 50 minutes to form a black image on a non-image portion having no red image, green image, and blue image. A light-shielding image (black matrix) was formed. As described above, a color filter composed of a red image, a green image, and a blue image and a black matrix formed therebetween was obtained.

[Examples 2 to 4]
In “Composition of coating solution for light-shielding photosensitive resin layer” in Example 1, dipentaerythritol caprolactone-modified polyacrylate compound according to the present invention (trade name: KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd., viscosity: 2200 mPa · A color filter of the present invention was produced in the same manner as in Example 1 except that s) was changed to acrylic esters of dipentaerythritol caprolactone shown in Table 1, respectively.

  The liquid crystal panels produced using the color filters obtained in Examples 1 to 4 had a good light shielding property at the black matrix portion, and the result that alignment disorder did not occur practically was obtained.

  Moreover, after applying and drying the light-sensitive photosensitive resin layer coating solution used in Examples 1 to 4 directly on the color filter substrate obtained in Example 1 above using an extruder type coating machine, the back surface When exposed and developed, a good color filter with a black matrix could be obtained as in Examples 1 to 4.

[Comparative Example 1]
In “Composition of coating solution for light-shielding photosensitive resin layer” in Example 1, dipentaerythritol caprolactone-modified polyacrylate compound according to the present invention (trade name: KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd., viscosity: 2200 mPa · A comparative color filter was produced in the same manner as in Example 1 except that s) was changed to dipentaerythritol hexaacrylate (DPHA) (viscosity 6700 mPa · s).

[Comparative Example 2]
In “Composition of Coating Solution for Light-Sensitive Photosensitive Resin Layer” in Example 1, acrylic acid ester of dipentaerythritol caprolactone (trade name: KAYARAD DPCA-20, Nippon Kayaku Co., Ltd., viscosity: 2200 mPa · s) A comparative color filter was produced in the same manner as in Example 1, except that the dipentaerythritol pentaacrylate (trade name: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd., viscosity 3300 mPa · s) was used.

<Evaluation>
The optical density and film thickness (μm) of the light-shielding image portion (black matrix portion) of the color filter obtained above were evaluated as follows. The evaluation results are shown in Table 1 below.

1. Optical Density The optical density was measured with a Macbeth transmission type densitometer TD-904 (black and white density (visual); manufactured by Macbeth).

2. Film thickness (μm)
The film thickness (μm) of the black matrix was measured by a fine shape measuring instrument P-10 type (manufactured by KLA Tencor).

As can be seen from Table 1, the color filter of the example formed using the photosensitive composition and photosensitive transfer material of the present invention containing the dipentaerythritol polyacrylate compound of the present invention having a viscosity of 4000 mPa · s is The optical density of the black matrix was high, and no film loss occurred. For this reason, it was excellent in light-shielding property, and alignment disorder was not seen. Furthermore, when the photosensitive resin layer was formed, the average light transmittance at a wavelength of 400 nm to 650 nm was 5% or less.
On the other hand, the color filter of the comparative example was inferior in the optical density of the black matrix and could not obtain a desired film thickness. For this reason, it was inferior to light-shielding property and orientation disorder was recognized.
From these results, it can be seen that the photosensitive composition of the present invention is sufficiently cured to the deep part of the film even with the same amount of irradiation.

Claims (7)

A photosensitive resin composition containing at least an alkali-soluble binder, a photopolymerization initiator, a polyfunctional monomer, and a light-shielding agent,
The photosensitive resin composition, wherein the polyfunctional monomer is a dipentaerythritol polyacrylate compound having a viscosity of 4000 mPa · s or less.   2. The photosensitive resin composition according to claim 1, wherein the dipentaerythritol polyacrylate compound is a compound in which at least one alcohol portion of dipentaerythritol is acrylated via a divalent linking group. Stuff.   The dipentaerythritol polyacrylate compound is a compound that is acrylated after addition reaction of at least one alcohol portion of dipentaerythritol with a lactone or an alkylene oxide compound. Photosensitive resin composition.   The dipentaerythritol polyacrylate compound is a compound that is acrylated after addition reaction with ε-caprolactone in at least one alcohol portion of dipentaerythritol. Photosensitive resin composition.   A photosensitive transfer material comprising a photosensitive resin layer formed by using at least the photosensitive resin composition according to claim 1 on a temporary support. An image forming method using a photosensitive transfer material having at least a photosensitive resin layer using the photosensitive resin composition according to any one of claims 1 to 4 on a temporary support,
A laminating step for bringing the photosensitive resin layer of the photosensitive transfer material into close contact with the substrate;
Removing the temporary support from the photosensitive transfer material;
An exposure step of pattern exposing the photosensitive resin layer;
An image forming step of developing the pattern-exposed photosensitive resin layer to form an image on the substrate;
An image forming method comprising:   The image forming method according to claim 6, wherein the substrate is light transmissive, and in the exposure step, pattern exposure of the photosensitive resin layer is performed by irradiating light from the substrate side. .