KR20040019252A - Photo-curable composition, components for lcd and solid state imaging device using the same, and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A radiation curing composition, a component for LCD using the composition, a component for a solid state imaging device and their preparation method are provided, to improve radiation curing property, developability, coating property, uniformity of coating, liquid saving property and transmittance. CONSTITUTION: The radiation curing composition comprises an alkali-soluble radiation curing resin; a radiation curing monomer; a photopolymerization initiator; and a solvent, wherein the alkali-soluble radiation curing resin is at least one copolymer selected from the compound having repeating units of the formulas a1, a2, b1, b2, c1 and d, the compound having repeating units of the formulas a1, a2, b1, b2, c2 and d, and the compound having repeating units of the formulas a1, a2, b1, b2, c3, c4 and d. In the formulas, R is H or CH3; R1 is an alkyl group of C1-C18, a, phenyl group, a phenyl group substituted with an alkyl or alkoxy group of C1-C4, or an aryl or aralkyl group of C7-C12; R2 and R4 are independently an alkylene group of C1-C18, a phenyl carbamate substituted with an alkyl group of C1-C4, or a carbamate having an alicyclic group of C3-C18; R3 is a linear or branched alkylene group of C2-C16; R5 is an alkylene group of C1-C4; l is an integer of 2-30; m is an integer of 0-20; and n is an integer of 2-20.

Description

Photocurable composition, components for liquid crystal display device and components for solid-state image sensor using same, and manufacturing method thereof {PHOTO-CURABLE COMPOSITION, COMPONENTS FOR LCD AND SOLID STATE IMAGING DEVICE USING THE SAME, AND MANUFACTURING METHOD THEREOF}

The present invention provides a photocurable composition suitable for producing a primer layer (spacer), a planarization layer (protective layer) or a contact hole in a liquid crystal display device or a solid state image pickup device, a component for LCD and a component for a solid state image pickup device using the same, It relates to their manufacturing method.

In the liquid crystal display device, a spacer is usually formed between the color filter and the array substrate in order to make the liquid crystal layer a constant film thickness. The spacer is conventionally formed in a form in which spherical particles made of polymethyl methacrylate, spherical silica, and the like are mixed in the liquid crystal layer, thereby securing a gap of 3 to 10 탆.

Since the spherical particles move in the liquid crystal layer, when the liquid crystal layer is pressed with a finger or the like, the gap varies due to the movement and the thickness of the liquid crystal changes. As a result, the color of the liquid crystal display may be blurred or the image may be deformed.

In order to solve the above problem, it is proposed to form a spacer with a photosensitive resin composition instead of spherical particles. That is, although a part of the photosensitive coloring composition layer for forming a color filter can be thickened to be used in place of a spacer, in the coloring composition layer containing a pigment, it can be formed simultaneously with the color filter, but a large exposure amount is required for curing, There was a problem that the bottom of the colored composition layer was not sufficiently cured. Moreover, the pigment is expensive and the process of obtaining a pigment dispersion liquid needed, and manufacturing cost became high. For this reason, the development of the transparent photosensitive composition for forming the said spacer was needed.

As a component for a solid state image pickup device, a transparent resin primer layer (spacer) for improving the adhesion of the color filter layer on a silicon wafer in addition to the color filter, or a planarization layer (protective layer) for applying the surface of the color filter to planarize the surface thereof. ) May be formed. Background Art [0002] The materials of these primer layers and planarization layers, which are components for conventional solid-state image pickup devices, are often used in thermosetting materials such as epoxy resins because of the simplicity of the process of producing a cured film with low volume shrinkage. However, thermosetting resins tend to yellow and have optical problems. Moreover, since hardening by heat is required, there existed a problem that a process requires time.

On the other hand, Patent Document 1 (Japanese Patent Laid-Open No. 7-248625) discloses a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable compound as a radiation-sensitive composition for forming permanent films such as an interlayer insulating film and a protective film of a liquid crystal display. The use of is disclosed. However, in this technique, since hardening by heat is required after forming a photosensitive layer in order to acquire required physical property, time was required in a normal process. Moreover, in order to provide alkali developability, since a considerable amount of carboxylic acid or an acid component replacing this is required, an epoxy ring reacts, and it has the drawback that it will thicken and solidify during storage.

In addition, Patent Document 2 (Japanese Patent Laid-Open No. H11-323057) and Patent Document 3 (Japanese Patent Laid-Open No. 2002-204423) disclose a radiation curable composition for spacers for LCDs. The former uses two types of specific (meth) acrylate type compounds, and the latter uses the (meth) acrylate type compound which has specific (meth) acryloyl group content and acid value.

Although these techniques are excellent in photocurability because thermosetting is unnecessary, there was room for improvement in developability, coatability and the like. Specifically, the developing region (developing range) was narrow, the production titration was inferior, the resolution was bad, and the formation of the predetermined size was impossible. In addition, there was still insufficient function as a spacer because there was still a coating stain after development and a thickness imbalance of the coating.

In addition, Patent Document 4 (Japanese Patent Laid-Open No. 10-204321) discloses a black matrix excellent in light shielding properties, adhesiveness, and resistivity, comprising a high molecular compound, a dispersing aid, and two or more metal oxides. The black pigment composition characterized by containing a composite metal oxide pigment is described, and the (meth) acrylic-acid copolymer is disclosed as the high molecular compound. However, also in this technique, developability, applicability | paintability, coating film uniformity, etc. were not enough.

The present invention has been made to improve all the above-mentioned drawbacks of the prior art, and its object is to have excellent photocurability and developability, and is excellent in coating property, coating film uniformity and liquid saving property, and furthermore, photocurability with improved transmittance. The composition, the components for LCD, the components for solid-state image sensor using the same, and its manufacturing method are provided.

As a result of various studies, the inventors have found that the above object is achieved by using a specific alkali-soluble photocurable resin.

In other words,

(1) Compound (1-1) and compound (1) wherein the alkali-curable photocurable resin comprises the following structural unit in the photocurable composition containing an alkali-soluble photocurable resin, a photocurable monomer, a photopolymerization initiator, and a solvent. -2) and at least one copolymer selected from compounds (1-3).

Compound (1-1): the following structural units (a1), (a2), (b1), (b2), (c1) and (d)

Compound (1-2): the following structural units (a1), (a2), (b1), (b2), (c2) and (d)

Compound (1-3): the following structural units (a1), (a2), (b1), (b2), (c3), (c4) and (d)

The structural ratio of each structural unit in the compounds (1-1) to (1-3) is 10% to 70% by weight in total, a1 and a2 in mole%, b1 and b2 in total, 5 to 40%, c1 is 5-40%, c2 is 5-40%, c3 and c4 are 5-40% in total, d is 5-30%,

R represents a hydrogen atom or a methyl group,

R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxyl group, an aryl group having 7 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms,

R ₂ and R ₄ each independently represent a phenylcarbamic acid ester containing an alkylene group having 1 to 18 carbon atoms, an alkyl group having 1 to 4 carbon atoms as a substituent, or a carbamic acid ester having an alicyclic group having 3 to 18 carbon atoms. Indicate,

R <_3> represents a C2-C16 linear or branched alkylene group,

R ₅ represents an alkyl group having 1 to 4 carbon atoms,

l represents the integer of 2-30,

m represents 0 or the integer of 1-20,

n represents an integer of 2 to 20,

X represents a group selected from the following general formulas (1) to (9).

(2) The photocurable composition according to the above (1), wherein the photocurable resin for alkali grams contains 0.1 to 5.0 meq / g of (meth) acryloyl group, and the acid value is 20 to 200.

(3) The photocurable composition as described in said (1) or (2) whose mass mean molecular weight (Mw) of the said alkali-soluble photocurable resin is 5,000-30,000.

(4) The photocurable composition as described in any one of said (1)-(3) which further contains a coloring agent.

(5) The component for LCD formed from the photocurable composition in any one of said (1)-(4).

(6) A component for solid-state image pickup device, which is made of the photocurable composition according to any one of (1) to (4).

(7) At least the coating film forming step of slit-coating the photocurable composition of any one of said (1)-(5), the photocuring process process of light-irradiating the coating film obtained through the said film forming process in pattern shape, A method of manufacturing a component for an LCD or a component for a solid state image pickup device comprising an alkali developing step using an alkaline developer after the photocuring treatment step.

The photocurable composition of this invention is characterized by using the copolymer of the specific molecular structure which contains a specific structural unit in a specific structural ratio as a photocurable resin for alkali use. In order to achieve the above object of the present invention, among the structural units, particularly c1, c2 and d are important. Structural units c1 and c2 have the advantage that the presence of acryloyl group in the side chain of the alkali-soluble photocurable resin molecular chain can realize excellent photocurability and does not require thermal curing after photocuring. Moreover, the structural unit d can improve the fluidity | liquidity as the coating liquid of a photocurable composition by introduce | transducing ethylene oxide chain | strand and / or a propylene oxide group into the side chain of the alkali soluble photocurable resin molecular chain, and apply | coats, coating film uniformity, It is possible to greatly improve liquid saving properties and the like, and is particularly suitable for slit coating.

By utilizing such features of the present invention, as a component for LCD, a primer layer (spacer), a contact hole forming layer, an interlayer insulating layer, a planarization layer (protective layer), a scattering layer, and the like are also used for a solid state image pickup device (image sensor). Formation of a spacer, a planarization layer, etc. becomes easy, and the characteristic can be made excellent.

In addition, even if a color filter such as an organic pigment, an inorganic pigment, various dyes, and carbon black is contained in the photocurable composition of the present invention and used for a color filter, a color filter having good characteristics can be obtained. In particular, the photocurable composition of the present invention has excellent flow characteristics and leveling properties as a coating liquid, good slit coating aptitude, so that a large area can be applied, and a color filter excellent in characteristics for large screen LCDs such as TV applications. And a component for a solid state image pickup device (image sensor) such as a CCD can be obtained.

Hereinafter, the compounding component used for the photocurable composition of this invention and the usage method of the composition are demonstrated.

The photocurable composition of this invention consists of an alkali photocurable resin, a photocurable monomer, a photoinitiator, and a solvent as an essential component.

[Ⅰ] photocurable resins for alkali soluble

The alkali-soluble photocurable resin used for the composition of this invention is 1 or more types of copolymers chosen from the compound (1-1), the compound (1-2), and the compound (1-3) containing the following structural unit.

Compound (1-1): the following structural units (a1), (a2), (b1), (b2), (c1) and (d)

Compound (1-2): the following structural units (a1), (a2), (b1), (b2), (c2) and (d)

Compound (1-3): the following structural units (a1), (a2), (b1), (b2), (c3), (c4) and (d)

The structural ratios of the structural units in the compounds (1-1) to (1-3) are 10 to 70% in total, a1 and a2 in molar ratios, 5 to 40% in total, b1 and b2, and c1. 5 to 40% of silver, 5 to 40% of c2, 5 to 40% of c3 and c4 in total, d to 5 to 30%,

R represents a hydrogen atom or a methyl group,

R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxyl group, an aryl group having 7 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms,

R ₂ and R ₄ each independently represent a phenylcarbamic acid ester containing an alkylene group having 1 to 18 carbon atoms, an alkyl group having 1 to 4 carbon atoms as a substituent, or a carbamic acid ester having an alicyclic group having 3 to 18 carbon atoms. Indicate,

R <_3> represents a C2-C16 linear or branched alkylene group,

R ₅ represents an alkyl group having 1 to 4 carbon atoms,

l represents the integer of 2-30,

m represents 0 or the integer of 1-20,

n represents an integer of 2 to 20,

X represents a group selected from the following general formulas (1) to (9).

About compound (1-1), compound (1-2), and compound (1-3) in this invention, some structural units (a1), copper (a2), copper (b1), copper (b2), The reaction is completed after copolymerization of copper (d) to form part of the structural units (b2) as structural units (c1) to (c4).

For example, if it is a compound (1-1), the copolymer of a structural unit (a1), copper (a2), copper (b1), copper (b2), and copper (d) is synthesize | combined, and a structural unit ( It is obtained by adding the acrylate compound which has an isocyanate group with respect to a part of component of b2).

Moreover, if it is a compound (1-2), the copolymer of a structural unit (a1), copper (a2), copper (b1), copper (b2), and copper (d) is synthesize | combined, and thereafter, a structural unit (b2) It is obtained by adding the acrylate compound which has an epoxy group with respect to a part of component of the.

And if it is a compound (1-3), the copolymer of a structural unit (a1), copper (a2), copper (b1), copper (b2), and copper (d) is synthesize | combined, and thereafter, a structural unit (b2) It is obtained by adding a group selected from general formulas (1) to (9) with respect to a part of the component of.

Each structural unit is demonstrated in detail below.

R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxyl group, an aryl group having 7 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

The alkyl group having 1 to 18 carbon atoms may be any of linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, Amyl group, i-amyl group, t-amyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, etc. are mentioned. Preferably it is a C1-C8 alkyl group.

As a C1-C4 alkyl group as a substituent of a phenyl group, there exist a methyl group, an ethyl group, a propyl group, i-propyl group, a butyl group, i-butyl group, t-butyl group, etc., for example, and C1-C4 as a substituent of a phenyl group As an alkoxyl group of 4, a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, butoxy group, i-butoxy group, t-butoxy group, etc. are mentioned, for example.

The aryl group having 7 to 12 carbon atoms may have a substituent, and examples thereof include a phenyl group, a tril group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group and a naphthyl group.

The aralkyl group having 7 to 12 carbon atoms may have a substituent, and examples thereof include a benzyl group, a phenethyl group, a naphthyl methyl group, and the like.

R ₂ and R ₄ each independently represent a phenylcarbamic acid ester containing an alkylene group having 1 to 18 carbon atoms, an alkyl group having 1 to ₄ carbon atoms as a substituent, or a carbamic acid ester having an alicyclic group having 3 to 18 carbon atoms. .

Examples of the alkylene group having 1 to 18 carbon atoms include linear and branched alkylene groups, and examples thereof include methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group. Preferably it is a C4-C8 alkylene group.

As each ester of the phenyl carbamic acid ester containing a C1-C4 alkyl group, or the carbamic acid ester which has a C3-C18 alicyclic group, there exists a C1-C6 alkyl ester.

As a C2-C16 linear or branched alkylene group which R <_3> represents, a linear and branched alkylene group is mentioned, For example, a methylene group, ethylene group, a propylene group, butylene group, hexylene group, octylene group, etc. There is this. Preferably it is a C4-C8 alkylene group.

As a C1-C4 alkyl group which R <_5> represents, a methyl group, an ethyl group, a propyl group, i-propyl group, a butyl group, i-butyl group, t-butyl group etc. are mentioned, for example.

l represents the integer of 2-30, Preferably it is an integer of 2-10. m represents the integer of 0 or 1-20, Preferably it is 0 or the integer of 1-2. n represents the integer of 2-20, Preferably it is an integer of 2-6.

X represents a group selected from the general formulas (1) to (9). Among them, general formulas (1) and (2) are preferred.

In this invention, the structural ratio of each said structural unit in said compound (1-1)-(1-3) is mol%, and a1 and a2 are 10-70% in total, Preferably it is 15-60 %, b1 and b2 are 5 to 40% in total, preferably 15 to 30%, c1 is 5 to 40%, preferably 10 to 20%, c2 is 5 to 40%, preferably 10 to 20% , c3 and c4 are 5 to 40% in total, preferably 10 to 20%, d is 5 to 30%, preferably 10 to 20%.

In the present invention, the alkali-curable photocurable resin is preferably a (meth) acryloyl group, preferably 0.1 to 5.0 meq / g, more preferably 0.5 to 3.0 meq / g, particularly preferably 0.8 to 2.0 meq / g. It contains. Moreover, it is preferable that the acid value of alkali photocurable resin is 20-200, More preferably, it is 25-100, Especially preferably, it is 30-80.

The mass average molecular weight (Mw) of the alkali-soluble photocurable resin of the present invention is preferably 5,000 to 30,000, more preferably 7,000 to 15,000, and particularly preferably 8,000 to 12,000.

In the composition of the present invention, the content of the alkali-soluble photocurable resin is not limited, but when it contains a colorant, it is preferably 5 to 55% by mass, more preferably 15 to 45% by mass in the total solids. Moreover, when it does not contain a coloring agent, Preferably it is 20-70 mass% in total solid, More preferably, it is 30-60 mass%.

[II] Colorant

By further containing a coloring agent in the alkali soluble photocurable composition of this invention, the photocuring film of the color filter for liquid crystal display devices and a solid-state image sensor (image sensor) can be obtained. As a coloring agent which can be used, various pigments and dyes can be used 1 type or in mixture of 2 or more types.

As a pigment which can be used for this invention, various conventionally well-known inorganic pigments or organic pigments can be used. In addition, considering that the pigment is preferably a high transmittance, either inorganic pigments or organic pigments, the use of fine ones is good, but considering the handling properties, the average particle diameter is preferably 0.01 μm to 0.1 μm, more preferably. The pigment of 0.01 micrometer-0.05 micrometers is used. Inorganic pigments are metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and the metal complex An oxide can be illustrated.

As an organic pigment,

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 0range 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;

Carbon black etc. are mentioned.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity of a photocurable monomer and a pigment is having an influence.

Although the following are mentioned as a pigment which can be used preferably in this invention, It 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 0range 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 are used individually or in combination in order to raise color purity. A specific example is shown below. Examples of the red pigment include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, and disazo yellow pigments, isoindolin yellow pigments, quinophthalone yellow pigments, or perylene-based red pigments. Mixing with a pigment is used. For example, as an anthraquinone pigment, CI pigment red 177 and a perylene pigment are CI pigment red 155, CI pigment red 224, and diketopyrrolopyrrole pigments, CI pigment red 254 is mentioned. In view of color reproducibility, mixing with CI Pigment Yellow 83 or CI Pigment Yellow 139 is preferable. As for the mass ratio of a red pigment and a yellow pigment, 100: 5-100: 50 are preferable. By setting it as 100: 5 or more, since the light transmittance of 400 nm to 500 nm can be suppressed and color purity can be improved, it is preferable. Moreover, it is preferable to set it as 100: 50 or less because a dominant wavelength becomes short wavelength and the difference from an NTSC target color is hardly seen. Especially the range of 100: 10-100: 30 is optimal. In the case of the combination of red pigments, it adjusts according to chromaticity.

As the green pigment, a halogenated phthalocyanine-based pigment alone or a mixture with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment or an isoindolin-based yellow pigment is used. For example, CI pigment green 7, Mixing with 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow 185 is preferred. As for mass ratio of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable. By setting it as 100: 5 or more, since the light transmittance of 400 nm to 450 nm can be suppressed and color purity can be improved, it is preferable. Moreover, it is preferable to set it as 100: 150 or less because a dominant wavelength becomes long wavelength and the difference from an NTSC target color is hardly seen. More preferable mass ratio is in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment alone or a mixture with a dioxadine-based purple pigment is used, and for example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferable. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 10 or less.

In addition, a pigment-containing photosensitive resin having good dispersibility and dispersion stability can be obtained by using a powdered processing pigment obtained by finely dispersing the pigment into an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, and an ethyl cellulose resin.

As a black matrix pigment, carbon black, titanium carbon, iron oxide, etc. are used individually or in mixture. Among them, in the case where carbon black and titanium carbon are mixed and used, the mixing ratio is preferably in a mass ratio of 100: 0 to 100: 60 in terms of dispersion stability.

The processing method of a pigment is demonstrated below. Generally these pigments are synthesized and then dried and supplied in various ways. Usually, it is dried from an aqueous medium and supplied as a powder, but since large latent heat of evaporation is required for water to dry, large thermal energy is given to dry and powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are collected.

It is not easy to disperse the pigment forming such aggregates into fine particles. Therefore, it is preferable to process a pigment with various resin previously. As these resin, the above-mentioned alkali-soluble resin can be illustrated. As a method of treatment, there is a flashing treatment, a kneading method by a kneader, an extruder, a ball mill, two or three roll mills, or the like. Of these, flashing treatment or kneading by two or three roll mills is preferable for finer grains.

Flashing is a method of mixing a water dispersion of a pigment and a resin solution dissolved in a solvent which is not mixed with water, extracting the pigment into an organic medium in an aqueous medium, and treating the pigment with a resin. According to this method, since the pigment is not dried, aggregation of the pigment can be prevented and dispersion becomes easy. In kneading by two or three roll mills, after mixing a pigment and a solution of a resin or a resin, a method of treating the pigment by coating the resin on the surface of the pigment by kneading the pigment and the resin while applying a high shear (shear force). to be. Pigment particles aggregated in this process are dispersed from the lower-dimensional aggregates to the primary particles.

Moreover, in this invention, the processed pigment previously processed with acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin, etc. can also be used suitably. In the present invention, as a form of the processed pigment treated with the various resins, a powder, a paste form, and a pellet form in which the resin and the pigment are uniformly dispersed are preferable. Moreover, it is unpreferable in the form of the nonuniform mass which gelatinized resin. The colored dispersion thus obtained is mixed with the photocurable monomer and provided as a photocurable composition.

Although the coloring agent content rate in the total solid of the photocurable composition of this invention is not specifically limited, Preferably it is 30-60 mass%.

In the present invention, a conventionally known pigment dispersant or a surfactant can be added for the purpose of improving the dispersibility of the pigment. Although many kinds of compounds are used as these dispersing agents, For example, a phthalocyanine derivative (commercially available EFKA-745 (made by Efka Co.)), Solsperth 5000 (made by Genca); Organosiloxane Polymer KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow Nos. 75, No.90, No.95 (Kyoeisha Yukagaku Kogyo Co., Ltd.), W001 (Yumese Cationic surfactants such as products); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, butyric acid fatty acid ester Nonionic surfactants such as these; Anionic surfactant, such as W004, W005, W017 (made by Yumese); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (more than Morishitasan), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Polymeric dispersants such as Perth Aid 9100 (manufactured by Sanofuco); Various Solsper dispersants (manufactured by Geneca Co., Ltd.) such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adecapulonikkku L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by Asahi Denka) and Isonet S -20 (Sanyo Kasei product) is mentioned.

The dye which can be used by this invention does not have limitation in particular, A well-known dye can be used for a conventional color filter. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Patent Registration 2592207, United States Patent 4,808,501, US 5,667,920, US 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. Hei 6-194828, Japanese Patent Laid-Open No. Hei 8-211599, Japanese Patent Laid-Open No. Hei 4-249549, Japanese Patent Laid-Open No. Hei 10-123316, Japanese Patent Laid-Open No. Hei 11-302283, Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 94821, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, and Japanese Patent Japanese Patent Laid-Open No. Hei 8-146215, Japanese Patent Laid-Open No. Hei 11-343437, Japanese Patent Laid-Open No. 8-62416 Japanese Patent Laid-Open No. 2002-14220, Japanese Patent Laid-Open No. 2002-14221, Japanese Patent Laid-Open 2002-14222, Japanese Patent Laid-Open 2002-14223, Japanese Patent Laid-Open No. 8-302224, Japanese Patent The pigment | dye disclosed in Unexamined-Japanese-Patent No. 8-73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. can be used. Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzilidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiadine, Dye, such as a pyro pyrazole azomethine type, a xanthine type, a phthalocyanine type, a benzopyran type, an indigo type, can be used.

Moreover, in the case of the resist system which performs water or alkali image development, an acid dye and / or its derivative can be used preferably from a viewpoint of removing a binder and / or dye completely by image development.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes and / or derivatives thereof may also be usefully used.

The acid dye will be described. The acid dye is not particularly limited as long as it has an acid group such as sulfonic acid or carboxylic acid, but is not particularly limited, solubility in an organic solvent or developer, salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, It selects in consideration of all the required performances, such as heat resistance.

As the derivative of the acid dye, inorganic salts of acid dyes having acid components such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen compounds, sulfonamides of acid dyes, and the like can be used. It will not specifically limit, if it can be used, but it selects in consideration of all the required performances, such as the solubility with respect to the organic solvent and a developing solution, absorbance, interaction with the other components in curable composition, light resistance, heat resistance, etc.

The salt of an acidic dye and a nitrogen compound is demonstrated. The method of salt-forming an acidic dye and a nitrogen compound may be effective in improving the solubility of acidic dye (providing solubility to an organic solvent), and improving heat resistance and light resistance.

The nitrogen compound which forms a salt with an acid dye and the nitrogen compound which forms an amide bond with an acid dye are demonstrated. Nitrogen-containing compounds are selected in consideration of all of solubility in salts and amide compounds in organic solvents and developing solutions, salt formation properties, absorbance and color value of dyes, interaction with other components in the curable composition, heat resistance and color resistance as colorants, and the like. do. When it selects only from a viewpoint of absorbance and a color value, it is preferable that the said nitrogen-containing compound is as low as possible in molecular weight, It is preferable that it is molecular weight 300 or less, It is more preferable that it is molecular weight 280 or less, It is especially preferable that it is molecular weight 250 or less.

The molar ratio (hereinafter referred to as n) of the nitrogen compound / acid dye in the salt of the acid dye and the nitrogen compound will be described. n is a value which determines the molar ratio of the amine compound which is an acid dye molecule and a counter ion, and can be selected freely according to the salt formation conditions of an acid dye-amine compound. Specifically, the numerical value between 0 <n≤5 of the number of functional groups of an acid in an acid dye is used practically, and the solubility, salt formation, absorbance, and the interaction with other components in an organic solvent and a developing solution are curable. It selects in consideration of all the required performances, such as light resistance and heat resistance. In view of absorbance alone, n preferably takes a value between 0 <n ≦ 4.5, more preferably takes a value between 0 <n ≦ 4, and takes a value between 0 <n ≦ 3.5. Is particularly preferred.

Next, the use concentration of organic solvent soluble dye is demonstrated. Although the density | concentration of the solvent-soluble dye in the total solid component of the coloring agent containing curable composition of this invention changes with dye, 0.5-80 mass% is preferable, 0.5-60 mass% is more preferable, 0.5-50 mass% is especially desirable.

[III] photocurable monomer

Next, the photosensitive monomer used in the composition of this invention is demonstrated.

As said photocurable monomer, the compound which has at least 1 addition-polymerizable ethylene group, and has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure is preferable, and the tetrafunctional or more than four functional acrylate compound is more preferable.

As a compound which has the said at least 1 addition-polymerizable ethylenically unsaturated group and whose boiling point is 100 degreeC or more at normal pressure, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate Monofunctional acrylates and methacrylates such as these; Polyethylene glycol di (meth) acrylate, trimetholethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimeme (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as tyrolethane; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708 Urethane acrylates described in Japanese Patent Application Laid-Open No. 50-6034 and Japanese Patent Laid-Open No. 51-37193, Japanese Patent Publication No. 48-64183, and Japanese Patent Publication Polyfunctional acrylates and metas such as the polyester acrylates described in Japanese Patent Laid-Open Nos. 52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids. Acrylate. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesive association Vo1.20, No. 7, pages 300-308.

Moreover, the compound which (meth) acrylated after adding ethylene oxide or a propylene oxide to the said polyfunctional alcohol is the specific example as General Formula (1) and (2) in Unexamined-Japanese-Patent No. 10-62986. And these can also be used as the photocurable monomer.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via an ethylene glycol and a propylene glycol residue are preferable. These oligomer types are also used. These photocurable monomers can be used individually by 1 type or in combination of 2 or more types. The usage-amount of these photocurable monomers becomes like this. Preferably it is 20-200 mass% in the total solid of a composition, More preferably, it is 50-120 mass%.

[IV] Photopolymerization Initiator

As a photoinitiator, active halogen compounds, such as halomethyloxadiazole and halomethyl-s-triazine, a 3-aryl substituted coumarin compound, at least 1 type of lophine dimer, etc. are mentioned.

Among the active halogen compounds such as halomethyl oxadiazole and halomethyl-s-triazine, as the halomethyl oxadiazole compound, 2-halomethyl represented by the following general formula VII in JP-A-57-6096 -5-vinyl-1,3,4-oxadiazole compound is mentioned.

In general formula:

W represents a substituted or unsubstituted aryl group, X represents a hydrogen atom, an alkyl group or an aryl group.

Y represents a fluorine atom, a chlorine atom or a bromine atom.

n represents the integer of 1-3.

Specific compounds of the general formula (VII) include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4 -Oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, etc. are mentioned.

As the halomethyl-s-triazine-based compound, vinyl-halomethyl-s-triazine compound represented by the following general formula VII described in JP-A-59-1281, JP-A-53-133428 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula VII and 4- (p-aminophenyl) -2 represented by the following general formula XI And a 6-di-halomethyl-s-triazine compound.

General formula weight:

Q represents Br or Cl.

P represents -CQ ₃ (Q means the same as above), -NH ₂ , -NHR, -N (R) _2, or -OR (where R represents a phenyl or alkyl group).

W represents the monovalent group represented by the aromatic group which may be substituted, the heterocyclic group which may be substituted, or the following general formula (A).

In general formula (A), Z is -O- or -S- and R is synonymous with the above.

In general formula:

X represents Br or Cl.

m and n are integers of 0-3.

R 'represents a group represented by the following general formula (XA).

(In General Formula XA, R ₁ represents a hydrogen atom or ORc (Rc represents an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents Cl, Br, alkyl, alkenyl, aryl, or an alkoxy group.)

In formula XI:

R ₁ and R ₂ are the same or different and represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by the following general formula XIA or XIB.

R <_3> , R <_4> is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group.

X and Y are the same or different and represent Cl or Br.

m and n are the same or different and represent 0, 1 or 2.

R <_5> , R <_6> , R <_7> represents an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group in general formula XIA and XIB. Examples of the substituent in the substituted alkyl group and the substituted aryl group include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, and the like. Can be.

In the formula XI, R ₁ and R ₂ may be the verses form a ring having a non-metallic atoms together with the nitrogen atom linking them, there is shown in that case, as to this section ring.

Specific examples of the general formula IX include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethyl Aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

Specific examples of the general formula (X) include 2- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine and 2- (4-methoxy-naphtho-1-yl) -4 , 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4- Butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6 -Bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-Butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho-1-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dime Methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine and the like.

Specific examples of general formula XI include 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN , N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -(pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyl carbonylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4 -[mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro Tyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl)- s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o- Bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl]- 2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m- Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (tri Loromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s -Triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine and the like Can be mentioned.

The following sensitizers can be used together in these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9- pullolenone, 2-chloro-9- pullolenone, 2-methyl-9- pullolenone, 9-anthrone, 2-bro Mo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6 -Dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethyl Amino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, etc. The benzothiazole type compound of Unexamined-Japanese-Patent No. 51-48516 is mentioned.

Moreover, the said 3-aryl substituted coumarin compound is a compound represented, for example by the following general formula (XII).

R ₈ is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group), and R ₉ is a hydrogen atom, An alkyl group, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula XIIA (preferably methyl group, ethyl group, propyl group, butyl group, group represented by general formula XIIA, particularly preferably represented by general formula XIIA) Mark).

R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), and a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group and a fluoro group). Methyl group, trifluoromethyl group, etc.), alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group), aryl group having 6 to 10 carbon atoms (for example, phenyl group), amino group, N (R ₁₆ ) (R ₁₇ ) and halogen atoms (eg Cl, Br, F). Preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl _{group, -N (R 16) (R} 17), Cl.

R <_12> represents the C6-C16 aryl group (for example, a phenyl group, a naphthyl group, a tril group, cumyl group) which may be substituted. Examples of the substituent group, -N (R ₁₆₎ (R _17), alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl, propyl, butyl, octyl), a haloalkyl group (e.g. having 1 to 8 carbon atoms; Chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group halogen atom (e.g. Cl, Br, F ).

R <_13> , R <_14> , R <_16> , R <_17> is the same or different, and represents a hydrogen atom and a C1-C8 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), respectively. R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are bonded to each other to form a heterocyclic ring (for example, piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring and benzotriazole ring together with a nitrogen atom). Etc.) may be formed.

R ₁₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (eg methoxy group, ethoxy group, butoxy group) ), An optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an amino group, N (R ₁₆ ) (R ₁₇ ), and a halogen atom (for example, C1, Br, F). Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably it is = O, = S, = C (CN) ₂ , Especially preferably, it is = O. R ₁₈ and R ₁₉ are the same or different and represent a cyano group, -COOR ₂₀ , -COR ₂₁ . R ₂₀ and R ₂₁ each represent an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group, a fluoromethyl group, and a tree). Fluoromethyl group etc.) and the C6-C10 aryl group (for example, a phenyl group) which may be substituted.

Particularly preferred 3-arylsubstituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula (XIII).

In General Formula (XIII), R ₁₂ to R ₁₅ are as described above.

Ropin dimer means the 2,4,5-triphenyl imidazolyl dimer which consists of two lopin residues, The basic structure is shown below.

Specific examples thereof include 2- (o-crophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, and 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4, 5-diphenyl imidazolyl dimer etc. are mentioned.

In the present invention, other known ones can be used in addition to the above initiators.

For example, bisinal polyketolaldenyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, US Pat. No. 2,448,828, etc. Acyloin ethers, aromatic acyloin compounds substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. Combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in the specification of 3,549,367, benzothiazole compound / trihalomethyl-s-triazine compound disclosed in Japanese Patent Publication No. 51-48516 Etc. can be mentioned.

Asahi Denka Co., Ltd. Adekaopto SP-150, copper 151, copper 170, copper 171, copper N-1717, copper N1414, etc. can also be used as a polymerization initiator.

As for the usage-amount of an initiator, 0.1-10.0 mass% of the total solid of a photocurable composition is preferable, More preferably, it is 0.5-5.0 mass%. If the amount of the initiator is in the above range, the polymerization proceeds easily and a firm film strength is obtained.

[Ⅴ] solvents

As a solvent used when preparing the photocurable composition of this invention, ester, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, butyric acid Isopropyl, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxy acetate, ethyl oxy acetate, butyl oxy acetate, methyl methoxy acetate, ethyl methoxy acetate, butyl butyl acetate, methyl ethoxy acetate 3-oxypropionic acid alkyl esters such as ethyl ethoxy acetate, methyl 3-oxypropionate and ethyl 3-oxypropionate; Methyl 3-methoxy propionate, 3-methoxy ethylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2-oxo part Methyl carbonate, ethyl 2-oxobutyrate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons, for example, toluene, xylene, and the like can be given.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

You may use these solvents individually or in combination of 2 or more types.

[VI] Fluorine Compound

In the photocurable composition of this invention, the surface smoothness of the coating film of a photocurable composition can be improved by containing the fluorine-type compound represented by following formula (XIV) further.

C ₈ F ₁₇ SO ₂ N (R _One ) CH ₂ CH ₂ O (CH ₂ CH ₂ O) nR ₂ (XIV)

In formula (XIV), R <_1> and R <_2> respectively represent a hydrogen atom or a C1-C4 alkyl group, and n represents the integer of 2-30.

In the formula (XIV), preferably R ₁ is a methyl group, an ethyl group or an iso-propyl group, and R ₂ is a hydrogen atom. The preferable range of n is 10-25, and the especially preferable range is 10-20.

By further containing the fluorine compound represented by said formula (XIV) in the composition of this invention, the liquid characteristic of a composition further improves. That is, the fluidity as the coating liquid is improved, and the adhesion of the coating liquid in the nozzles and piping of the spin coater used in the coating process, the slits and slit heads used in the slit coating, and the containers of the various coating apparatuses is improved, and the contamination is improved. Since the remaining residues can be almost eliminated, the amount and working time of the cleaning liquid required for cleaning at the time of replacement of the coating liquid can be reduced, and the processability is improved. In addition, it is thought that the said fluorine-type compound acts as a nonionic surfactant in the composition of this invention.

As addition amount of the fluorine-type compound represented by Formula (XIV) in this invention, Preferably it is 0.01-2.0 mass% with respect to the whole coating solution, More preferably, it is 0.05-1.0 mass%.

As a fluorine-type compound represented by said Formula (XIV), Megapack F-141 (n = 5), F-142 (n = 10), F-143 (made by Dainippon Ink & Chemical Co., Ltd.) n = 15) and F-144 (n = 20).

Moreover, the composition of this invention can mix | blend surfactants other than the said fluorine-type compound with the same quantity or less with respect to 100 mass parts of fluorine-type compounds normally in the range which does not impair the achievement of the objective of this invention.

Although many kinds of compounds can be used as surfactant which can be mix | blended, For example, a phthalocyanine derivative (commercially available EFKA-745 (made by Morishita Sangyo)); organosiloxane polymer KP341 (made by Shin-Etsukagaku Kogyo), (meta ) Cationic surfactants such as acrylic acid-based (co) polymer polyflow Nos. 75, No. 90, No. 95 (manufactured by Kyoeisha Yukagaku Kogyo Co., Ltd.), and W001 (Yumese Co., Ltd.); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; F-top EF301, EF303, EF352 (made by Shin Akita Kasei), mega pack F171, F172, F173 (made by Dainippon Ink & Chemical Co., Ltd.), Floroid FC430, FC431 (made by Sumitomo 3M), Asahi Guard AG710, suffron S382, Fluorine-based surfactants such as SC-101, SC-102, SC-103, SC-104, SC-105, and SC-1068 (manufactured by Asahi Glass); Anionic surfactants such as W004, W005, and W017 (manufactured by Yumese); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (more than Morishita Sangyo) Polymer dispersants such as Disperse Ade 6, Disperse Ade 8, Disperse Ade 15 and Disperse Ade 9100 (manufactured by Sannobuco); Various Solsper dispersants (manufactured by Geneca Co., Ltd.) such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P123 (made by Asahi Denka) and Isonet S- There are 20 (Sanyokasei products).

These compounds are often used as a dispersant of a pigment.

[Ⅶ] other ingredients

In the composition of the present invention, various additives, for example, fillers, polymer compounds other than the alkaline photocurable resins, surfactants other than those described above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like may be blended, if necessary. have.

Specific examples of these additives include fillers such as glass and alumina; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, addition of acid anhydride to a polymer having a hydroxyl group, formed of alcohol-soluble nylon, bisphenol A and epicrohydrin Alkali-soluble resins such as phenoxy resins; Surfactants such as nonionic, cationic and anionic systems; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane ; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And anti-agglomerating agents such as sodium polyacrylate.

Moreover, when promoting alkali solubility of a non-irradiated part and further improving developability of the composition of this invention, organic carboxylic acid, low molecular weight organic carboxylic acid of molecular weight 1000 or less is preferably used for the composition of this invention. Can be added. Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, lactic acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid, caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, azipine acid, pimeric acid, sublinic acid, azeline acid, sebacic acid, buracic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid, sheet Aliphatic dicarboxylic acids such as laconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and canhoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemeric acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, cumalic acid, and unberic acid. have.

In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t- Butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mer Captobenzoimidazole and the like are useful.

[Iii] How to Use the Composition of the Present Invention

The photocurable composition of the present invention can be prepared by mixing and dispersing an alkali photocurable resin, a photocurable monomer, a photopolymerization initiator, and other additives which can be further used as necessary, by mixing and dispersing the mixture using various mixers and dispersers. have.

The photocurable composition of this invention is apply | coated and dried to a board | substrate by application | coating methods, such as a rotary coating, a flexible coating, a slit coating, and a roll coating, forms a radiation sensitive layer, exposes through a predetermined | prescribed mask pattern, and is made into a developing solution. By developing, a colored pattern is formed. Among them, the slit coating has an advantage that it is possible to apply a large area to the coated object at high speed. The photocurable composition of this invention is excellent in this slit coating suitability, and can obtain the coating film of uniform film thickness in a large area, without causing a liquid interruption even at high speed application.

The slit coating is formed with a slit head having a slit having a width (tens of microns) and a length (one side of the application area), and a gap between the substrate and several tens of microns to derive a resist from the slit. It is a method of applying a resist to a substrate by moving a slit head, and compared with the rotary coating etc., the amount of coating liquid can form a desired coating film in a small amount (1/10 of the rotary coating), and the film thickness distribution is equivalent to that of the rotary coating. Has the characteristic of having performance. Since the amount of the coating liquid is reduced, the manufacturing cost can be reduced. In addition, in slit coating, there is an advantage that other coating methods such as rotary coating that the central portion of the substrate also obtains a uniform coating film.

In the present invention, there is provided a component for LCD and a component for a solid state image pickup device (image sensor) made of the photocurable composition.

As the LCD component, for example, a spacer, a contact hole forming layer, an interlayer insulating film, a planarization layer, a scattering layer, and the like can be given.

As a component for a solid state image pickup device, a transparent resin primer layer (spacer) formed on a color filter and a silicon wafer to improve the adhesion of the color filter, and a planarization layer for applying the surface of the color filter to planarize the surface (protection) Layer).

Moreover, in this invention, the manufacturing method of the components for LCD and components for a solid-state image sensor are also provided. That is, the manufacturing method of this invention is characterized by including the coating film forming process which slit-coats the said photocurable composition at least, and the photocuring process process which irradiates the coating film obtained through the said coating film forming process.

Especially as a light source used for a photocuring process process, ultraviolet rays, such as g line | wire, h line | wire, and i line | wire, are used preferably.

A more preferable manufacturing method is to develop a (colored) pattern by developing with a developer after the coating film forming step of slit-coating the above-mentioned photocurable composition and the photocuring process of light irradiation to the coating film obtained through the said film forming process. How to form.

In the case of using the composition of the present invention for forming a spacer for LCD, it is possible to form between the array substrate and the color filter substrate. Specifically, (1) forming on the ITO electrode layer of the array substrate, (2) forming on the colored layer of the color filter substrate, and (3) forming on both sides of the array substrate and the color filter substrate side. . Moreover, it is also possible to form on alignment films (alignment film is formed on a color filter colored layer), such as polyimide.

Moreover, when using the composition of this invention for forming the planarization layer of LCD, it forms on the color filter colored layer as a protective layer of a color filter. Moreover, it is also possible to form on the alignment film.

There is a system in which holes need to be opened in the protective layer in order to impart conductivity to a part of the array substrate and the CF substrate for LCD. In that case, after forming a layer with the composition of this invention, the part corresponding to a hole is made non-exposure in an exposure process, and a non-exposure part is removed by developing. In this case, stepper exposure is preferable, but exposure may be sufficient. By doing so, a hole having a skirt having a gentler slope than that of the semiconductor resist can be formed, and the liquid crystal can be injected smoothly by forming the panel.

As a component for a solid state image pickup device, a transparent resin primer layer (spacer) for improving the adhesion of the color filter layer on a silicon wafer, or a planarization layer (protective layer) for applying the surface of the color filter to planarize the surface thereof, etc. Can be formed. The composition of the present invention can be used for these primer layers or planarization layers. The composition of the present invention can be cured by radiation such as i-ray or h-ray, and can be used as a primer layer or a planarization layer for improving the adhesion of the color filter layer.

In this invention, as a dry film thickness of a curable composition layer, in the case of a primer layer (spacer), 1-50 micrometers is preferable, More preferably, it is 1.0-20 micrometers, More preferably, it is 1.5-10 micrometers, and planarization In the case of a layer, 0.1-3 micrometers is preferable, More preferably, it is 0.2-1.5 micrometers, In the case of a contact hole, 0.1-6.0 micrometers is preferable, More preferably, it is 0.2-3.0 micrometers.

As the form of the pattern of the spacer, there are a dot, stripe, checkerboard grid, and the like, and the pitch is rational to the color Peter, and this integer multiple is preferable. The shape may be a square pillar, a cylinder, an elliptic cylinder, a square weight, a square die having a trapezoidal cross section, or a polygon thereof.

Examples of the substrate include a color filter substrate, for example, soda glass, alkali-free glass, pyrex glass, quartz glass used in liquid crystal display devices and the like, and a transparent conductive film attached thereto, a photoelectric conversion device substrate used in a solid state imaging device, For example, there is a silicon substrate. These substrates are generally formed with a black stripe that isolates each pixel.

As a developing solution, any thing can be used as long as it melt | dissolves the radiation sensitive layer of a non-irradiation part, and does not melt one radiation irradiation part. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As an organic solvent, the above-mentioned solvent used when preparing the composition of this invention can be illustrated.

As alkali, For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, The alkaline aqueous solution which melt | dissolved alkaline compounds, such as choline, a pyrrole, and piperidine, so that concentration may be 0.001-10 mass%, Preferably it is 0.01-1 mass% is used. Moreover, when using the developing solution which consists of such alkaline aqueous solution, it wash | cleans with water after developing in general.

EXAMPLE

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by a following example.

(Example 1)

<Synthesis of alkaline soluble photocurable resin>

45 mass parts of benzyl methacrylate, 27 mass parts of styrene, 18 mass parts of methacrylic acid, 63 mass parts of hydroxyethyl methacrylate to the 5-neck flask with a reflux cooler, a thermometer, a nitrogen gas introduction tube, and a stirring apparatus. , 27 parts by mass of methoxy polyethylene glycol monomethacrylate, 280 parts by mass of ethyl ethoxypropionate, and 140 parts by mass of cyclohexanone were added. Azoisobutyronitrile was added as a polymerization initiator, and it heated and stirred at 80 degreeC for 8 hours, and completed superposition | polymerization. Moreover, 64 mass parts of monoaddition products of the hydroxyethyl acrylate of hexamethylene diisocyanate were thrown in, and it stirred by heating at 60 degreeC for 8 hours, and obtained the alkali soluble photocurable resin. The (meth) acryloyl group equivalent of obtained resin was 1.73 meq / g, the acid value was 51, and the mass mean molecular weight (Mw) was 11,500.

<Preparation of photocurable composition>

The following components were stirred and mixed to prepare a photocurable composition (resist liquid).

60 parts by mass of an alkali-soluble photocurable resin solution obtained above

Dipentaerythritol pentahexaacrylate

(Photocurable monomer) 20 parts by mass

4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2, 6-di (trichloro

0.5 part by mass of methyl) -S-triazine (photopolymerization initiator)

195 parts by mass of ethyl ethoxy propionate (solvent)

Megapack F-144

0.01 parts by mass (Dainippon Ink & Chemicals Co., Ltd. product, fluorine-based surfactant)

(Examples 2 to 19 and Comparative Examples 1 to 7)

In Example 1, the synthesis was carried out in the same manner as in Example 1 except that the alkali-soluble photocurable resin was changed to that shown in Table 1, and a photocurable composition was prepared under the same conditions as in Example 1.

<Evaluation of the photocurable composition>

About the photocurable composition obtained by each said Example and the comparative example, the slit coating suitability, coating-film thickness uniformity, and the developing range were evaluated by the following method.

(1) slit coating aptitude:

On the glass substrate of 360 nm x 465 mm, the prepared photocurable composition was slit-coated at a slit width of 300 mm, a clearance of 100 mu m, and a discharge amount of 20 cc / min, and the slit spreading speed was measured.

(2) Coating thickness uniformity:

The above-mentioned photocurable composition was slit-coated on the glass substrate of 360 mm x 465 mm, and the film thickness from the edge to the inside part of 30 mm was measured in the diagonal direction at the center part of an application board | substrate. The coating thickness nonuniformity was represented by the following formula and represented by%.

(3) Development scope:

After slit-coating the photocurable composition prepared as mentioned above as above, it cut out to the size of 10 cm x 10 cm in all directions, and prebaked 90 degreeC for 60 second in oven. Subsequently, 200mJ / cm <2> proximity exposure (roughness: 20mW / cm <2>; Proximity gap: 100micrometer) was performed using the mask which has a dot of 10 micrometers square on all sides, Alkali developer CD (made by Fujifilm Arch) It was developed at 30 ° C. with a 10% dilution of. Developing time was performed at 10 second intervals from 10 to 200 seconds. The number of developing seconds in which a 10 탆 square pattern is present is expressed as a developing range.

The above result is shown in Table 2.

Slit spreading speed (mm / sec.) Coating thickness uniformity (%) Development range (second) Example 1 75 0.5 20 to 160 sec. Example 2 100 0.8 20 to 150 sec. Example 3 100 0.8 10 to 130 sec. Example 4 75 0.8 30 to 180 sec. Example 5 75 0.5 40 to 190 sec. Example 6 75 0.5 30 to 200 sec. Example 7 75 0.5 20 to 140 sec. Example 8 75 0.5 20 to 160 sec. Example 9 75 0.8 30 to 170 sec. Example 10 100 0.5 10 to 120 sec. Example 11 75 0.5 30 to 160 sec. Example 12 75 0.5 20 to 170 sec. Example 13 75 0.5 20 to 150 sec. Example 14 75 0.5 30 to 150 sec. Example 15 75 0.8 40 to 180 sec. Example 16 100 0.5 10 to 120 sec. Example 17 75 0.5 30 to 180 sec. Example 18 75 0.5 40 to 190 sec. Example 19 100 0.5 20 to 160 sec. Comparative Example 1 50 4.5 10 to 200 sec. Comparative Example 2 100 5.0 Peeled at 10sec. Comparative Example 3 100 0.8 10 to 20 sec. Comparative Example 4 25 8.7 120 to 160 sec. Comparative Example 5 75 3.0 30 to 40 sec. Comparative Example 6 Phase separation of liquid when preparing resist solution Comparative Example 7 25 10.3 100 to 130 sec.

As apparent from Table 2, the photocurable composition of the present invention exhibited excellent characteristics in coating film thickness uniformity and development range as compared with the comparative example. In particular, satisfying both the application limit speed and the development range can only be seen in the examples.

(Example 20)

<Manufacture of Component Parts for LCD>

Using the photocurable composition of Example 1, the spacer for LCD was manufactured as follows.

On the glass substrate of 100 mm x 100 mm, the composition obtained in Example 1 was applied dropwise to the center using a spinner. Subsequently, the prebaking process was performed in an oven for 60 second at 90 degreeC, and 200 mW / cm <2> proximity exposure (roughness is 20 mW / cm <2>) through the mask in which 10 micrometer dots exist in one ratio at 80 micrometers x 200 micrometers. The proximity gap was 100 µm, and then developed and washed with water at 30 ° C. with a 10% dilution of alkaline developer CD (manufactured by Fujifilm Arch Co., Ltd.). Then, it post-baked in 230 degreeC and oven for 30 minutes, and created the columnar spacer of 5 micrometers in height.

(Comparative Example 8)

In Example 20, the columnar spacer of 5 micrometers in height was created on the same conditions as Example 20 except having changed the photocurable composition into the thing of the comparative example 7.

Mask dimension reproducibility and indentation displacement of the columnar spacers of Example 20 and Comparative Example 8 were evaluated by the following method.

(1) Mask dimension reproducibility:

The mask dimensions were evaluated by the size of the spacer obtained at the development time. The closer the spacer size is to the mask dimension, the better the mask dimension reproducibility is.

(2) Indentation displacement:

The indentation displacement was measured by applying a load with an ultra-micro hardness tester DUH-200 (manufactured by Shimadzu Corporation) for the individual patterns on the substrate obtained through the above process. The measurement temperature of the indentation displacement was room temperature (25 ° C.), the pressure head was a diamond-shaped cone trapezoid (flat section with a diameter of 50 µm), and the test load was 2 g.

Pattern dimension (㎛) Indentation displacement (μm) Remarks Example 20 10 0.8 Comparative Example 8 16 0.5 Japanese Patent Publication No. 2002-20442

As apparent from Table 3, the columnar spacers obtained by using the photocurable composition of the present invention faithfully reproduced the mask dimensions in terms of pattern dimensions, and also increased the indentation displacement amount.

(Example 21)

Manufacture of Components for Solid State Imaging Devices

Using the photocurable composition of Example 1 as a primer layer, the color filter which is a component for solid-state image sensors (image sensors) was manufactured as follows.

1) Fabrication of silicon wafer substrate with primer layer formed

A 6 inch silicon wafer was heated in an oven at 200 ° C. × 30 minutes. Next, the photocurable composition of Example 1 was apply | coated so that a dry film thickness might be set to 2.0 micrometers on the said silicon wafer, and it heat-dried at 220 degreeC * 1 hour in oven, and obtained the silicon wafer substrate in which the primer layer was formed.

2) Production of color filter layer

Color coating liquid (Fuji Film Arch Co., Ltd. product SR-3000L) is spin-coated on the primer layer of the silicon wafer board | substrate with the primer layer obtained above, and it heat-processes (prebakes) 100 degreeC * 120 second by the hotplate, The dry film thickness was set to 1.0 m. Moreover, it irradiated with the exposure amount of 40-520mJ / cm <2> through the 3.0-micrometer island pattern mask using the I-line stepper exposure apparatus FPA-3000i5 + (made by Canon Corporation).

After exposure, the developer CD-2000 (manufactured by Fuji Film Arch Co., Ltd.) was diluted with water so as to have a concentration of 60% by mass, and used as a spin shower developer (DW-30 type (Chemtronics Co., Ltd.)). Paddle development was carried out at ℃. The substrate was rotated and pure water was supplied from the top into a shower, rinsed, and then spray dried. Furthermore, the color filter was produced by heat-processing (post-baking) at 200 degreeC x 5 minutes with a hotplate.

(Comparative Example 9)

In Example 21, the color filter was similarly produced without forming a primer layer.

The developability of the color filters of Example 21 and Comparative Example 9 was evaluated by the following method.

Whether the pattern was formed at intervals of 10 seconds from 30 seconds to 100 seconds or not was observed with an optical microscope (500 times), and the picture was taken.

As a result, in Example 21, although the formation of the pattern was confirmed from 30 to 100 seconds, in Comparative Example 9 in which the primer layer was not formed, the pattern could be formed at 30 seconds and 40 seconds, but dropped at 50 seconds. (缺 落) was.

The photocurable composition of the present invention has excellent photocurability (no need for thermosetting) and developability, and is excellent in coating property, coating film uniformity and liquid saving property, and also excellent in transmittance.

Therefore, it is possible to easily obtain excellent component for LCD and component for solid-state image sensor (image sensor) from the composition of this invention.

Claims (7)

In a photocurable composition containing an alkali-soluble photocurable resin, a photocurable monomer, a photopolymerization initiator, and a solvent, the compound (1-1) and compound (1-2) in which the alkali-curable photocurable resin includes the following structural units And at least one copolymer selected from compounds (1-3). Compound (1-1): the following structural units (a1), (a2), (b1), (b2), (c1) and (d) Compound (1-2): the following structural units (a1), (a2), (b1), (b2), (c2) and (d) Compound (1-3): the following structural units (a1), (a2), (b1), (b2), (c3), (c4) and (d) The structural ratio of each structural unit in the compounds (1-1) to (1-3) is 10% to 70% by weight in total, a1 and a2 in mole%, b1 and b2 in total, 5 to 40%, c1 is 5-40%, c2 is 5-40%, c3 and c4 are 5-40% in total, d is 5-30%, R represents a hydrogen atom or a methyl group, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxyl group, an aryl group having 7 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, R ₂ and R ₄ each independently represent a phenylcarbamic acid ester containing an alkylene group having 1 to 18 carbon atoms, an alkyl group having 1 to 4 carbon atoms as a substituent, or a carbamic acid ester having an alicyclic group having 3 to 18 carbon atoms. Indicate, R <_3> represents a C2-C16 linear or branched alkylene group, R ₅ represents an alkyl group having 1 to 4 carbon atoms, l represents the integer of 2-30, m represents 0 or the integer of 1-20, n represents an integer of 2 to 20, X represents a group selected from the following general formulas (1) to (9). The photocurable composition according to claim 1, wherein the alkali-soluble photocurable resin contains 0.1 to 5.0 meq / g of a (meth) acryloyl group and an acid value of 20 to 200. The photocurable composition according to claim 1 or 2, wherein a mass average molecular weight (Mw) of the alkali-soluble photocurable resin is 5,000 to 30,000. The photocurable composition according to any one of claims 1 to 3, further comprising a colorant. An LCD component, which is made of the photocurable composition according to any one of claims 1 to 4. A component for a solid state image pickup device, which is made of the photocurable composition according to any one of claims 1 to 4. The coating film forming process which slit-coats the photocurable composition of any one of Claims 1-4, the photocuring process of irradiating the coating film obtained through the said film forming process in pattern form, and the said photocuring process process A method of manufacturing a component for an LCD or a component for a solid state image pickup device comprising an alkali development step using an alkaline developer after.