JP2009048159A - Photosensitive transfer material, color filter and manufacturing method thereof - Google Patents

Abstract

Provided is a photosensitive transfer material in which transfer failure hardly occurs even if transfer is performed at high speed, and reticulation and thermoplastic resin layer do not occur even when stored in a high humidity atmosphere.
An alkali-soluble thermoplastic resin layer containing a compound having an I / O value of 0.30 to 0.45, in order from the temporary support side, and a photosensitive resin layer on the temporary support. Is a photosensitive transfer material. The I / O value of the compound is preferably 0.32 to 0.43, and the thermoplastic resin layer contains the compound in an amount of 0.5 to 20 mass with respect to the total mass of the thermoplastic resin layer. % Content is preferable.
[Selection figure] None

Description

  The present invention relates to a photosensitive transfer material, a color filter, and a manufacturing method thereof.

  There are various methods for manufacturing a color filter. For example, a method using a photosensitive transfer material is known (for example, see Patent Document 1). In this method, a method is used in which a photosensitive transfer material is laminated on a transparent substrate, and then a temporary support is peeled off, followed by exposure and development to form desired pixels on the transparent substrate. In this case, a transfer defect that traps bubbles between the photosensitive resin layer and the substrate may occur on the uneven substrate.

In order to prevent the transfer failure, it has been proposed to provide a thermoplastic resin layer on the photosensitive transfer material (for example, see Patent Document 2).
However, in recent years, the transfer speed of photosensitive transfer materials has increased, and excellent transfer failure prevention techniques have been demanded. In order to enable high-speed transfer, a method of adding a plasticizer to the thermoplastic resin layer has been proposed. Examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, Examples include cresyl phosphate, cresyl phenyl phosphate, and biphenyl diphenyl phosphate (for example, see Patent Document 3).
Japanese Patent Laid-Open No. 9-197665 JP-A-5-72724 JP-A-9-199665

  Addition of a plasticizer to the thermoplastic resin layer is advantageous for high-speed transfer. However, on the other hand, since the plasticizer is hydrophilic, the photosensitive transfer material is soft, causing reticulation (wrinkle generation), and when the photosensitive transfer material is wound and stored. There is a problem that the thermoplastic resin layer oozes out from the side of the photosensitive transfer material. This is because the addition of a hydrophilic plasticizer decreases the viscosity of the thermoplastic resin layer at a high temperature when transferring the photosensitive transfer material and the elastic modulus and viscosity of the thermoplastic resin layer at room temperature. What happens.

  In view of the above problems, the present invention is a photosensitive transfer material in which transfer failure hardly occurs even if transfer is performed at high speed, and reticulation and thermoplastic resin layer do not easily exude even if stored in a high humidity atmosphere. Another object of the present invention is to provide a color filter using the same and a manufacturing method thereof.

Specific means for achieving the above object are as follows.
<1> An alkali-soluble thermoplastic resin layer containing a compound having an I / O value of 0.30 to 0.45 and a photosensitive resin layer on the temporary support in this order from the temporary support side. A photosensitive transfer material.
<2> The photosensitive transfer material according to <1>, wherein the compound has an I / O value of 0.32 to 0.43.
<3> The thermoplastic resin layer according to <1> or <2>, wherein the thermoplastic resin layer contains the compound in an amount of 0.5 to 20% by mass with respect to the total mass of the thermoplastic resin layer. It is a photosensitive transfer material.
<4> The photosensitive property according to any one of <1> to <3>, wherein at least one intermediate layer is provided between the thermoplastic resin layer and the photosensitive resin layer. It is a transfer material.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the thermoplastic resin layer further contains a plasticizer.

<6> Using the photosensitive transfer material according to any one of <1> to <5>, a transfer step of transferring at least a photosensitive resin layer onto a substrate, and at least transferred onto the substrate It is a manufacturing method of the color filter which has the exposure process which exposes the said photosensitive resin layer, and the image development process which develops the said photosensitive resin layer after the said exposure.
<7> A color filter manufactured by the method for manufacturing a color filter according to <6>.

  According to the present invention, there is provided a photosensitive transfer material in which transfer failure is unlikely to occur even when transfer is performed at high speed, and reticulation or thermoplastic resin layer does not ooze out even when stored in a high humidity atmosphere. The used color filter and the manufacturing method thereof can be provided.

<Photosensitive transfer material>
The photosensitive transfer material of the present invention comprises, on the temporary support, in order from the temporary support side, an alkali-soluble thermoplastic resin layer containing a compound having an I / O value of 0.30 to 0.45, Although it has a photosensitive resin layer, an intermediate layer and other layers may be further provided.

[Temporary support]
As the temporary support, a material that has flexibility and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heat can be used. Examples of such materials include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

There is no restriction | limiting in particular in the thickness of a temporary support body, The range of 5-200 micrometers is common, and the range of 10-150 micrometers is especially preferable at points, such as handleability and versatility.
Further, the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like.

[Thermoplastic resin layer]
The thermoplastic resin layer in the present invention is configured to be alkali-soluble and contains at least one compound having an I / O value of 0.30 to 0.45. By containing this compound, a low viscosity can be obtained at a high temperature, the transferability can be maintained, and the viscosity can be maintained during storage (at room temperature) to prevent the occurrence of reticulation and bleeding. Further, it preferably contains a plasticizer, and may contain other components.

-Compound having an I / O value of 0.30 to 0.45-
The compound used in the thermoplastic resin layer of the present invention has an I / O value of 0.30 to 0.45, preferably 0.32 to 0.43. If the I / O value is less than 0.30, a phenomenon in which this compound precipitates outside the thermoplastic resin layer during storage of the photosensitive transfer material-so-called crying-out occurs, and the I / O value If it exceeds 0.45, the reticulation (wrinkle generation) of the photosensitive transfer material is deteriorated.
The I / O value is a scale representing the hydrophilicity / hydrophobicity of a compound, and is described in detail in, for example, “Yoshio Koda, Organic Conceptual Diagram-Basics and Applications” (Sankyo Publishing Co., Ltd., published in 1984). ing. I represents inorganic and O represents organic, and the larger the I / O value, the greater the inorganicity (high polarity and high hydrophilicity).

The compound used in the thermoplastic resin layer of the present invention is not particularly limited as long as the I / O value is 0.30 to 0.45, but is preferably a thermoplastic compound. , Stearic acid (0.42), behenic acid (0.34), palmitic acid amide (0.42), stearic acid amide (0.38), behenic acid amide (0.31), oleic acid amide (0. 38), erucic acid amide (0.31), dioctyl adipate (0.43), dinonyl adipate (0.35), dioctyl sebacate (0.35) and the like. The number in parenthesis indicates the I / O value of the compound.
Among these, dioctyl adipate, dinonyl adipate, and dioctyl sebacate are particularly preferred compounds in terms of solubility in a solvent.

  0.5-20 mass% is preferable with respect to the total mass of a thermoplastic resin layer, and, as for content in the thermoplastic resin layer of the said compound, 0.8-10 mass% is more preferable. If the added amount is 0.5% by mass or more, there is an effect of improving transferability, and if it is within 20% by mass, this compound is prevented from being deposited outside the layer during the storage of the photosensitive transfer material. be able to.

-Alkali soluble-
The alkali-soluble in the present invention means that it is soluble in an aqueous solution of the following alkaline substance or a mixture of this with an organic solvent miscible with water.
Suitable alkaline substances are alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium bicarbonate, potassium bicarbonate). ), Alkali metal silicates (sodium silicate, potassium silicate), alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxide (Eg tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is preferably 0.01% by mass to 30% by mass in terms of processing speed, and the pH is preferably 8 to 14 in terms of the processing speed.

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

-Thermoplastic resin-
In the thermoplastic resin layer of the present invention, in addition to the above compounds, thermoplastic resins such as acrylic resins, polystyrene resins, polyesters, polyurethanes, rubber resins, vinyl acetate resins, polyolefin resins, and copolymers thereof Can be used.

  Specifically, saponified product of ethylene and acrylate copolymer, saponified product of styrene and (meth) acrylic ester copolymer, styrene / (meth) acrylic acid / (meth) acrylic ester ternary copolymer Saponification products such as saponified polymers, vinyl toluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate , At least from organic polymers soluble in alkaline aqueous solution among organic polymers according to "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by Industrial Research Council, published October 25, 1968), etc. One is mentioned.

These thermoplastic resins may be used individually by 1 type, and may use 2 or more types together. In view of sufficient cushioning properties and ease of removal after transfer, it is preferable to use a mixture of resins having two different characteristics (preferably polymer P ^H and polymer P ^L described later).
In the present invention, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.

  Among the above thermoplastic resins, a resin having a weight average molecular weight of 50,000 to 500,000 and a glass transition temperature (Tg) of 0 to 140 ° C. [hereinafter also referred to as a thermoplastic resin (a)] More preferably, a resin having a weight average molecular weight of 60,000 to 200,000 and a glass transition temperature (Tg) of 30 to 110 ° C. can be selected and used. Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-44615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP-A-60-159743, OLS3254254, JP-A-60-247638, JP-A-60-208748, JP-A-60-214354, JP-A-60-230135, JP-A-60-258539 JP-A 61-169829, JP-A 61-213213, JP-A 63-147159, JP-A 63-213837, JP-A 63-26 No. 448, JP-A 64-55551, JP-A 64-55550, JP 2-191955, JP 2-199403, JP 2-199404, JP 2-208602, and Japanese Patent Application No. 2-208602. Examples include resins that are soluble in an alkaline aqueous solution described in JP-A-4-39653 and JP-A-5-241340. Particularly preferred is a methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

  Of the various resins described above, on the low molecular side, a resin having a weight average molecular weight of preferably 3,000 to 30,000 and a glass transition temperature (Tg) of 30 to 170 ° C. [hereinafter, a thermoplastic resin. (Also referred to as (b)], more preferably, a resin having a weight average molecular weight of 4,000 to 20,000 and a glass transition temperature (Tg) of 60 to 140 ° C. can be selected and used. Preferable specific examples can be selected from those described in the above-mentioned publications and the like, and particularly preferably, styrene / (metabolites described in JP-B-55-38961 and JP-A-5-241340. ) Acrylic acid copolymer.

  If the weight average molecular weight of the thermoplastic resin (a) is 50,000 or more, or the glass transition temperature (Tg) is 0 ° C. or more, the occurrence of reticulation is prevented and the thermoplastic resin protrudes to the surroundings during transfer. Can be suppressed. If the weight average molecular weight of the thermoplastic resin (a) is 500,000 or less, or if the glass transition temperature (Tg) is 140 ° C. or lower, bubbles may enter between pixels during transfer, or the aqueous alkali solution of the thermoplastic resin can be removed. Can be suppressed.

  If the thermoplastic resin (b) constituting the thermoplastic resin layer has a weight average molecular weight of 3,000 or more or a glass transition temperature (Tg) of 30 ° C. or more, the occurrence of reticulation is prevented and the thermoplasticity is transferred during transfer. It can suppress that resin protrudes to the circumference | surroundings. If the weight average molecular weight of the thermoplastic resin (b) is within 30,000, or if the glass transition temperature (Tg) is 170 ° C. or lower, bubbles may enter between pixels during transfer, or the aqueous alkali solution of the thermoplastic resin can be removed. Can be suppressed.

Furthermore, a resin having two characteristics that are different as described above, specifically, it is preferable to use a mixture of a high molecular weight polymer P ^H and a low molecular weight polymer P ^L. Here, the low molecular weight polymer is a polymer having a weight average molecular weight of 4,000 or more and less than 12,000, and the high molecular weight polymer is a polymer having a weight average molecular weight of 12,000 or more.
The preferred form in terms of the ease of removal after transfer with sufficient cushioning property, the weight-average molecular weight of ^{P L} and weight average molecular weight of less than 10,000 5,000 is less than 60,000 120,000 This is a case of using a mixture of P ^H and, as a preferable example, methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer (P ^H ) and styrene / (meth) acrylic acid copolymer (P ^L ) And a mixture thereof.

  When mixing resins having two different types of properties, for example, when the thermoplastic resin (a) and the thermoplastic resin (b) are mixed and used, the mixing ratio is the thermoplastic resin (a). The ratio is preferably 95% by mass to 5% by mass. If the ratio of the thermoplastic resin (a) is within 95%, it is difficult for bubbles to enter between the pixels at the time of transfer, and if the ratio of the thermoplastic resin (a) is 5% or more, the thermoplastic resin is difficult to protrude to the surroundings. Moreover, since it becomes possible to prevent the thermoplastic resin layer from becoming brittle, it is difficult for fine chips to be scattered in the cutting process.

-Plasticizer-
In the present invention, the thermoplastic resin layer is made of various polymers, supercooling substances, adhesion improvers or surfactants, release agents, and the like as plasticizers in order to adjust the adhesive force and / or transferability with the temporary support. By adding a mold or the like, it is possible to finely adjust the glass transition temperature (Tg) of the thermoplastic resin layer. The plasticizer here is a compound other than the compound having an I / O value of 0.30 to 0.45.
Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, epoxy resin and polyethylene glycol mono (meth) ) Addition reaction product with acrylate, addition reaction product of organic diisocyanate and polyethylene glycol mono (meth) acrylate Things, the addition reaction product of an organic diisocyanate and polypropylene glycol mono (meth) acrylate, phthalic acid diesters, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate. Among these plasticizers, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane is particularly preferable.

The combination of the thermoplastic resin and the plasticizer is preferably 1) methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer, styrene / (meth) acrylic acid copolymer, bisphenol A and polyethylene Combination of condensation reaction product with glycol mono (meth) acrylate 2) Condensation of methacrylic acid / benzyl methacrylate copolymer, styrene / (meth) acrylic acid copolymer, bisphenol A and polyethylene glycol mono (meth) acrylate Combination of reaction products, 3) Combination of methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer, styrene / (meth) acrylic acid copolymer, phthalic acid diesters, 4) Crylic acid / benzyl methacrylate copolymer, styrene / (meth) acrylic acid copolymer, combination of phthalic acid diesters, 5) Methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylate copolymer, styrene / acrylic acid copolymer Examples thereof include a combination of a polymer and a condensation reaction product with 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane.
The amount of the plasticizer is preferably 0 to 200%, more preferably 20 to 100% in terms of a mass ratio with respect to the total of the thermoplastic resins constituting the thermoplastic resin layer.

  The thickness of the thermoplastic resin is preferably 6 μm or more. When the thickness of the thermoplastic resin is 6 μm or more, the underlying irregularities of 1 μm or more can be sufficiently absorbed. The upper limit is about 100 μm or less, preferably about 50 μm or less, from the viewpoint of the ability to remove alkaline aqueous solution and the suitability for production.

  As the coating solution for the thermoplastic resin layer in the present invention, it can be used without particular limitation as long as the resin constituting this layer is dissolved. For example, methyl ethyl ketone, n-propanol, i-propanol and the like can be used.

[Photosensitive resin layer]
As the photosensitive resin composition constituting the photosensitive resin layer in the present invention, a crosslinkable binder (hereinafter also referred to as “polymer compound (A)” having a crosslinkable group, simply “resin (A)”). The polymerizable compound (B) (hereinafter also simply referred to as “monomer”) and the photopolymerization initiator (C) are preferably contained. Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.

-Resin (A)-
In the photosensitive resin composition of the present invention, the resin (A) is a crosslinkable binder, and has a function as a binder component when a laminate such as a spacer or a colored pixel is formed.
For example, a polymer resin (polymer substance) having an allyl group capable of being polymerized by light described in paragraphs [0031] to [0054] of JP-A No. 2003-131379, which is itself crosslinkable / polymerizable, is preferable. As mentioned.
Moreover, the polymer which has crosslinkable polar groups, such as a carboxylic acid group and a carboxylate group, in a side chain is mentioned.

The polymer substance may be either a monomer homopolymer appropriately selected according to the purpose, or a copolymer composed of a plurality of monomers. You may make it use together.
Examples of the polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain include 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, crotonic acid copolymer as described in JP-A-25-25957, JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer.
Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Particularly preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid, and other Mention may be made of multicomponent copolymers with monomers.

Examples of the monomer of the polymer substance having an allyl group include a monomer having an allyl group, a monomer capable of becoming an allyl group, and other monomers. There is no restriction | limiting in particular, According to the objective, another monomer can be selected suitably. These include, for example, alkyl (meth) acrylates, aryl (meth) acrylates, hydroxyalkyl (meth) acrylates, vinyl compounds, allyl group-containing (meth) acrylates, and the like. In the present specification, (meth) acrylate represents acrylate or methacrylate.
These monomers may be used in combination of two or more in addition to being used alone.

  Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyisobutyl (meth) acrylate, hydroxypentyl ( And (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and the like. Among others, hydroxyethyl (meth) acrylate, hydroxy n-propyl (meth) acrylate, hydroxy n-butyl (meth) acrylate, etc. Is preferred.

  As the vinyl compound, for example, styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like are preferable. Can be mentioned.

  Examples of the allyl group-containing (meth) acrylate include allyl (meth) acrylate, 2-methylallyl acrylate, crotyl acrylate, chloroallyl acrylate, phenylallyl acrylate, and cyanoallyl acrylate. ) Acrylate is particularly preferred.

  Among the above-described polymer substances, a resin having at least allyl group-containing (meth) acrylate as a monomer unit is preferable, and is selected from allyl group-containing (meth) acrylate, (meth) acrylic acid, and allyl group-free (meth) acrylate. A resin having a monomer as a monomer unit is more preferable.

As a preferred specific example of the polymer substance, a binary copolymer resin of (meth) acrylic acid (M ¹ ) and allyl (meth) acrylate (M ² ) [preferred copolymerization ratio [molar ratio] is M ¹ : M ² = 2 to 90:10 to 98] or a terpolymer resin of (meth) acrylic acid (M ³ ), allyl (meth) acrylate (M ⁴ ) and benzyl (meth) acrylate (M ⁵ ). [Preferable copolymerization ratio [molar ratio] is M ³ : M ⁴ : M ⁵ = 5 to 40:20 to 90: 5 to 70].

  When the polymer substance has an allyl group, the content of the allyl group-containing monomer is preferably 10 mol% or more, preferably 10 to 100 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 20 mol%. 85 mol%.

  The weight average molecular weight of the polymer substance is preferably 5,000 to 100,000, and more preferably 8,000 to 50,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting the weight average molecular weight within the range of 5,000 to 100,000, the film strength can be improved.

Furthermore, the resin (A) contains a group having a branched and / or alicyclic structure in the side chain: X (x mol%), a group having an acidic group in the side chain: Y (y mol%), and a side chain. A group having an ethylenically unsaturated group: one containing Z (z mol%) is preferable, and may have another group (L) (1 mol%) as necessary.
A plurality of X, Y, and Z may be combined in one group in the resin (A).

-Group having branched and / or alicyclic structure in side chain: X-
The “group having a branched and / or alicyclic structure in the side chain” will be described.
First, as the group having a branch, a branched alkyl group having 3 to 12 carbon atoms is shown, for example, i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, Examples include neopentyl group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are more preferable.

  Next, the group having an alicyclic structure represents an alicyclic hydrocarbon group having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, Examples thereof include an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, and a tricyclopentanyl group. Among these, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like are preferable, and a cyclohexyl group, a norbornyl group, an isobornyl group, a tricyclopentenyl group, and the like. Is preferred.

  Examples of the monomer containing a group having a branched and / or alicyclic structure in the side chain include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like ( (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, (meth ) T-butyl acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylic acid 3-octyl, t-octyl (meth) acrylate, and the like are mentioned. Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, and the like are preferable, and more preferable. I-propyl methacrylate, t-butyl methacrylate and the like.

  Next, a specific example of the monomer containing a group having an alicyclic structure in the side chain is (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic. Acid-3-methyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-1-adamantyl, (meth) acrylic acid-3-ethyladamantyl, (meth) acrylic acid-3-methyl-5-ethyl -1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2- Methyl-2-adamantyl, (meth) acrylic acid 2-ethyl-2-adamantyl, (meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid Kutahydro-4,7-mentanoinden-5-yl, (meth) acrylate octahydro-4,7-mentanoinden-1-ylmethyl, (meth) acrylate-1-menthyl, (meth) acrylate tricyclo Decyl, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo [ 4.1.0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2,5-trimethylcyclohexyl, (meth) And cyclohexyl acrylate. Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 1-menthyl, (meth) acrylic acid tricyclodecyl, etc. are preferable, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, ( Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

  Furthermore, specific examples of the monomer containing a group having an alicyclic structure in the side chain include compounds represented by the following general formula (1) or (2). Here, in the general formulas (1) and (2), x represents 1 or 2, and R represents hydrogen or a methyl group. m and n each independently represent 0-15. Among general formulas (1) and (2), x = 1 or 2, m = 0 to 8, and n = 0 to 4 are preferable, and m = 1 to 4 and n = 0 to 2 are more preferable. Preferable specific examples of the compound represented by the general formula (1) or (2) include the following compounds D-1 to D-5 and T-1 to T-8.

As the monomer containing a group having an alicyclic structure in the side chain, an appropriately produced monomer may be used, or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M,
H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M and the like can be mentioned. Among these, FA-512A (S) and 512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

-Group having an acidic group in the side chain: Y-
There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things, For example, a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned. Among these, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

  The monomer having an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like (meth) Acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Specific examples of the monomer having an acidic group in the side chain can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate. Ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone A mono (meth) acrylate etc. are mentioned. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  As said commercial item, Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB-1, NK ester CBX-1, manufactured by Kyoeisha Oil Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

—Group having an ethylenically unsaturated group in the side chain: Z—
The “ethylenically unsaturated group in the side chain” is not particularly limited, and the ethylenically unsaturated group is preferably a (meth) acryloyl group. The connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group. The method of introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known ones, for example, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group, or having a hydroxyl group Examples include a method of adding a (meth) acrylate having an isocyanate group to the group, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, and the like.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

  The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these. For example, in the compound represented by the following structural formula (1) and the following structural formula (2) The compounds represented are preferred.

In the Structural Formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

In the Structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable than the structural formula (2). In the structural formulas (1) and (2), it is more preferable that L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) or a structural formula (2), For example, the following exemplary compounds (1)-(10) are mentioned.

-Other groups: L-
The monomer of the other group is not particularly limited, for example, (meth) acrylic acid ester having no branched and / or alicyclic structure, styrene, vinyl ether group, dibasic acid anhydride group, vinyl ester group, And monomers having a hydrocarbon alkenyl group.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in the said resin (A), it is preferable that molar composition ratio is 0-30 mol%, and it is more preferable that it is 0-20 mol%.

  Specific examples of the resin (A) include compounds represented by the following compounds P-1 to P-35.

―About manufacturing method―
The resin (A) is produced from a two-stage process including a (co) polymerization process of monomers and a process of introducing ethylenically unsaturated groups.
First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

-Molecular weight-
The weight average molecular weight of the copolymer suitable as the resin (A) is preferably 7,000 to 100,000, more preferably 8,000 to 80,000, and particularly preferably 9,000 to 50,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of the copolymer.

-Glass transition temperature-
The glass transition temperature (Tg) suitable for the resin (A) is preferably 40 to 180 ° C, more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.

-Acid value-
The preferred range of the acid value suitable for the resin (A) varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH / g. It is particularly preferred that When the acid value is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.

The resin (A) has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 7,000 to 100,000, whereby a photospacer having good developability and mechanical strength can be obtained. This is preferable.
Furthermore, the preferable example of the said resin (A) has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

The copolymer composition ratio of the respective components of the resin (A) is determined in consideration of the glass transition temperature and the acid value, and cannot be generally stated, but “group having a branched and / or alicyclic structure in the side chain” "Is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%. When the group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and the developer resistance of the image area is also good.
Moreover, 5-70 mol% is preferable, and "group which has an acidic group in a side chain" has more preferable 10-60 mol%, and 20-50 mol% is especially preferable. When the group having an acidic group in the side chain is within the above range, good curability and developability can be obtained.
Moreover, 10-70 mol% is preferable, "group which has an ethylenically unsaturated group in a side chain", 20-70 mol% is still more preferable, and 30-70 mol% is especially preferable. When the group having an ethylenically unsaturated group in the side chain is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.

  As content of the said resin (A), 5-70 mass% is preferable with respect to the photosensitive resin composition total solid, and 10-50 mass% is more preferable. The resin (A) can contain other resins described later, but only the resin (A) is preferable.

-Other resins-
As the resin that can be used in combination with the resin (A), a compound exhibiting swelling property with respect to an alkaline aqueous solution is preferable, and a compound that is soluble in an alkaline aqueous solution is more preferable.
As the resin exhibiting swellability or solubility with respect to an alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain And the like, and a maleamic acid copolymer are preferable.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

-Ratio of resin (A) to other resins-
The total content of the resin (A) and the resin that can be used in combination is preferably 5 to 70% by mass and more preferably 10 to 50% by mass with respect to the total solid content of the photosensitive resin composition. When the solid content is 5% by mass or more, weakening of the film strength of the photosensitive resin layer described later can be suppressed and deterioration of the tackiness of the surface of the photosensitive resin layer can be prevented. Moreover, if it is within 70 mass%, the fall of exposure sensitivity can be suppressed. In addition, the said content has shown that solid content.

-Polymerizable compound (B) and other components-
In the present invention, other than those described above, the polymerizable compound (B), the photopolymerization initiator (C), and other components constituting the known composition can be suitably used. For example, JP-A-2006-23696 Ingredients listed in paragraph Nos. [0010] to [0020] of JP, No. 2006-64921, and components described in paragraph Nos. [0027] to [0053] of JP-A No. 2006-64921.

  In the relationship with the resin (A), the mass ratio ((B) / (A) ratio) of the polymerizable compound (B) to the resin (A) is preferably 0.3 to 1.5, and It is more preferably 4 to 1.4, and particularly preferably 0.5 to 1.2. When the ratio (B) / (A) is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.

-Colorant-
In the photosensitive resin composition of the present invention, various conventionally known pigments suitable for color filter use can be selected and used as a colorant, depending on the purpose.

In the photosensitive resin composition of the present invention, conventionally known various pigments suitable for color filter applications can be selected and used in combination according to the purpose.
As the pigment that can be used in the photosensitive resin composition according to the present invention, various conventionally known inorganic pigments or organic pigments can be used. In addition, it is preferable to use a pigment having a particle size as small as possible considering that it is preferable that the formed photosensitive resin composition has a high light transmittance regardless of whether it is an inorganic pigment or an organic pigment. In consideration of handling properties, the average particle size of the pigment is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As an organic pigment, for example,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment Black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 1

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as red pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments And the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 5 or more, the light transmittance from 400 nm to 500 nm can be suppressed, and the color purity can be increased. If it is 100: 50 or less, the dominant wavelength is less likely to be shorter than the short wavelength, and deviation from the NTSC target hue can be suppressed. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If the mass ratio is 100: 5 or more, the light transmittance of 400 nm to 450 nm can be suppressed, and the color purity can be increased. In addition, if it is within 100: 150, the dominant wavelength is less likely to be longer than the long wavelength, and deviation from the NTSC target hue can be suppressed. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture of this and a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon pigments other than the black pigment, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of the black pigment and titanium carbon is preferable. The mass ratio of the black pigment to titanium carbon is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

The pigment in the present invention preferably has an average particle diameter r (unit: nm) satisfying 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. By using such a pigment having an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

-Pigment dispersant-
In the present invention, when a pigment is used as the colorant, a known pigment dispersant can be used in combination. Examples of the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic. -Based copolymers, naphthalenesulfonic acid formalin condensates], and polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  The content of the color pigment in the photosensitive resin composition is preferably 30% by mass or more and 90% by mass or less, and preferably 40% by mass or more and 85% by mass or less based on the total solid content constituting the composition. Is more preferable, and it is further more preferable that it is 50 to 80 mass%.

-Fine particles (D)-
In the photosensitive resin composition, it is preferable to add fine particles. For example, it is suitable for forming a spacer for liquid crystal display. The fine particles (D) are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A No. 2003-302039 [0035] to [0041] are preferable. Colloidal silica is preferred from the viewpoint of obtaining a photospacer having good developability and mechanical strength.

  The average particle diameter of the fine particles (D) is preferably 5 to 50 nm, more preferably 10 to 40 nm, and more preferably 15 to 30 nm from the viewpoint that a photospacer having high mechanical strength can be obtained. Is particularly preferred.

  In addition, the content of the fine particles (D) is 5 to 50% by mass with respect to the total solid content in the photosensitive resin composition in the present invention from the viewpoint that a photospacer having high mechanical strength is obtained. It is preferably 10 to 40% by mass, more preferably 15 to 30% by mass.

-Surfactant-
The photosensitive resin composition in the present invention preferably further contains at least one surfactant. By containing the surfactant, display unevenness (including color unevenness due to film thickness variation) can be effectively prevented, and an image with high display quality can be obtained. For example, when a liquid crystal display device is configured by producing a color filter, an image with high display quality can be displayed while suppressing display unevenness of the image.

  As the surfactant, those which are mixed with the constituent components of the photosensitive resin composition can be appropriately selected. Specifically, as preferable surfactants, paragraph numbers [0015] to [0024] of JP-A No. 2003-337424, paragraph numbers [0012] to [0017] of JP-A No. 2003-177522, JP 2003 Paragraph numbers [0012] to [0015] of JP-A-177523, paragraph numbers [0010] to [0013] of JP-A-2003-177521, and paragraph numbers [0010] to [0013] of JP-A-2003-177519. JP, 2003-177520, paragraph Nos. [0012] to [0015], JP-A No. 11-133600, paragraph numbers [0034] to [0035] and JP-A No. 6-16684 are disclosed as inventions. The surfactant which is mentioned is mentioned.

From the viewpoint of obtaining a higher effect, a fluorosurfactant and / or a silicone surfactant (a fluorosurfactant, a silicone surfactant, a surfactant containing both a fluorine atom and a silicon atom) It is preferable to select any one of them, or two or more thereof, and a fluorosurfactant is most preferable.
When using the said fluorosurfactant, the number of fluorine atoms of the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. . When the number of fluorine atoms is in the above range, solubility in an ordinary solvent not containing fluorine is ensured, and film thickness fluctuation caused by unevenness due to coating or the like can be effectively prevented.

  Commercially available surfactants can also be used as they are. Commercially available surfactants include, for example, F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co.), MegaFuck F171, F173, F176, F189, F780F, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), etc. Fluorine type surfactant or silicone type surfactant can be mentioned. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicone surfactant.

  As content in surfactant in the photosensitive resin layer, 0.01-10 mass% is preferable with respect to solid content (mass) of the photosensitive resin layer, and 0.1-7 mass% is more preferable. When the content of the surfactant is particularly in the above range, it is effective for preventing display unevenness in a high-contrast display image.

[Middle layer]
The photosensitive transfer material is preferably provided with an intermediate layer for the purpose of preventing mixing of components during the application of a plurality of layers and during storage after the application. For example, it can be formed between a thermoplastic resin layer and a photosensitive resin layer.
As the intermediate layer, an oxygen barrier film having an oxygen barrier function, which is described as “separation layer” in JP-A-5-72724, is preferable, which increases the sensitivity during exposure and reduces the time load of the exposure machine. And productivity is improved.

The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones.
For example, it may be configured using a resin such as polyvinyl alcohol resin, polyvinyl pyrrolidone resin, cellulose resin, acrylamide resin, polyethylene oxide resin, gelatin, vinyl ether resin, polyamide resin, or a copolymer thereof. Among them, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

You may add additives, such as surfactant, to an intermediate | middle layer as needed.
The thickness of the intermediate layer is preferably in the range of 0.1 to 5 μm, more preferably in the range of 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not deteriorated, and it is possible to prevent the intermediate layer removal time during development from increasing.

  The intermediate layer can be applied by applying a coating solution prepared using the resin and, if necessary, an additive. A solvent can be used for the preparation of the coating solution, and the solvent is not particularly limited as long as the resin can be dissolved, and water or a mixed solvent obtained by mixing water-miscible organic solvent is particularly preferable. .

-Other layers-
The photosensitive transfer material of the present invention can be suitably configured by further providing a protective film or the like on the surface of the photosensitive resin layer.

A thin protective film is preferably provided on the surface of the photosensitive resin layer in order to protect it from contamination and damage due to impurities such as dust during storage. As the protective film, a film that can be easily peeled off from the photosensitive resin layer can be used, and a film made of the same or similar material as the temporary support can be suitably selected.
Suitable materials that can be used for the protective film include, for example, silicon paper, polyolefin films and sheets, and polytetrafluoroethylene films and sheets.

[Production of photosensitive transfer material]
The photosensitive transfer material of the present invention has a thermoplastic resin layer and a photosensitive resin layer in order from the temporary support side, and at least one intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. It is preferable to have.
In this photosensitive transfer material, a thermoplastic resin layer coating solution is applied onto a temporary support, dried to provide a thermoplastic resin layer, and then an intermediate layer coating solution is applied onto the thermoplastic resin layer. Then, the intermediate layer is laminated by drying, and a coating solution for the photosensitive resin layer is further coated on the intermediate layer, and dried to laminate the photosensitive resin layer.
Here, the coating solution for the thermoplastic resin layer is a compound having an I / O value of 0.30 to 0.45 or, as necessary, a solution in which an additive is dissolved together with a thermoplastic organic polymer. The intermediate layer coating solution can be prepared, and is preferably a preparation solution prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer. Moreover, it is preferable to prepare the said coating liquid for photosensitive resin layers using the solvent which does not melt | dissolve an intermediate | middle layer.

  When a photosensitive resin layer is coated on a temporary support, a photosensitive resin layer coating solution prepared to be photosensitive is formed by a known coating method (for example, coating using a coating machine such as a slit coater). Can do. The same can be applied to the case where other layers such as a thermoplastic resin layer and an intermediate layer other than the photosensitive resin layer are provided.

  Examples of the known coating methods include spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, gravure coating, slit coating, or US Patent No. Examples include an extrusion coating method using a popper described in US Pat. No. 2,681,294.

  Among these, it is preferable to apply by means of a slit-like nozzle having a slit-like hole in a portion from which the liquid is discharged or by a slit coater. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Application Laid-Open No. 2001-310147 and the like are preferably used.

  In addition to the above, prepare a first sheet provided with a thermoplastic resin layer and an intermediate layer in order from the temporary support side on the temporary support, and a second sheet provided with a photosensitive resin layer on the protective film, It can also produce by bonding together so that the intermediate | middle layer surface of a 1st sheet | seat and the surface of the photosensitive resin layer may contact | connect. Furthermore, a first sheet provided with a thermoplastic resin layer on a temporary support and a second sheet provided with a photosensitive resin layer and an intermediate layer in order from the protective film side on a protective film are prepared. It can also be produced by bonding so that the surface of the intermediate layer of the sheet is in contact with the surface of the thermoplastic resin layer of the second sheet.

<Color filter and manufacturing method thereof>
The method for producing a color filter of the present invention comprises a transfer step of transferring at least a photosensitive resin layer onto a substrate using the above-described photosensitive transfer material of the present invention, and at least a photosensitive resin layer transferred onto the substrate. An exposure process for exposure and a development process for developing the exposed photosensitive resin layer are provided.

  In the transfer step, the photosensitive transfer material of the present invention is used, the photosensitive resin layer provided on the temporary support is overlaid so that the surface thereof is in contact with the surface of the substrate that is the transfer material, and further heated. And the photosensitive resin layer is transcribe | transferred to a board | substrate surface by bonding by pressure-bonding or thermocompression bonding with the pressurized roller or flat plate, and peeling after that.

  Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

A transparent substrate is suitable for the substrate to be transferred. For example, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic glass plate. A film etc. can be mentioned. Moreover, the substrate can be made to have good adhesion with the photosensitive resin layer of the photosensitive tree transfer material by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used.
In addition, as thickness of a board | substrate, 700-1200 micrometers is generally preferable.

  In the exposure step, the photosensitive resin layer transferred and formed on the substrate in the transfer step is exposed in a pattern. Specifically, for example, a predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and further above the mask (mask photosensitive resin) via the mask and optionally a thermoplastic resin layer and an intermediate layer. From the side not facing the photosensitive resin layer).

As a light source used for exposure, a light source that can be irradiated with light in a wavelength range that belongs to the sensitive wavelength of the photosensitive resin layer and can be cured (eg, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

In the developing step, at least the photosensitive resin layer exposed in the exposing step is developed using a developer. There is no restriction | limiting in particular as a developing solution, Well-known developing solutions, such as a thing described in Unexamined-Japanese-Patent No. 5-72724, can be used.
The developer preferably has a developing behavior in which the photosensitive resin layer exhibits solubility. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / l is preferable. Further, a small amount of an organic solvent miscible with water may be added.

Examples of water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, Examples include 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 organic solvent is preferably 0.1 to 30% by mass.
Further, a known surfactant may be further added to the developer, and the concentration of addition is preferably 0.01 to 10% by mass.

As a development method, any of paddle development, shower development, shower & spin development, dip development and the like may be used.
In the case of shower development, an uncured portion can be removed by spraying a developer onto the photosensitive resin layer after the exposure process. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.
Further, before development, it is preferable to spray an alkaline solution having a low solubility of the photosensitive resin layer by a shower or the like in advance to remove the thermoplastic resin layer, the intermediate layer, and the like. After the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.

  As the cleaning agent, known ones can be used. For example, T-SD1 (containing phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer) manufactured by Fuji Film Co., Ltd. or T- SD2 (containing sodium carbonate and phenoxyoxyethylene surfactant) can be preferably used.

  Further, the developed photosensitive resin layer can be baked by heating. The baking treatment is preferably performed at 200 to 240 ° C. for about 10 to 20 minutes.

  As described above, by using the photosensitive transfer material of the present invention, a cured product (a light shielding film such as a black matrix when carbon black is mainly included as a colorant and is black-colored) can be formed. it can. For example, when a black matrix is formed on a substrate using the photosensitive transfer material of the present invention, a color filter is prepared by providing red (R), green (G), and blue (B) colored pixels on the substrate. can do. Specifically, a method of forming a photosensitive resin layer colored R, G, or B on a substrate with a black matrix and repeating the operation of exposing and developing at least the number of desired colors is known. Can be produced by a method.

Hereinafter, the method for producing a color filter of the present invention will be described in more detail by taking as an example the case of transferring a black matrix.
i) Substrate cleaning First, an alkali-free glass substrate (hereinafter abbreviated as “glass substrate”) is prepared, and cleaning is performed in advance to remove stains on the glass substrate surface before the transfer step. For example, glass cleaner liquid adjusted to 25 ° C. (trade names: T-SD1, T-SD2, manufactured by Fuji Film Co., Ltd.) is washed with a rotating brush having nylon hair while spraying for 20 seconds in a shower, and further purified water Perform shower cleaning.

ii) Silane coupling treatment In order to enhance the adhesion of the photosensitive resin layer by lamination in the subsequent transfer step, it is preferable to carry out a silane coupling treatment. As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds by a shower, and pure water shower washing is performed. To do. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate with a laminator.

iii) Lamination (transfer process)
The glass substrate after the cleaning and silane coupling treatment is heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to a laminator. Then, after peeling off the protective film of the photosensitive transfer material, the exposed photosensitive resin layer is transferred to a glass substrate surface already heated to 100 ° C. using a laminator, with a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and conveyed. Lamination is performed at a speed of 2.2 m / min. If the rubber roller is 150 ° C. or higher, the transfer material will be wrinkled, and if it is 100 ° C. or lower, the adhesion of the photosensitive resin layer may be weak.

iv) Exposure (exposure process)
Next, after peeling off the temporary support, exposure is performed in a pattern with a proximity type exposure machine equipped with an ultrahigh pressure mercury lamp. When the substrate size is 50 cm or more, it is preferable that the substrate and the mask (quartz exposure mask having an image pattern) are both exposed in a vertical state in order to prevent the mask from being bent. The shorter the distance between the exposure mask surface and the photosensitive resin layer surface, the better the resolution, but foreign matter tends to adhere, so 100 to 300 μm is desirable. The exposure amount is desirably 10 to 80 mJ / cm ² .

v) Removal of thermoplastic resin layer and intermediate layer After exposure, triethanolamine developer T-PD1 (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent; Fuji Film ( The thermoplastic resin layer and the intermediate layer are developed and removed by, for example, a product of KK Corporation. At this time, ideally, it is desirable that the photosensitive resin layer is set to a condition in which development is not performed at all. For example, it is desirable to supply in a shower form at a flat nozzle pressure of 0.04 MPa at 30 ° C. for 50 seconds.

vi) Development of photosensitive resin layer (development process)
Next, the photosensitive resin layer is developed with alkali to form a pattern forming a black matrix. For example, sodium carbonate developer T-CD1 (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% by weight of sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer Contained; manufactured by FUJIFILM Corporation). The condition is, for example, a shower at 35 ° C. for 35 seconds and a cone type nozzle pressure of 0.15 MPa. As the developing solution, KOH type or TMA type may be used.

vii) Residue removal Subsequently, the residue is removed using a cleaning agent (T-SD1, T-SD2, etc. manufactured by Fuji Film Co., Ltd.) to remove the remaining components of the photosensitive resin layer in the unexposed area. The conditions include, for example, a shower at a cone type nozzle pressure of 0.02 MPa for 20 seconds at 33 ° C. and rotation by a rotating brush having nylon bristles.

viii) Post-exposure Next, the glass substrate is subjected to post-exposure from the side where the pattern is formed with an ultra-high pressure mercury lamp at about 500 mJ / cm ² . Thereby, the polymerization effect in the subsequent baking is enhanced, and the cross-sectional shape of the black matrix after baking can be adjusted by the amount of post exposure. You may implement from both surfaces and can select in the range of 100-800 mJ / cm < ² >.

ix) Baking process (baking process)
In order to react the monomer or oligomer to form a hard film, baking is preferably performed. The baking is preferably performed at 200 to 240 ° C. for about 10 to 20 minutes. In the case where the RGB colored pixels are formed in the same manner as described above after the black matrix is formed, the baking process may be performed collectively after the black matrix and the colored pixels are formed.

  The color filter of the present invention is produced as described above by the method for producing a color filter of the present invention. Since the photosensitive transfer material of the present invention described above is used, a transferred image (black matrix) is produced. Are not likely to cause transfer defects even when transferred at high speed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

<Example 1>
(Photosensitive transfer material)
Each component of the following formulation 1 is mixed on a 75 μm-thick polyethylene terephthalate film temporary support (PET temporary support), and further sebacic acid so as to be 0.8% by mass of the total mass of the thermoplastic resin layer. Dioctyl (I / O value = 0.35) was added to prepare a coating solution for a thermoplastic resin layer. This was applied and dried at 100 ° C. for 5 minutes to form a thermoplastic resin layer having a dry layer thickness of 15 μm.

[Formulation 1 of coating solution for thermoplastic resin layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55/12/5/28 [molar ratio], weight average molecular weight 90,000)
.... 93.1 parts
Styrene / acrylic acid copolymer (= 63/37 [molar ratio], weight average molecular weight 8000)
... 113.7 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
... 106.5 parts-Surfactant 1 (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc.)
··· 6.0 parts · Methanol · · · 175.0 · · 1-methoxy-2-propanol · · · 80.0 · · Methyl ethyl ketone · · · 425.7 parts

  Next, an intermediate layer coating solution having the following formulation B was applied onto the formed thermoplastic resin layer and dried at 100 ° C. for 5 minutes to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol (PVA-205, saponification rate 80%, manufactured by Kuraray Co., Ltd.)
・ ・ ・ ・ 32.2 parts ・ Polyvinylpyrrolidone (PVP K-30, manufactured by IS Japan Co., Ltd.)
··· 14.8 parts · Methanol · · · 429 parts · Distilled water · · · 524 parts

Next, a dark color composition K1 (photosensitive resin layer coating solution) prepared as shown below was further applied onto the formed intermediate layer, dried at 100 ° C. for 5 minutes, and dried layer thickness 2 A 3 μm photosensitive resin layer was laminated.
The K pigment dispersion 1 having the formulation shown below and propylene glycol monomethyl ether acetate were measured in the amounts shown in Table 1 below, and mixed at a temperature of 24 ° C. While stirring this mixture at 24 ° C. and 150 rpm for 10 minutes, the amounts of methyl ethyl ketone, cyclohexanone, binder 2, phenothiazine, DPHA solution, 2,4-bis (trichloromethyl) -6 shown in Table 1 below. -[4 '-(N, N-bisdiethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine and the surfactant 1 were added in this order. Then, the dark color composition K1 was obtained by stirring for 30 minutes at the rotation speed of 150 rpm under the temperature of 40 degreeC.
In addition, the quantity of the following Table 1 is a mass part, and the detail of each composition is as follows.

[K pigment dispersion 1]
・ Carbon black (Nippex 35 manufactured by Degussa) ... 13.1%
・ Dispersant (compound 1 below) ・ ・ ・ ・ 0.65%
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000)
・ ・ ・ ・ 6.72%
・ Propylene glycol monomethyl ether acetate 79.5%

[Binder 2]
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

[DPHA solution]
・ Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate: 24%

  After forming the laminated structure of the PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer as described above, a polypropylene film having a thickness of 12 μm is further formed on the surface of the photosensitive resin layer as a cover film. A photosensitive transfer material was obtained by pasting by heating and pressing.

[Evaluation of photosensitive transfer material]
The photosensitive transfer material of Example 1 was evaluated as follows.
-Evaluation of transferability-
A glass substrate (thickness: 1.1 mm) in which a square having a side of 500 μm and a pixel having a height of 2.3 μm was formed in a checkered pattern on the front surface of the substrate was prepared. Both were laminated so that the photosensitive resin layer of the photosensitive transfer material from which the polypropylene sheet had been peeled and the side on which the pixels of the glass substrate were formed faced each other, and were laminated using a laminator (VP-11 manufactured by Osaka Laminator Co., Ltd.). Lamination conditions were a roller temperature of 130 ° C., a pressure of 10 kg / cm, and a speed of 0.8 m / min.
After the lamination, the size of bubbles generated was evaluated by observing the substrate with an optical microscope. When bubbles were generated, the shape was either a circle, an ellipse, or a diamond with a corner. Therefore, the diameter of the circle, the length of the major axis of the ellipse, and the length of the longer diagonal of the rhombus were classified as the bubble size as follows.
A: No bubble is generated B: Bubble size is less than 30 μm C: Bubble size is 30 μm or more and less than 60 μm D: Bubble size is 60 μm or more and less than 100 μm E: Bubble size is 100 μm or more It is shown in FIG.

-Evaluation of rechation-
The photosensitive transfer material with the cover film peeled off was stored for 3 days in an atmosphere of 45 ° C./75% RH. Thereafter, the photosensitive resin layer and the intermediate layer were peeled off, and the surface of the thermoplastic resin layer was observed with an optical microscope to observe the occurrence of reticulation. The degree of rechuking was classified into the following three ranks and evaluated.
A: No recursion occurred B: Recuration slightly occurred and irregularities were observed on the surface of the thermoplastic resin layer C: Reticulation occurred and a wrinkled pattern was observed on the surface of the thermoplastic resin layer The evaluation results are shown in Table 8.

-Evaluation of seepage of thermoplastic resin layer-
The photosensitive transfer material with the cover film attached is cut into a size of 5 cm × 5 cm, and 20 sheets of the photosensitive transfer material are coated on the surface of the cover film (the surface on which the photosensitive resin layer is not provided). And the surface of the temporary support (the surface on which the photosensitive resin layer is not provided) were sequentially overlapped and placed on a horizontally placed table. On top of this, a weight of 5 kg was applied and stored for 3 days. Thereafter, it was observed whether or not the thermoplastic resin layer oozed out to the periphery of the photosensitive transfer material and the photosensitive transfer material was stuck to each other. Those that cause sticking are not preferred. Here, the degree of sticking was classified into the following three ranks and evaluated.
A: No sticking has occurred B: Slight sticking has occurred, but the sticking is slightly removed C: Sticking has occurred and the photosensitive transfer materials are firmly connected to each other Table 8 shows the evaluation results.

(Color filter)
As shown below, a color filter is produced by transfer using the photosensitive transfer material of Example 1 (black photosensitive transfer material K201) obtained as described above and the following colored photosensitive transfer materials (R201, G201, B201). did. The black photosensitive transfer material K201 was stored for 3 days in an atmosphere of 45 ° C./75% RH with the cover film attached.

[Preparation of colored photosensitive transfer materials R201, G201, B201]
Apply a coating solution for a thermoplastic resin layer consisting of the following formulation H1 to the surface of a 75 μm thick polyethylene terephthalate temporary support (PET temporary support) using a slit nozzle so that the dry film thickness is 14.6 μm. And dried to form a thermoplastic resin layer. Next, on this thermoplastic resin layer, the intermediate layer coating solution comprising the above-mentioned formulation B was applied using a slit nozzle so that the dry film thickness was 1.6 μm, and dried to laminate the intermediate layer.
Three PET temporary supports on which the thermoplastic resin layer and the intermediate layer were laminated as described above were prepared.

-Formulation H1- of coating liquid for thermoplastic resin layer
· Methanol ···· 11.1 parts · Propylene glycol monomethyl ether ··· 6.36 parts · Methyl ethyl ketone ····· 52.4 parts · Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer Copolymer (copolymerization ratio [molar ratio] = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 90,000, Tg≈70 ° C.)
... 5.83 parts styrene / acrylic acid copolymer (copolymerization ratio [molar ratio] = 63/37, weight average molecular weight = 8,000, Tg≈100 ° C.)
··· 13.6 parts · BPE-500 ··· 9.1 parts (compound obtained by dehydration condensation of 2 equivalents of pentaethylene glycol monomethacrylate to bisphenol A; manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ Surfactant 1 (methyl isobutyl ketone 30 mass% solution) 0.54 parts

  Next, a red photosensitive resin composition R201 having a composition shown in Table 2 below, a green photosensitive resin composition G201 having a composition shown in Table 3 below, and a blue photosensitive resin composition B201 having a composition shown in Table 4 below, respectively. Prepared according to the preparation procedure in each table. Next, each of the obtained red photosensitive resin composition R201, green photosensitive resin composition G201, and blue photosensitive resin composition B201 is slit on an intermediate layer on a separate PET temporary support. Are further laminated and applied so that the film thickness becomes 2.4 μm, dried, and the colored photosensitive resin layers R, G, and B of red (R), green (G), or blue (B) are dried. Formed. A polypropylene film having a thickness of 12 μm was further pressure-bonded onto the formed colored photosensitive resin layer of each color to provide a protective film. As described above, a colored photosensitive transfer material for forming a colored pixel, which has a laminated structure of a temporary PET support / thermoplastic resin layer / intermediate layer / red, green or blue colored photosensitive resin layer / protective film. R201, G201, and B201 were produced.

  First, an alkali-free glass substrate (hereinafter abbreviated as “glass substrate”) was prepared, and this substrate was preliminarily adjusted to 25 ° C. before being transferred to a glass detergent solution T-SD1 (manufactured by Fuji Film Co., Ltd.). Was washed with a rotating brush having nylon bristles while spraying for 20 seconds in a shower to perform pure water shower washing. Then, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and a pure water shower Washed. Thereafter, the glass substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device.

  After peeling off and removing the protective film of the black photosensitive transfer material K201 obtained as described above, the exposed black colored photosensitive resin layer is overlaid so as to be in contact with the surface of the glass substrate heated to 100 ° C. They were bonded together under the conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveying speed of 2.2 m / min using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.). Next, the PET temporary support was peeled off and transferred onto the glass substrate in the order of the black colored photosensitive resin layer / intermediate layer / thermoplastic resin layer (transfer process).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer were arranged to face each other. The distance between the mask surface and the surface of the black colored photosensitive resin layer in contact with the intermediate layer of the black colored photosensitive resin layer is set to 200 μm in a state where the glass substrate stands substantially parallel and vertically, and from the thermoplastic resin layer side through the mask. The entire surface was exposed with an exposure amount of 50 mJ / cm ² (exposure process).

After exposure, pure water is sprayed from a shower nozzle to uniformly wet the surface of the black colored photosensitive resin layer, and then KOH-based developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd .; KOH and nonionic interface) An activator-containing alkaline developer) diluted 100 times with pure water was sprayed from a flat nozzle at 25 ° C. and a nozzle pressure of 0.04 MPa for 60 seconds to perform a shower development to obtain a black pattern (development process) .
Subsequently, ultrapure water was sprayed onto the glass substrate on which the black pattern was formed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle to remove the residue, and then heat treated (baked) at 220 ° C. for 30 minutes. (Baking process) A black matrix was formed on an alkali-free glass substrate.

Next, colored pixels of R, G, and B colors were formed in order as follows.
First, using the colored photosensitive transfer material R201 obtained above on a glass substrate on which a black matrix is formed, transfer, exposure, development, and baking are performed in the same manner as in the formation of the black matrix, and glass is formed. Red pixels (R pixels) were formed on the side of the substrate where the black matrix was formed. At this time, the development time with a KOH developer (25 ° C.) was set to 100 seconds. Thereafter, the glass substrate on which the R pixel is formed is again cleaned with a brush using a cleaning agent as described above, shower-washed with pure water, and then sent to a substrate preheating device without using a silane coupling solution. And heated at 100 ° C. for 2 minutes.

Next, as in the case of forming the R pixel, the transfer, exposure, development, and baking processes are performed using the colored photosensitive transfer material G201, and the green pixel is provided on the side where the black matrix and the R pixel are provided. (G pixel) was formed. However, the exposure amount in the exposure step was 40 mJ / cm ² , and the development process in the development step was 34 ° C. for 45 seconds. After that, the glass substrate on which the R pixel and the G pixel are formed is again cleaned with a brush using a cleaning agent as described above, shower-washed with pure water, and then pre-heated without using a silane coupling liquid. It was sent to the apparatus and heated at 100 ° C. for 2 minutes.
Subsequently, as in the case of forming the R pixel and the G pixel, transfer, exposure, and development processes (excluding the baking process) are performed using the colored photosensitive transfer material B2, and the black matrix of the glass substrate is formed. In addition, a blue pixel (B pixel) was formed on the side where the R pixel and the G pixel were provided. However, the exposure amount in the exposure step was 30 mJ / cm ² , and the development process in the development step was 36 ° C. for 40 seconds.
Thereafter, the glass substrate on which each of the R, G, and B pixels was formed was baked at 240 ° C. for 50 minutes by a substrate preheating device to obtain a color filter (color filter substrate).

[Evaluation of color filter]
The color filter of Example 1 was evaluated as follows.
-Display unevenness-
The color filter was irradiated with an Na lamp from an oblique direction in a dark room and observed visually and with a magnifying glass to determine whether unevenness occurred. The degree of display unevenness was evaluated as follows.
A: Display unevenness was not recognized at all.
B: Display unevenness was slightly recognized.
C: Display unevenness was noticeable.
The evaluation results are shown in Table 8.

<Examples 2 to 11>
In the production process of the photosensitive transfer material of Example 1, in the coating liquid component for the thermoplastic resin layer, 0.8% by mass of dioctyl sebacate was changed to the compound types shown in Table 8 with Example 1 In the same manner, a photosensitive transfer material was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.
In the color filter manufacturing process of Example 1, the photosensitive transfer material of Example 1 (black photosensitive transfer material K201) was replaced with the photosensitive transfer material of Examples 2 to 11 (black photosensitive transfer material K202). Each color filter was manufactured in the same manner as in Example 1 except that it was replaced with ~ K211). Evaluation similar to Example 1 was performed about the photosensitive transfer material and color filter of Examples 2-11. The evaluation results are shown in Table 8.

<Example 12>
In the manufacturing process of the photosensitive transfer material of Example 1, the red photosensitive resin composition R201, the green photosensitive resin composition G201, and the blue photosensitive resin composition B201 are each represented by the red photosensitive resin described in Tables 5 to 7 below. Colored photosensitive transfer materials R301, G301 for forming colored pixels, except that the photosensitive resin composition R301, the green photosensitive resin composition G301, and the blue photosensitive resin composition B301 were changed. And B301 were produced.
Further, in the color filter manufacturing process of Example 1, the red photosensitive transfer material R201, the green photosensitive transfer material G201, and the blue photosensitive transfer material B201 are respectively converted into a red photosensitive transfer material R301 and a green photosensitive transfer material G301. A color filter was produced in the same manner as in Example 1, except that the blue photosensitive transfer material B301 was used. Evaluation similar to Example 1 was performed about the photosensitive transfer material of Example 12, and a color filter. The evaluation results are shown in Table 8.

  The preparation methods of R pigment dispersion composition 2, R pigment dispersion composition 3, Y pigment dispersion composition 1, G pigment dispersion composition 2, and G pigment dispersion composition 3 in Tables 5 to 7 are shown below.

(Preparation of R pigment dispersion composition 2)
The following composition was stirred for 1 hour using a homogenizer at 3,000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain an R pigment dispersion composition 2.
-Composition-
・ C. I. Pigment Red 254 12 parts Dispersant 6 parts (Brand name: Disperbyk-161, 30% solution manufactured by Big Chemie)
Alkali-soluble resin: 1.8 parts (benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5,000)
・ Solvent: 80 parts (propylene glycol monomethyl ether acetate)

(Preparation of R pigment dispersion composition 3)
The following composition was stirred for 1 hour using a homogenizer at 3,000 rpm. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain an R pigment dispersion composition 3.
-Composition-
・ C. I. Pigment Red 177 ... 13.1 parts, Dispersant ... 5.3 parts (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
・ Solvent: 81.6 parts (propylene glycol monomethyl ether acetate)

(Preparation of Y pigment dispersion composition 1)
The following composition was stirred for 1 hour using a homogenizer at 3,000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain Y pigment dispersion composition 1.
-Composition-
・ C. I. Pigment Yellow 150 ・ ・ ・ 18.1 parts ・ Dispersant ・ ・ ・ 2 parts (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
Alkali-soluble resin: 3.5 parts (benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5,000)
・ Solvent: 76.4 parts (propylene glycol monomethyl ether acetate)

(Preparation of G pigment dispersion composition 2)
The following composition was stirred for 1 hour using a homogenizer at 3,000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain G pigment dispersion composition 2.
-Composition-
・ C. I. Pigment Green 36 ・ ・ ・ 12 parts ・ C.I. I. Pigment Yellow 150 3 parts Dispersant 2.2 parts (Product name: Disperbyk-161, 30% solution manufactured by Big Chemie)
Alkali-soluble resin: 3.7 parts (benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5,000)
・ Solvent: 76.1 parts (propylene glycol monomethyl ether acetate)

(Preparation of G pigment dispersion composition 3)
The following composition was stirred for 1 hour using a homogenizer at 3,000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain G pigment dispersion composition 3.
-Composition-
・ C. I. Pigment Green 36 ... 8.25 parts C.I. I. Pigment Yellow 150 ... 6.75 parts, Dispersant ... 2.2 parts (Brand name: Disperbyk-161, 30% solution manufactured by Big Chemie)
Alkali-soluble resin: 3.7 parts (benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5,000)
・ Solvent: 76.1 parts (propylene glycol monomethyl ether acetate)

<Comparative Example 1>
In the production process of the photosensitive transfer material of Example 1, a photosensitive transfer material (black photosensitive transfer material) was prepared in the same manner as in Example 1 except that dioctyl sebacate was not used in the coating liquid component for the thermoplastic resin layer. Example 1 except that the photosensitive transfer material of Example 1 (black photosensitive transfer material K201) was replaced with the black photosensitive transfer material K301 in the color filter manufacturing process of Example 1 in the manufacturing process of the color filter of Example 1. A color filter was produced in the same manner as described above. The photosensitive transfer material and color filter of Comparative Example 1 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.

<Comparative example 2>
In the production process of the photosensitive transfer material of Example 1, the coating liquid for the thermoplastic resin layer was not used in the coating liquid component for the thermoplastic resin layer, and the coating liquid for the thermoplastic resin layer was changed to the following formulation 2 and Example 1 was used. Similarly, a photosensitive transfer material (black photosensitive transfer material K302) is manufactured, and in the color filter manufacturing process of Example 1, the photosensitive transfer material of Example 1 (black photosensitive transfer material K201) is converted to black photosensitive. A color filter was produced in the same manner as in Example 1 except that the color transfer material K302 was used. The photosensitive transfer material and color filter of Comparative Example 2 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.
[Formulation 2 of coating solution for thermoplastic resin layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55/12/5/28 [molar ratio], weight average molecular weight 90000)
・ ・ ・ ・ 90.7 parts ・ Styrene / acrylic acid copolymer (= 63/37 [molar ratio], weight average molecular weight 8000)
... 110.8 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
... 111.8 parts ・ Surfactant 1 (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc.)
··· 6.0 parts · Methanol · · · 175.0 · · 1-methoxy-2-propanol · · · 80.0 · · Methyl ethyl ketone · · · 425.7 parts

<Comparative Example 3>
In the production process of the photosensitive transfer material of Example 1, in the coating liquid component for the thermoplastic resin layer, dioctyl sebacate was not used, and the coating liquid for the thermoplastic resin layer was changed to the following formulation 3 and Example 1 Similarly, a photosensitive transfer material (black photosensitive transfer material K303) was manufactured, and in the color filter manufacturing process of Example 1, the photosensitive transfer material of Example 1 (black photosensitive transfer material K201) was converted to black photosensitive. A color filter was produced in the same manner as in Example 1 except that the color transfer material K303 was used. The photosensitive transfer material and the color filter of Comparative Example 3 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.
[Formulation 3 of coating solution for thermoplastic resin layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55/12/5/28 [molar ratio], weight average molecular weight 90000)
・ ・ ・ ・ 88.3 parts ・ Styrene / acrylic acid copolymer (= 63/37 [molar ratio], weight average molecular weight 8000)
... 107.9 parts of 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
... 117.2 parts Surfactant 1 (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc.)
・ ・ ・ 6.0 parts ・ Methanol ・ ・ ・ 175.0 parts ・ 1-methoxy-2-propanol ・ ・ ・ ・ 80.0 parts ・ Methyl ethyl ketone ・ ・ ・ 425.6 parts

<Comparative example 4>
In the production process of the photosensitive transfer material of Example 1, the coating liquid for the thermoplastic resin layer was not used in the coating liquid component for the thermoplastic resin layer, and the coating liquid for the thermoplastic resin layer was changed to the following formulation 4 with Example 1 and Similarly, a photosensitive transfer material (black photosensitive transfer material K304) is manufactured, and in the color filter manufacturing process of Example 1, the photosensitive transfer material of Example 1 (black photosensitive transfer material K201) is converted to black photosensitive. A color filter was produced in the same manner as in Example 1 except that the color transfer material K304 was used. The photosensitive transfer material and color filter of Comparative Example 4 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.
[Formulation 4 of coating solution for thermoplastic resin layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55/12/5/28 [molar ratio], weight average molecular weight 90000)
.... 93.1 parts Styrene / acrylic acid copolymer (= 63/37 [molar ratio], weight average molecular weight 8000)
・ ・ ・ 113.7 parts ・ Octadocosanoic acid ・ ・ ・ 106.5 parts ・ Surfactant 1 (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc.)
··· 6.0 parts · Methanol · · · 175.0 · · 1-methoxy-2-propanol · · · 80.0 · · Methyl ethyl ketone · · · 425.7 parts

  In Table 8, the amounts of the compound and the plasticizer are all amounts (% by mass) based on the total mass of the thermoplastic resin layer in the black photosensitive transfer material.

As can be seen from Table 8, reticulation and oozing worsened as the amount of plasticizer increased (Comparative Examples 1 and 3) in the case of using only a plasticizer in the thermoplastic resin layer (Comparative Examples 1 to 4). ) Even when the amount of plasticizer was small, bubbles were generated during transfer (Comparative Example 1).
On the other hand, the thermoplastic resin layer contains a compound having an I / O value of 0.30 to 0.45, and the content of the compound is in a preferred range (0.8 to 20% by mass) (Example 1) ˜9, 12), comprehensively excellent evaluation results were obtained in reticulation, lamination and exudation.
Moreover, the color filter (Examples 1-12) which the thermoplastic resin layer manufactured using the photosensitive transfer material containing the compound whose I / O value is 0.30-0.45 has all display unevenness. There wasn't.

Claims (7)

  Photosensitive having an alkali-soluble thermoplastic resin layer containing a compound having an I / O value of 0.30 to 0.45 and a photosensitive resin layer in this order from the temporary support side. Transfer material.   The photosensitive transfer material according to claim 1, wherein the compound has an I / O value of 0.32 to 0.43.   3. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer contains the compound in an amount of 0.5 to 20 mass% with respect to the total mass of the thermoplastic resin layer. .   4. The photosensitive transfer material according to claim 1, further comprising at least one intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. 5.   The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer further contains a plasticizer. A transfer step of transferring at least a photosensitive resin layer onto a substrate using the photosensitive transfer material according to any one of claims 1 to 5,
An exposure step of exposing at least the photosensitive resin layer transferred onto the substrate;
A development step of developing the photosensitive resin layer after the exposure;
The manufacturing method of the color filter which has.   A color filter manufactured by the method for manufacturing a color filter according to claim 6.