TW202237669A - Photosensitive resin, photosensitive resin composition containing the same, cured product, and color filter - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition and a photosensitive resin using the same capable of providing a cured product having good alkali developability, linearity, and pattern shape, good balance between surface curability and deep curability, and suppressed generation of wrinkles on the surface. Provided is a resin and a photosensitive resin composition using the same, the resin is represented by the following general formula (1).

Here, R₁, R₂, R₃ and R₄ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. E represents -CR_xR_y-, -CO-, -SO₂-, -O-, -S-, -SS-, -SO-, -OCO-, -SiR_xR_y- or a linear bond, and R_x and R_y each represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with hydrogen, a halogen atom, or a halogen atom. R_x and R_y may be bonded to each other to form a ring. A represents a tetravalent tetracarboxylic acid residue. G₁ represents an alkylene group having 1 or more carbon atoms, D represents a hydrogen atom, a substituent having a polymerizable unsaturated group, or a substituent having a carboxyl group and a polymerizable unsaturated group, and n₁ and n₂ each independently represents an integer of 0 or more. J represents a hydrogen atom or a substituent having a carboxyl group. However, one or more of D in the general formula (1) represents a substituent having a carboxyl group and a polymerizable unsaturated group.

Description

Photosensitive resin, photosensitive resin composition using the photosensitive resin, cured product of the photosensitive resin composition, and color filter

The present invention relates to a photosensitive resin that can be cured by irradiation with light such as ultraviolet rays or electron rays, and can be patterned by performing an alkaline development treatment, and a photosensitive resin composition using the resin, and further relates to a photosensitive resin composition using the photosensitive resin. Cured products of resin compositions, and color filters using cured products.

In recent years, most displays such as TVs, monitors, and smartphones use color liquid crystal displays (LCDs) or organic EL displays (OLEDs). A member composed of a pattern formed of a photosensitive resin composition is used. Among these components, for example, color filters are used in almost all LCDs, and in OLEDs, color filters are used mainly in large TVs, and are one of the important components affecting visibility. The manufacturing method of color filters usually uses the following method: form a black matrix (black matrix) on the surface of a transparent substrate such as glass or plastic sheet, and then form red, green, and blue ( RGB) with different hues. The size of the pattern will vary depending on the purpose of the color filter or individual colors, RGB The pixel line is thinned to 100 μm to 50 μm or less, and the black matrix is thinned to 20 μm to 10 μm or less. Therefore, a photosensitive resin composition for obtaining a color filter is required to be patterned with high dimensional accuracy. Also, if the surface hardening properties and deep hardening properties of the photosensitive resin composition cannot be balanced, wrinkles will be generated on the matrix surface during the firing step of the color filter. Depending on the application of the color filter, the surface of the filter will be uneven and affect the visual recognition of LCD and other displays, so the balance between surface hardening and deep hardening is also one of the important characteristics.

In addition, in the manufacture of LCD, a transparent hardened film (hereinafter referred to as protective film) is formed on the surface of the color filter as a protective film. The purpose of forming the protective film is to flatten the surface of the color filter or to improve the color. The durability of the filter relative to the heat treatment or chemical treatment in the subsequent steps, and the improvement of the reliability of the LCD. The protective film of the color filter requires transparency, chemical resistance, adhesion, hardness, flatness, and heat resistance. And electrical reliability (electrical reliability) and so on.

The method of forming the protective film includes thermal hardening and photolithography. In the panel design and processing step design of the color filter, it is based on the characteristics that the protective film should have (the required characteristics of the aforementioned protective film) and It is selected whether it is patterned or not. When forming a protective film by photolithography, in order to form an appropriate pattern, in addition to the above-mentioned characteristics, the photosensitive resin composition also requires the ability to absorb short-wavelength ultraviolet light (high sensitivity) that does not affect the color display of LCD.

Generally speaking, the photosensitive resin composition used in this application or the resin composition used in semiconductors often use resins (including monomers or oligomers) that are polymerizable or alkali-soluble, or have both properties. ) or a photopolymerization initiator, etc.

For example, Japanese Unexamined Patent Application Publication No. 2017-219838 (Patent Document 1) discloses a photosensitive resin (copolymer) and a photosensitive resin composition using the photosensitive resin, wherein the photosensitive resin is prepared by using the terpene compound and The reactant of tetracarboxylic dianhydride is added to (meth)acrylate containing epoxy group and winner. In this document, although the characteristics of the photosensitive resin composition are useful, the "polymerization imparting reaction" and the "alkali solubility imparting reaction" cannot be separated in the production method, and when individual characteristics are changed, other characteristics will definitely be affected. Therefore there is still room for improvement.

In addition, Japanese Patent Application Laid-Open No. 2008-156613 (Patent Document 2) and Japanese Patent Application Publication No. 2008-268854 (Patent Document 3) disclose a photosensitive resin and use of the resin with high sensitivity and a large development adhesion limit range The photosensitive resin composition, wherein, regarding the photosensitive resin, a copolymer containing a carboxyl group is obtained by reacting a diol compound containing a polymerizable unsaturated group with a tetracarboxylic acid or an acid dianhydride thereof, and further making the The photosensitive resin is obtained by reacting the carboxyl group-containing copolymer with the epoxy compound containing the polymerizable unsaturated bond group, and further reacting with the dicarboxylic acid or its monoacid anhydride. However, this document does not mention the balance between surface hardening properties and deep hardening properties. In the inventions described in these documents, there are many acryl groups (acrylates), so they are highly sensitive. Therefore, the pattern surface and deep hardening properties cannot be balanced, and there are disadvantages such as wrinkles on the surface and thick lines.

That is, it is conceivable to increase the concentration of polymerizable unsaturated groups (acrylic acid ester concentration) for high sensitivity, but simply increasing the acrylate concentration will easily cause a photohardening reaction near the surface of the composition. When forming a pattern, if you want to If it is formed like a mask pattern, the light hardening of the deep part is likely to be insufficient, and the deep part will dissolve during development, making the pattern thinner (the so-called undercut state). At this time, if the exposure amount is increased, the undercut can be eliminated, but there is a possibility that only a pattern thicker than the mask pattern can be formed. In addition, it is not enough to simply increase the concentration of acrylate to achieve high sensitivity, and this phenomenon is more remarkable when forming a black resist with low light transmittance. Therefore, in the photosensitive resin composition, in order to form an appropriate pattern corresponding to the mask pattern, it is very important to obtain a balance between the surface hardening property and the deep hardening property, but no solution has been proposed in the prior art.

In addition, in order to obtain a photosensitive resin composition with a good balance between surface hardening properties and deep hardening properties, as another attempt, there are also blends of alkali-soluble resins that do not have polymerizable unsaturated groups and photopolymerizable monomers. However, if you do not mix more than a certain amount of resin components at this time, there are other problems that it is difficult to form a pattern with a small contact area with a substrate such as glass, such as peeling during development, or reliability tests. There is a risk that sufficient adhesion cannot be obtained, and these phenomena are more remarkable when the resin component content is small like black resist.

[Prior Art Literature]

[Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2017-219838.

Patent Document 2: Japanese Unexamined Patent Publication No. 2008-156613.

Patent Document 3: Japanese Patent Application Laid-Open No. 2008-268854.

Therefore, in the situation where this prior art exists, the inventors of the present application intensively studied the development of a photosensitive resin composition having a balance between sensitivity and alkali developability. Acryl group introduction reaction" and "use specific (D) component to block the terminal structure, so that acid value adjustment and sensitivity adjustment can be individually carried out" can be achieved.

Therefore, an object of the present invention is to provide a photosensitive resin composition using a photosensitive resin having a balance between sensitivity and alkali developability.

Another object of the present invention is to provide a photosensitive resin composition using a photosensitive resin having a balance between surface hardening properties and deep hardening properties.

That is, the gist of the present invention is as follows.

[1] A resin represented by the following general formula (1).

Wherein, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. Also, E represents -CR _x R _y -, -CO-, -SO ₂ -, -O-, -S-, -SS-, -SO-, -OCO-, -SiR _x R _y - or a direct bond, R _x and R _y represent hydrogen, a halogen atom, or a hydrocarbon group having 1 to 12 carbons which may be substituted by a halogen atom. Also, R _x and R _y may be bonded to each other to form a ring. A represents a tetravalent tetracarboxylic acid residue. In addition, _G1 represents an alkylene group having 1 or more carbon atoms, D represents a hydrogen atom, a substituent having a polymerizable unsaturated group, or a substituent having a carboxyl group and a polymerizable unsaturated group, and _n1 and _n2 independently represent An integer of 0 or more. Also, J represents a hydrogen atom or a substituent having a carboxyl group. However, one or more of the plurality of Ds in the general formula (1) represents a substituent having a carboxyl group and a polymerizable unsaturated group.

[2] The resin as described in [1], wherein, in the general formula (1), D represents a hydrogen atom or a substituent represented by the following general formula (2), and J represents a hydrogen atom or the following general formula (3 ) as a substituent.

Wherein, G2 independently represents a single bond, or an alkylene group having ₁ or more carbons, R5 represents a hydrogen atom or a methyl group, and Q represents a trivalent hydrocarbon group having ₂ to 8 carbons. Also, n ₃ represents an integer of 1 or more, and when n ₃ is 2 or more, the plurality of G ₂ in the formula may be the same or different.

Wherein, L represents 2 or 3 valent carboxylic acid residues, n ₄ represents 1 or 2.

[3] A photosensitive resin composition comprising the following (i) to (ii).

(i) The resin mentioned in [1] or [2];

(ii) A photopolymerization initiator.

[4] The photosensitive resin composition according to [3], further comprising (iii) a photopolymerizable monomer having at least one ethylenically unsaturated bond.

[5] The photosensitive resin composition as described in [3] or [4], further comprising (iv) a dispersoid.

[6] A cured product obtained by curing the photosensitive resin composition described in any one of [3] to [5].

[7] A color filter comprising the cured product described in [6].

In the present invention, a compound containing a bis-hydroxyl (alkoxy) group is reacted with a tetracarboxylic acid or its acid dianhydride, and the resulting reactant is reacted with an oxirane compound (epoxide) having a polymerizable unsaturated group. compound) and further react with dicarboxylic acids or their acid monoanhydrides to obtain a copolymer containing carboxyl groups and photopolymerizable unsaturated groups (hereinafter referred to as photosensitive resin) that is suitable as a photosensitive resin composition material. In addition, the photosensitive resin has good alkali developability, so the linearity and pattern shape are good, and the balance between surface hardening property and deep hardening property is also good, so a photosensitive resin composition can be obtained, which can be used even in the production of color by thick film method. The optical filter has almost no wrinkles on the surface after heat treatment.

The present invention will be described in detail below.

The present invention is characterized by using a resin represented by the general formula (1) in order to achieve the aforementioned object. In addition, the photosensitive resin composition in the present invention uses the resin represented by the general formula (1) and the photopolymerization initiator as essential components, and a photopolymerization agent having at least one ethylenically unsaturated bond is combined according to the application. Sexual monomers, or dispersoids, etc., thereby exerting functions. The resin represented by the general formula (1) not only has free radical polymerizability derived from photopolymerizable unsaturated groups, but also has acidic groups derived from dicarboxylic acid or its acid monoanhydride used as a blocking agent, so it has alkali Soluble.

Regarding the resin represented by the general formula (1), at first bis-phenol compound or a compound containing a bis-hydroxyalkoxy group (hereinafter referred to as a compound containing a bis-hydroxyl (alkoxy) group) and a tetracarboxylic acid or its acid Dianhydride reaction. Here, since the bis-hydroxy (alkoxy) group-containing compound does not contain a polymerizable unsaturated group, the sensitivity of the entire resin can be controlled only by the polymerizable unsaturated group-imparting reaction of the subsequent reaction. Moreover, the weight average molecular weight of the whole resin can be controlled by using tetracarboxylic acid or its acid dianhydride. Next, the obtained reactant is reacted with an oxirane compound (epoxy compound) having a polymerizable unsaturated group, and then further reacted with dicarboxylic acids or their acid monoanhydrides to obtain a carboxyl group-containing and photopolymerizable compound. Copolymers with unsaturated groups. In this way, "impartment of polymerizable unsaturated group" and "imposition of alkali-soluble group (carboxyl group)" can be controlled separately, so when changing the characteristics of the photosensitive resin composition, each parameter can be changed independently. The resin in the present invention has both a polymerizable unsaturated group and an alkali-soluble group (carboxyl group), so it can impart excellent photocurability to the photosensitive resin composition, good developability with respect to an alkali developer, and the results achieved thereby Excellent patterning properties can improve the properties of photoresists used in the semiconductor and display fields.

The resin represented by the general formula (1) in the present invention is a carboxyl group- and photopolymerizable unsaturated group-containing copolymer manufactured using at least four components from the following (A) component to (D) component. (A) component is a compound containing bis-hydroxyl (alkoxy) group, (B) component is tetracarboxylic acid or its acid dianhydride, (C) component is an oxirane compound having a polymerizable unsaturated group ( Epoxy compound), (D) component is dicarboxylic acid, tricarboxylic acid or its Acid monoanhydride. That is, let "the carboxyl group-containing compound produced by the reaction of the hydroxyl group possessed by the component (A) and the acidic group possessed by the component (B)" be the compound (AB), and "the compound possessed by the compound (AB) A compound having a polymerizable unsaturated group produced by the reaction of the acidic group of the compound (ABC) with the epoxy group possessed by the component (C)" When the compound (ABC) is used, the The resin of the formula (1) which is the objective copolymer can be obtained by reacting the acidic group which a component has.

The synthesis method of compound (AB) is not particularly limited, for example, the reaction can be carried out at a reaction temperature of 90°C to 150°C, preferably 100°C to 140°C. Moreover, it is preferable that the molar ratio (B/A) of (A) component and (B) component reacts quantitatively so that it may be 50 % or more and less than 100 %. At this time, the weight average molecular weight varies depending on the raw material types and blending ratios of (A) and (B) components, and is not particularly limited, but may be about 1,000 to 12,000, preferably about 1,200 to 8,000.

The photosensitive resin represented by the general formula (1) can be obtained from the above-mentioned compound (AB). The compound (AB) has a structure in which D and J in the above-mentioned general formula (1) are still hydrogen atoms. In the structural formula, n The average value of ₁ is preferably in the range of 0-20, more preferably in the range of 0-8. Also, n ₂ is independently 0 or more, preferably 0-3, more preferably 1-2. G ₁ represents an alkylene group having 1 or more carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms.

Next, the synthesis method of compound (ABC) is not particularly limited, and general reaction conditions for the addition reaction of carboxylic acid and oxirane compound can be used, for example, the reaction temperature is preferably in the range of 40 to 120° C., more preferably 50° C. to about 100°C. Also, the molar ratio [C/(AB)] of the component (C) to the compound (AB) is preferably from 50% to 250%, more preferably from 100% to 200%. At this time, since the component (C) is an oxirane compound having a polymerizable unsaturated group, at least one reaction between the component (C) and the compound (AB) is carried out, thereby further combining with (D) described later. Component reactions complement each other, and at least one D in the general formula (1) becomes a substituent having a carboxyl group and a polymerizable unsaturated group. That is, according to the blending ratio of the (C) component of the reaction, it can be controlled The balance between surface hardening and deep hardening of the resin composition. At this time, the weight average molecular weight is not limited because it varies depending on the type of raw material and the blending ratio of the component (C), but it may be about 1000 to 15000, preferably about 1200 to 9000.

Next, the synthesis method of reacting compound (ABC) and component (D) is not particularly limited, for example, the reaction temperature is preferably in the range of 20 to 120°C, more preferably about 40 to 100°C. Also, the molar ratio [D/(ABC)] of the component (D) to the compound (ABC) is preferably from 10 to 500%, more preferably from 30 to 400%. The purpose of the molar ratio of the (D) component is to adjust the acid value of the resin represented by the general formula (1), so it can be changed arbitrarily. At this time, the weight average molecular weight varies with the raw material type and blending ratio of the (D) component, so it is not limited, and it can be about 1,500 to 20,000, preferably about 2,500 to 10,000. Also, the acid value (solid content acid value) of the resin of the general formula (1) obtained by reacting the (D) component will vary depending on the raw material type and the blending ratio of the (D) component, so it is not limited and can be 20 to about 200 mgKOH/g, preferably about 20 to 150 mgKOH/g.

First, the (A) component will be described.

Component (A) uses a compound containing a bis-hydroxyl (alkoxy) group, which has the addition of a bisphenol compound having the structure of E and R ₁ to R ₄ in general formula (1). A structure made of " _G1 structure of alkylene oxide". Among them, preferred specific examples of E include -CR _x R _y -, -CO-, -SO ₂ -, -O-, -S-, -SS-, -SO-, -OCO-, -SiR _x R _y - or direct bond etc. More preferably, there may be mentioned -CR _x R _y -, -CO-, -SO ₂ -, -O-, -SiR _x R _y - or a direct bond. Also, R ₁ to R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. Desirable specific examples of R _x and R _y include hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 12 carbon atoms which may be substituted by halogen atoms, or substituents in combination thereof. More preferred specific examples include A hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a cycloalkyl group having 3 to 9 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted by a halogen atom, or A substituent formed by combining these. In addition, R _x and R _y may be bonded to each other to form a ring, and examples of the formed ring include oxanediyl, adamantanediyl, and indanediyl groups.

From the perspective of preferred examples of E, preferred examples of compounds containing bis-hydroxyl (alkoxy) groups include bis(4-hydroxyphenyl)ketone, bis(4-hydroxyl-3,5- Dimethylphenyl) Ketone, Bis(4-Hydroxy-3,5-Dichlorophenyl) Ketone, Bis(4-Hydroxyphenyl) Phenyl, Bis(4-Hydroxy-3,5-Dimethylphenyl) ) Bis(4-hydroxy-3,5-dichlorophenyl) bis(4-hydroxy-3,5-dichlorophenyl) bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoro Propane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl) Dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl) Methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethyl Phenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis (4-Hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5 -Dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene, 9,9-bis(4-hydroxy -3-Chlorophenyl) fluorene, 9,9-bis[4-(2-hydroxyethoxy)phenyl] fluorene, 9,9-bis(4-hydroxy-3-bromophenyl) fluorene, 9, 9-bis(4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl) fluorine, 9,9-bis(4-hydroxy-3,5- Dimethylphenyl) fluorine, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) fluorine, 9,9-bis(4-hydroxy-3,5-dibromophenyl) fluorine, etc. 9,9-bis(hydroxy(poly)C2-4 alkoxyphenyl) terrene, 4,4'-biphenol, 3,3'-biphenol, etc. Among them, the one using 9,9-tertilene diyl is more preferable. These bis-hydroxy (alkoxy) group-containing compounds can be used alone or in combination of two or more.

Next, tetracarboxylic acids or acid dianhydrides of the (B) component that react with the above-mentioned bis-hydroxy (alkoxy) group-containing compound are preferably used in the compound containing bis-hydroxy (alkoxy) group Tetracarboxylic acid or its acid dianhydride reacted with the hydroxyl group. Preferable specific examples include saturated linear hydrocarbon tetracarboxylic acids such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, and cyclohexane tetracarboxylic acid. Tetracarboxylic acid, cycloheptane Alicyclic tetracarboxylic acids such as tetracarboxylic acid and norbornane tetracarboxylic acid, pyromeltaric acid, diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenylphosphonium Aromatic tetracarboxylic acids such as tetracarboxylic acids, or acid dianhydrides thereof. It is preferably biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, biphenyl ether tetracarboxylic acid or its acid dianhydride, and more preferably biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or Its acid dianhydride. These tetracarboxylic acids or their acid dianhydrides can be used alone or in combination of two or more. A in General formula (1) represents the tetracarboxylic-acid residue derived from this (B) component.

Next, the oxirane compound (epoxy compound) of component (C) that reacts with the reactant [compound (AB)] of component (A) and component (B) above is used: The epoxy group is capable of reacting with the carboxyl group of the compound (AB) and contains one or more polymerizable unsaturated groups in the molecule. The (C) component will form a substituent shown in the general formula (2) (but in this stage, the part of J is a hydrogen atom) after the reaction with the compound (AB), and the part that forms Q after the reaction will have Epoxy. Among them, in the component (C) and the general formula (1), G ₂ independently represents a single bond, or an alkylene group having 1 or more carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. R ₅ represents a hydrogen atom or a methyl group. n ₃ represents an integer of 1 or more, preferably 1 to 3. When n ₃ is 2 or more, the plurality of G ₂ may be the same or different. Also, Q after the reaction represents a trivalent hydrocarbon group having 2 to 8 carbon atoms, preferably a cycloalkyl group. Specific examples of the cycloalkyl group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.

Preferred specific examples of the (C) component include glycidyl (meth)acrylate (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether (4-hydroxybutyl ( meth)acrylate glycidyl ether), 3,4-Epoxycyclohexylmethacrylate (3,4-Epoxycyclohexylmethacrylate), 3,4-epoxycyclohexylmethyl (meth)acrylate (3,4-Epoxy Chlohexylmethyl (meth) acrylate) and the like. These ethylene oxide compounds may be used alone or in combination of two or more.

Then, dicarboxylic acids, tricarboxylic acids, or acid monoanhydrides of the (D) component that are further reacted with the compound (ABC) that is a reactant of the components (A) to (C) are used: to make the compound (ABC) have The hydroxyl group of (D) reacts with the acidic group which component (D) has. Desirable specific examples of the component (D) include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, and pentamethylene glycol Acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and other saturated straight-chain hydrocarbon dicarboxylic acids, hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norcamphene Alkanedicarboxylic acid, saturated cyclic hydrocarbon dicarboxylic acid such as hexahydrotrimellitic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid Unsaturated dicarboxylic acids such as dicarboxylic acid, chlorobridge acid, and trimellitic acid, or monoanhydrides of these acids, etc. Preferred are succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid or its monoanhydride, more preferably succinic acid, itaconic acid, Tetrahydrophthalic acid or its acid monoanhydride, these dicarboxylic acids or its acid monoanhydride can be used 1 type or in mixture of 2 or more types. J in the general formula (1) is derived from the component (D). In addition, in the skeleton of the general formula (1), L represents a 2- or 3-valent carboxylic acid residue, and n ₄ represents 1 or 2.

In the present invention, in the synthesis of the resin of the general formula (1) characterized by carboxyl groups and polymerizable unsaturated groups in the molecule, the solvent used is not particularly limited, for example, it can use a solvent that does not have a hydroxyl group and has a temperature higher than the reaction temperature. A solvent with a boiling point is used as a reaction solvent, and specific examples of the solvent can be Cellosolve solvents such as ethyl cellothreoacetate and butyl cellothreoacetate, or diglyme, ethyl High boiling point ether or ester solvents such as Ethylcarbitol Acetate, Butylcarbitol Acetate, and Propylene Glycol Monomethyl Ether Acetate, Ketone solvents such as cyclohexanone and diisobutyl ketone, etc.

Also, the catalyst used is not particularly limited, for example, ammonium salts such as tetraethylammonium bromide, triethylbenzyl ammonium chloride, triphenylphosphine, tris(2,6-dimethoxyphenyl Phosphines such as base) phosphines are known.

These solvents and catalysts may be used alone or in combination of two or more.

In order to exhibit the effect of a photosensitive resin composition, a component (ii) photoinitiator is used as an essential component. In addition, the photoinitiator used in the present invention includes a sensitizer. Specific examples of photopolymerization initiators include acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and dibenzophenone dimethyl ketal, Benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone and other benzophenone compounds, benzoin ethyl ether, Benzoin ether compounds such as benzoin tertiary butyl ether, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(N ,N-dimethylamino)-1-(4-morpholinophenyl)butane-1-one and other α-aminoalkylphenon compounds, thioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone, azobisisobutylnitrile, benzoyl peroxide, cumene peroxide and other organic peroxides, 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetraphenyl-1,2-diimidazole and other diimidazole compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloro Methyl-5-(p-cyanostyrene)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole Halomethylthiazole compounds such as oxadiazole, titanocene compounds such as bis(η 5-cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]titanium, 2,4 ,6-tris(trichloromethyl)-1,3,5-triazine, 2-[3,4-(methylenedioxy)phenyl]-4,6-bis(trichloromethyl)- Triazine compounds such as 1,3,5-triazine, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone Sulfur compounds such as ketones, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone and other anthraquinones, (2,4,6-trimethylanthraquinone Acyl phosphine oxide compounds such as diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, quinone compounds such as camphorquinone, 2- Mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, Methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy )-ethyl]-isocyanurate, neopentylthritol tetrakis(3-mercaptobutyrate), neopentylthritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercapto propionate), diperythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid and other thiol compounds, Tertiary amines such as triethanolamine and triethylamine, 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-O-benzoyl oxime, 1-[9-ethyl Base-6-(2-methylbenzoyl)carbazol-3-yl]ethanone, o-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropane Base-9H-Oxime-2-yl)-Acetyl oxime, Ethanone-1-[7-(2-Methylbenzoyl)-9,9-dipropyl-9H-Oxime-2-yl ]-1-(o-acetyl oxime), ethanone-1-(-9,9-dibutyl-7-nitro-9H-fen-2-yl)-1-o-acetyl oxime and other oximes There are no particular limitations on ester compounds and the like, and they may be used alone or in combination of two or more.

Regarding the usage amount of the photopolymerization initiator of the component (ii), the resin of the general formula (1) as the component (i), and the epoxy acrylate described later or its acid addition as other resin components optionally contained The compound and the photopolymerizable monomer having at least one ethylenically unsaturated bond added as the component (iii) described later depending on the application are based on a total of 100 parts by weight. The component (ii) photopolymerization initiator The usage amount is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight. When the usage-amount of a component (ii) photoinitiator is small, a photopolymerization speed will fall, and there exists a possibility that the sensitivity of a photosensitive resin composition may fall. On the other hand, if the amount used is large, the sensitivity of the photosensitive resin composition will be too high, and there may be problems that the pattern line width becomes thicker than expected and the pattern edges are not sharp.

Also, depending on the application, the essential component (iii) is a photopolymerizable monomer having at least one ethylenically unsaturated bond, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 2-ethylhexyl (meth)acrylate and other monomers with hydroxyl groups, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate base) acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane Tri(meth)acrylate, neopentylthritol di(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteoerythritol tetra (Meth)acrylate, Di-Neopentylthritol Penta(Meth)acrylate, Di-Neopentylthritol Hexa(meth)acrylate, Glyceryl (Meth)acrylate, Glycerin Di(meth)acrylate, Glyceryl tri(meth)acrylate, Sorbitan penta(meth)acrylate, Sorbitan hexa(meth)acrylate (Meth)acrylic esters such as acrylates, alkylene oxide modified hexa(meth)acrylates of phosphazene, caprolactone modified diperythritol hexa(meth)acrylates, etc. Dendritic polymers with (meth)acryl groups of double bond compounds, bisphenol A epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, bisphenol Type epoxy (meth) acrylate, diphenyl fennel type epoxy (meth) acrylate, phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate base) acrylates, phenol aralkyl type epoxy (meth)acrylates and other cardoepoxy (meth)acrylates or acid adducts thereof. These compounds may be used alone or in combination of two or more.

These components (iii) can be added according to the application. When adding, it is preferable to adjust the blending ratio of the aforementioned epoxy acrylate or its acid-added compound with respect to the aforementioned component (i) and other resin components that may be included as necessary. Mixing ratio, the mixing ratio of these components [[(i)+α]/(iii)] is preferably 20/80 to 100/0, more preferably 40/60 to 90/10. If the component (iii) is too much, the hardened product after photocuring will become weak, the acid value of the coating film in the unexposed part will be lowered, the solubility of the alkali developer will be reduced, and the edge of the pattern will not be sharp. Therefore, use ( In the case of iii), it is preferable to be in the said range. In addition, the above-mentioned α represents epoxy acrylate and its acid-added compound described later as other resins.

Moreover, the photosensitive resin composition in this invention can add a component (iv) dispersoid as needed according to a desired use or a function. The dispersant of component (iv) is not particularly limited, and organic pigments, titanium oxide pigments, composite oxide pigments, etc. selected from red, blue, green, purple, yellow, cyan, magenta, brown, black, white, etc. can be used Inorganic pigments, organic fillers such as acrylic polymer particles and urethane polymer particles, silica, talc, mica, glass fiber, carbon fiber, calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, barium sulfate, etc. Inorganic fillers, nanoparticles of metals or metal oxides, dyes, light-shielding materials, extender pigments, fillers, etc., can be used alone or in combination of two or more. Especially when using a light-shielding material such as black photoresist, carbon black, chromium oxide, iron oxide, titanium black, aniline black, perylene black, indigo black, etc., among which carbon black The light-shielding property, surface smoothness, dispersion stability, compatibility with resin, etc. are good, so it is preferable. Examples of extender pigments or fillers include glass fiber, silica, mica, alumina, and the like.

The dispersoid of component (iv) may be used together with a dispersant if necessary. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorine-based surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.

When the dispersoid of component (iv) is used, it may be 10 to 400 parts by weight relative to 100 parts by weight of the total amount of resin represented by general formula (1) of component (i), other resin components described later, and optional component (iii). , preferably in the range of 50 to 230 parts by weight. If it is too small, it will become difficult to exhibit the function expected from addition (iv). On the other hand, if it is too large, the dispersion stability of the photosensitive resin composition may be lowered, and the development characteristics and film forming ability may be impaired, so the above-mentioned range is preferable.

The photosensitive resin composition in the present invention may be used by dissolving in a solvent or blending various additives as necessary. That is, solvents other than the aforementioned essential components and optional components may be used. Examples of solvents include methanol, ethanol, n-propanol, isopropanol, alcohols such as ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, Ketones such as N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosulfur, ethyl cellosulfur, methyl carbitol, ethyl carbitol Must alcohol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Glycol ethers such as base ether, ethyl acetate, butyl acetate, cellothracetate, ethyl cellothracetate, butyl cellothracetate, carbitol acetate, ethyl Acetate esters such as carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate can be used singly or in combination of two or more use.

In addition, other resins, hardeners, hardening accelerators, surfactants, silane coupling agents, viscosity modifiers, defoamers, leveling agents, ultraviolet absorbers, thermal Known additives such as polymerization inhibitors, antioxidants, and plasticizers.

Among them, other resin components include, for example, vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, and epoxy resins. Examples of epoxy resins include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fennel type epoxy compounds, diphenyl fennel type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac Varnish type epoxy compound, phenol aralkyl type epoxy compound, phenol novolak compound containing naphthalene skeleton (eg NC-7000L, manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, triphenol Methane type epoxy compound (such as EPPN-501H, manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, methyl ether Copolymers of acrylic acid and glycidyl methacrylate are representative copolymers of monomers with (meth)acryl groups containing glycidyl (meth)acrylate as units, 3',4'- Epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate (such as celloxide 2021P, manufactured by Daicel Co., Ltd.), butanetetracarboxylic acid tetrakis (3,4-epoxycyclohexylmethyl) modified ε - Caprolactone (such as EPL GT401, manufactured by Daicel Co., Ltd.), epoxy compounds having an epoxycyclohexyl group (such as HiREM-1, manufactured by Shikoku Chemical Industry Co., Ltd.), many having a dicyclopentadiene skeleton Functional epoxy compound (such as HP7200 series, manufactured by DIC Co., Ltd.), 1,2-epoxy-4-(2-oxiranyl group of 2,2-bis(hydroxymethyl)-1-butanol ) cyclohexane adduct (such as EHPE3150, manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (such as NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.), epoxy compound with polysiloxane skeleton Wait.

Moreover, the compound which makes these epoxy compounds react with the compound (for example, acrylic acid, methacrylic acid etc.) which has a polymerizable unsaturated group to form epoxy acrylate, and its acid addition compound can also be used.

Examples of hardeners include amine compounds, polycarboxylic acid compounds, phenol resins, amine resins, dicyandiamine, Lewis acid complexes, etc. that help harden epoxy resins. Examples of hardening accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclic compounds, and the like. Examples of surfactants include fluorine-based surfactants, polysiloxane-based surfactants, and the like. Examples of silane coupling agents include 3-(epoxypropyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanoxypropyltriethoxysilane, 3 - Ureidopropyltriethoxysilane, etc. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like.

In the photosensitive resin composition in the present invention, in the solid content excluding the solvent, the solid content of the essential components (i), (ii) (including (iii) and (iv) depending on blending) contains 60% in total. % by weight or more, preferably more than 75% by weight, more preferably more than 90% by weight, the amount of solvent will vary according to the target viscosity, but it is preferably 10 to 90% by weight relative to the photosensitive resin composition.

According to the above-mentioned photosensitive resin of the present invention and the photosensitive resin composition using the photosensitive resin, a hardened product (pattern) with good alkali developability, linearity, and good pattern shape can be obtained, and due to surface hardening and deep part The balance of curability is good, so as confirmed in the examples described later, there are very few wrinkles on the surface after heat treatment in the case of thick film production.

The coating film (cured product) of the present invention can be obtained, for example, by applying a solution of the above-mentioned photosensitive resin composition on a substrate or the like, drying it, and irradiating it with light (including ultraviolet rays, radiation, etc.) to harden it. (hardening). A desired pattern can be formed by setting a portion irradiated with light (exposed portion) and a portion not irradiated (unexposed portion), curing only the exposed portion, and dissolving the unexposed portion (uncured portion) with an alkaline solution.

Next, the manufacturing method of this pattern is demonstrated. First, after coating the photosensitive resin composition on the surface of the substrate, prebaking is performed as a drying step to form a coating film. Next, a photomask is applied to this coating film and exposed, and an unexposed portion is dissolved and removed using an alkali developing solution. Thereafter, post-baking is performed as a firing step to obtain a desired pattern using a cured product. The pattern manufacturing method can be applied to the manufacture of color filters or touch panels, and semiconductor packaging.

When coating the photosensitive resin composition on a substrate, any method such as a solution dipping method or a spraying method may be used in addition to known spin coaters, slit coaters, roll coaters, and the like. By these methods, a coating film having a desired thickness is formed and prebaked to form a coating film. Prebaking can be performed with a hot plate, an oven, a vacuum dryer, or a combination of these. The temperature and time in the pre-baking will vary according to the solvent used and the application of the photosensitive resin composition, and it can be carried out at 60 to 120°C for 1 to 10 minutes.

For the light irradiation when forming the hardened product, for example, visible rays, ultraviolet rays, extreme ultraviolet rays, electron rays, X-rays, etc. can be used, and radiation in the wavelength range of 250 to 450 nm is preferable. In addition, suitable developers for alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, aqueous solutions of hydroxides of alkali metals, aqueous solutions of organic bases such as tetramethylammonium hydroxide and diethanolamine, and the like. It is especially preferred to use an alkaline aqueous solution containing 0.01 to 1% of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, etc., and develop at a temperature of 20 to 30°C for 10 to 120 seconds. It is also possible to use a shower Developing method, spray developing method, immersion developing method, liquid tank developing method, etc. to precisely form a fine pattern.

The conditions of post-baking after development will vary according to the blending and application of the photosensitive resin composition, and it can be carried out at 80 to 250°C for 10 to 120 minutes. The purpose of implementing this post-baking is to improve the adhesion between the patterned coating film and the substrate, or to improve the linearity of the pattern through heat flow, or to reduce the surface roughness, etc., and the same as the pre-baking, it can be heated by a heating plate, an oven, Vacuum dryer or a combination of these.

The substrate used for patterning can be, for example, glass, silicon wafer, resin film (such as polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) and the like. In addition, pre-treatments such as formation of transparent electrode layers, chemical treatment with silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum evaporation, etc. can be appropriately performed on these substrates as needed. .

(Example)

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. In addition, the present invention is not limited to these Examples and Comparative Examples. Moreover, unless otherwise specified, resin evaluation in the following examples etc. was performed as follows.

[Solid content concentration]

Impregnate about 1 g of the resin solution obtained in the examples (including comparative examples, etc.) into a glass filter [W ₀ (g)] that has been placed in an aluminum foil cup and weigh it [W ₁ (g)]. The weight [W ₂ (g)] after heating for 2 hours was calculated according to the following formula.

Solid content concentration (weight (%))=100×(W ₂ -W ₀ )/(W ₁ -W ₀ ).

[acid value]

The resin solution was dissolved in tetrahydrofuran and titrated with 1/10 N-KOH aqueous solution using a potentiometric titration device "COM-A19" (manufactured by Hiranuma Sangyo Co., Ltd.) to obtain the acid value per 1 g of the sample (synthetic resin solution).

[molecular weight]

Gel permeation chromatography (GPC) "HLC-8320GPC" (manufactured by TOSOH Co., Ltd., developing solvent is THF, column is PL1110-6540 (1 tube) + PL1110-6530 (1 tube) + PL1110-6525 ( 1 piece) + PL1110-6520 (1 piece), the column temperature is 40°C, the flow rate is 1.0mL/min), and the conversion value of standard polystyrene (polystyrene kit made by SAS Co., Ltd.) is calculated. Weight average molecular weight (Mw).

In addition, the abbreviations used in the examples are listed below.

BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl)tertilene.

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride.

GMA: glycidyl methacrylate.

ECHMMA: 3,4-epoxycyclohexylmethyl methacrylate.

4HBAGE: 4-Hydroxybutyl Acrylate Glycidyl Ether.

THPA: 1,2,3,6-tetrahydrophthalic anhydride.

PGMEA: Propylene Glycol Monomethyl Ether Acetate.

BHT: dibutylhydroxytoluene.

TPP: Triphenylphosphine.

[Example 1]

Add 74.9g (170.1mmol) of BPEF [component (A)], 25.1g (85.1mmol) of BPDA [component (B)], and 100g of PGMEA into a 300mL three-necked flask with a reflux cooling tube, and heat at 125 to 130°C The mixture was stirred for 26 hours to obtain a reaction product (AB-1). Then, 14.9 g (104.6 mmol) of GMA [component (C)] was added to 115.1 g of the reaction product (AB-1), and 0.02 g (0.1 mmol) of BHT and 0.011 g (0.5 mmol) of TPP were further added, and at 85 to 90 The reaction product (ABC-1) was obtained by stirring under heating at °C for 18 hours. The solid content concentration of the obtained (ABC-1) was 55.9%. Next, 19.6 g (129.0 mmol) of THPA [component (D)] was added to 90.3 g of this reaction product (ABC-1), and it stirred under heating at 85-90 degreeC for 8 hours, and the synthetic resin 1 was obtained.

The solid content concentration of the obtained resin was 55.7%, the solid content acid value was 129 mgKOH/g, and the weight average molecular weight (Mw) analyzed by GPC was 3400.

Furthermore, the component names and blending ratios of (A) to (D) components in Example 1, as well as the acid value and weight average molecular weight of the obtained synthetic resin 1 are summarized in Table 1 (the same applies to the following examples and comparative examples) .

[Example 2]

Add BPEF [component (A)] 111.6g (254.6mmol), BPDA [component (B)] 37.5g (127.3mmol) and PGMEA 60.1g into a 300mL three-necked flask with a reflux cooling tube, and heat the mixture between 135 and 140°C It stirred under heating for 20 hours, and obtained the reaction product (AB-2). Next, 23.7 g (121.0 mmol) of ECHMMA [component (C)] was added to 97.4 g of the reaction product (AB-2), and 0.02 g (0.1 mmol) of BHT and 0.22 g (0.8 mmol) of TPP were further added, and the temperature was adjusted at 85 to 90 The reaction product (ABC-2) was obtained by stirring under heating at °C for 16 hours. The solid content concentration of the obtained (ABC-2) was 65.0%. Next, 16.9 g (114.0 mmol) of THPA [(D) component] was added to 90.9 g of this reaction product (ABC-2), and it stirred under heating at 85-90 degreeC for 8 hours, and the synthetic resin 2 was obtained.

The solid content concentration of the obtained resin was 58.0%, the solid content acid value was 106 mgKOH/g, and the weight average molecular weight (Mw) analyzed by GPC was 3600.

[Examples 3 to 10]

Instead of the ingredients (A) to (D) (i.e. BPEF, BPDA, ECHMMA and THPA) used in Example 2 above, the raw materials and blending ratios listed in Table 1 are used, except that they are the same as in Example 2 The reaction was carried out in a manner to obtain synthetic resins 3 to 10.

[Comparative example 1]

The reaction product (ABC-2) obtained in Example 2 above was used as the resin 11. Furthermore, the solid content concentration of the composite of resin 11 is 65.5%, the solid content acid value is 19 mgKOH/g, and the weight average molecular weight (Mw) analyzed by GPC is 2700.

[Comparative example 2]

In the reaction product (ABC-2) of the above-mentioned Example 2, what used 4HBAGE instead of ECHMMA [component (C)] was used as the resin 12. Furthermore, the solid content concentration of the composition of resin 12 is 66.0%, the solid content acid value is 11 mgKOH/g, and the weight average molecular weight (Mw) of GPC analysis is 2900.

[Table 1]

The raw materials used and the blending ratio are described in Table 1 above. In the blending ratio, "B/A" represents the molar ratio of (B) component to (A) component, and "C/(AB)" represents (C) component "D/(ABC)" represents the molar ratio of (D) component to the compound (AB) formed from (A) component and (B) component. The molar ratio of the compound (ABC).

Next, a photosensitive resin composition was prepared using the resins (compounds) of the examples and comparative examples synthesized above. The ingredients used in the composition are listed below.

Component 1: The resin (compound) solution synthesized by the above-mentioned examples or comparative examples.

Component 2: Ester oxime type photopolymerization initiator (Irgacure OXE02, manufactured by BASF JAPAN Co., Ltd.).

Component 3: Photopolymerizable monomer (DPHA, manufactured by Nippon Kayaku Co., Ltd.).

Component 4: Carbon dispersion (pigment concentration 20.0%, dispersant 5.0%, total solid content 25.0%, PGMEA 75%).

Ingredient 5: other additives.

Component 6: Solvent (Propylene Glycol Monomethyl Ether Acetate).

Component 7: Solvent (cyclohexanone).

Among them, the other additives of component 5 are well-known additives exemplified in the aforementioned embodiments. In this evaluation, a silane coupling agent and a surfactant were added. The total weight (%) is shown in Table 2.

Components 1 to 7 shown above were mixed according to the compounding ratio of the following Table 2, and a photosensitive resin composition using any resin (compound) of Examples 1 to 10 and Comparative Examples 1 to 2 was prepared.

[Table 2]

[Examples 11 to 14, Comparative Examples 3 to 4]

Using the above-mentioned resins obtained in Examples 2, 3, 6, 10 and Comparative Examples 1 and 2, the photosensitive resin composition prepared according to the blending ratio in the above-mentioned Table 2, so that the film thickness after post-baking becomes 1.1 μm (Thick film wrinkle evaluation: 3.0 μm or more) was applied on a glass substrate (125 mm×125 mm) using a spin coater. The pre-bake was carried out at 90° C. for 1 minute. Thereafter, ultraviolet light was irradiated for 4 seconds (10 seconds for thick-film wrinkle evaluation substrates) through the pattern mask with an ultra-high pressure mercury lamp with an I-line illuminance of 20 mW/cm ² to carry out photohardening reaction. Next, the exposed coated substrate was rinsed with water after development using 0.05% by weight potassium hydroxide aqueous solution (24° C.) for 1.5 times the number of seconds required to confirm the desired pattern, and the unexposed portion was removed. Thereafter, the post-baking was implemented using an oven at 230° C. for 30 minutes, and a cured film pattern for a test was obtained. In addition, the development process was not implemented with respect to the board|substrate for thick-film wrinkle evaluation.

In the test cured film pattern obtained by the above method, in addition to the difference in development time, exposure sensitivity, taper shape, line shape, and thick film wrinkles were also confirmed. The confirmation method is as follows.

[Exposure Sensitivity]

In the exposure step, a pattern mask having a pattern with a line width of 20 μm was placed on the substrate, and a cured film pattern for testing was produced according to the conditions of the above-mentioned embodiment. The exposure sensitivity was confirmed by comparing the line width of the 20 μm portion of the mask opening formed after the post-baking. In addition, in this evaluation method, the higher the sensitivity, the thicker the line width.

×: Peeling occurred.

-: Even if the developing time was 180 seconds, the unexposed part was not dissolved.

[tapered shape]

Using a scanning electron microscope (SEM) (manufactured by KEYENCE Co., Ltd., product name: VE-7800), analyze the cross-section of the pattern with a mask opening of 20 μm in the cured film pattern for the test to confirm the cross-sectional shape of the pattern (cone shape shape). Viewed from the surface of the glass substrate, it becomes tapered when it becomes thinner toward the surface of the coating film, and is evaluated according to the following grades.

○: Straight taper.

△: Reverse taper.

×: Peeling occurred.

-: Even if the developing time was 180 seconds, the unexposed part was not dissolved.

[line shape]

When the pattern of the mask opening 20 μm of the test color filter was analyzed by SEM, the evaluation was performed according to the following ranks.

◯: Good linearity can be confirmed.

Δ: Somewhat rough, but no fringe or the like was confirmed.

×: Peeling occurred.

-: Even if the developing time was 180 seconds, the unexposed part was not dissolved.

[Thick film wrinkle observation]

A substrate was produced so that the film thickness after the post-baking would be 3.0 μm or more, and the substrate was used for implementation. Again, no development step was performed on the substrates in this evaluation. The produced substrate was magnified 200 times with a microscope and the exposed part was observed, and the results were evaluated according to the following grades.

○: No wrinkles.

Δ: There are wrinkles (low degree).

X: There are wrinkles (high degree).

Table 3 shows the results obtained in the examples and evaluation methods of the above-mentioned photosensitive resin composition.

[table 3]

From the above results, it can be seen that the present invention has successfully completed a method for synthesizing a photosensitive resin, which has a balance between sensitivity and alkali developability, and a balance between surface hardening and deep hardening.

(Industrial Utilization)

In the resin represented by general formula (1) in the present invention, "impartment of polymerizable unsaturated group" and "imposition of alkali-soluble group (carboxyl group)" can be controlled by the aforementioned (C) component and (D) component, respectively, Therefore, when changing the characteristics of the photosensitive resin composition, each parameter can be changed independently. In this way, the tapered shape can be adjusted, the wrinkles on the surface of the pattern can be suppressed, and the surface of the color filter can be flattened, etc., which can be widely used according to the application.

Claims (7)

A kind of photosensitive resin, is as shown in following general formula (1),

Among them, R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a phenyl group, and E represents -CR _x R _y -, -CO-, -SO ₂ -, -O-, -S-, -SS-, -SO-, -OCO-, -SiR _x R _y - or direct bond, R _x and R _y represent hydrogen, halogen atom, which can be substituted by halogen atom A hydrocarbon group with 1 to 12 carbons, R _x and R _y can be bonded to form a ring respectively, A represents a tetravalent tetracarboxylic acid residue, G ₁ represents an alkylene group with a carbon number of 1 or more, D represents a hydrogen atom, has a polymeric A substituent of a sexually unsaturated group, or a substituent having a carboxyl group and a polymerizable unsaturated group, n ₁ and n ₂ independently represent an integer of 0 or more, and J represents a hydrogen atom or a substituent having a carboxyl group, but the general formula (1 One or more of the plurality of D in ) represents a substituent having a carboxyl group and a polymerizable unsaturated group. The photosensitive resin as described in Claim 1, wherein, in the general formula (1), D represents a hydrogen atom or a substituent shown in the following general formula (2), and J represents a hydrogen atom or the following general formula (3) the indicated substituents,

wherein G2 independently represents a single bond or an alkylene group having ₁ or more carbons, R5 represents a hydrogen atom or a methyl group, Q represents a trivalent hydrocarbon group having ₂ to 8 carbons, and n3 represents an integer of ₁ or more , when n ₃ is more than 2, the plurality of G ₂ in the formula can be the same or different,

Wherein, L represents 2 or 3 valent carboxylic acid residues, n ₄ represents 1 or 2. A photosensitive resin composition containing the following (i) to (ii): (i) The photosensitive resin described in claim 1 or 2; (ii) A photopolymerization initiator. The photosensitive resin composition according to claim 3, further comprising (iii) a photopolymerizable monomer having at least one ethylenically unsaturated bond. The photosensitive resin composition as described in claim 3 or 4, which further contains (iv) dispersoid. A cured product obtained by curing the photosensitive resin composition described in any one of Claims 3 to 5. A color filter containing the cured product described in Claim 6.