CN118732390A - Photosensitive resin composition, cured film, substrate with cured film, and method for producing substrate with cured film - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a cured film, a substrate with a cured film, and a method for manufacturing a substrate with a cured film. The subject is to provide a photosensitive resin composition that can form a cured film pattern that has both low reflectivity and high precision of the film surface and excellent heat resistance and light resistance. The solution of the present invention is a photosensitive resin composition, which contains (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable compound having at least two unsaturated bonds, (C) a cyclic siloxane compound having two or more epoxy groups in the molecule, (D) a photopolymerization initiator, (G) inorganic microparticles, and (H) a solvent.

Description

Photosensitive resin composition, cured film, substrate with cured film, and method for manufacturing substrate with cured film

Technical Field

The present invention relates to a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, a substrate with the cured film, and a method for producing the substrate with the cured film.

Background Art

In recent years, due to the development of portable terminals, the number of display devices such as touch panels or liquid crystal panels used outdoors or in vehicles has increased. In the above display devices, a light shielding film is provided on the outer frame of the touch panel to shield the light leakage from the peripheral part of the liquid crystal panel on the back, and a light shielding film (black matrix) is provided to suppress the light leakage from the screen when the liquid crystal panel displays black and to suppress the mixing of adjacent color photoresists.

In display devices, etc., in order to suppress light leakage and improve the visibility of the screen of the above-mentioned display devices, the concentration of black pigment in the shading film is increased and the shading property of the shading film is increased (the light transmittance of the shading film is reduced). Compared with the refractive index of the transparent substrate or the curable resin, the refractive index of the black pigment is higher, so if the concentration of the black pigment in the shading film is increased, the reflectivity when viewed from the surface of the transparent substrate formed with the shading film will become higher. Therefore, a shading film with not only high shading property but also low reflectivity is required. In addition, it is not only used for the purpose of forming a photoresist (black photoresist) of a black matrix, but also has utility in having a low reflectivity in a transparent photoresist or RGB photoresist for the reason that it can suppress the reflection inside the display.

In order to achieve low reflectivity in applications such as black matrices, a technique of mixing transparent particles such as silicon dioxide having a refractive index lower than that of black pigments or curable resins has been proposed in the past (e.g., Patent Document 1). However, if silicon dioxide is mixed into a photosensitive resin composition, although it is useful for achieving low reflectivity, even a relatively small amount may affect adhesion to the substrate.

In addition, in recent years, in the use of small and medium-sized panels such as smart phones, ultra-high-definition (400 pixels per inch or more) technology is needed to obtain a resolution of Full High Definition, and high-definition is a necessary technical trend. In order to achieve high-definition, the size of each red, green, and blue pixel needs to be smaller, but in order to increase the brightness, the aperture ratio of the color filter (the area ratio of the RGB pixels through which the backlight penetrates) must not be reduced, and the black matrix is also required to be thinned. That is, the line width of the black matrix was 6 to 8μm in the past, but recently it is required to be less than 7μm or 4 to 5μm. In addition, for example, in the display of new devices such as augmented reality (AR) or virtual reality (VR), a high-definition of more than 1000ppi is required, so the line width of the black matrix is required to be less than 3μm. The black matrix that has been used to reduce the reflectivity so far cannot meet such recent high-definition (thinning), and the adhesion (fine line adhesion) with the glass substrate needs to be further improved.

In this regard, the following technology has been proposed in the past: when a resin film pattern is formed by photolithography using a substrate with a maximum heat-resistant temperature of 140° C. or less, in order to form a resin film pattern with excellent development adhesion or linearity and excellent solvent resistance or alkali resistance even with a relatively low temperature heat treatment (thermal curing), an alkali-soluble resin or a photopolymerization initiator or other components are used, and an epoxy compound or an epoxy compound hardener and/or a hardening accelerator are used in a specific amount (for example, Patent Document 2). However, it is difficult to say that the hydrophobicity is sufficient when using such an epoxy compound or hardener, and it is required to improve the resistance to the developer, and there is still room for further improvement in high precision and fine line adhesion.

[Prior art literature]

[Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2016-161926

Patent Document 2: Japanese Patent Application Publication No. 2019-070720

Patent document 3: Japanese Patent Publication No. 2018-004920.

Summary of the invention

[Problems to be solved by the invention]

The present invention has been studied in view of the above problems, and in particular, has newly found that as a photosensitive resin composition that can form a cured film pattern that has both low reflectivity and high precision on the film surface and also has heat resistance and light resistance, the reflectivity of the coating film surface can be reduced by blending inorganic fine particles into the composition, and a cyclic siloxane compound having two or more epoxy groups in the molecule is blended instead of the epoxy compound used in the past.

In addition, it is known that a cyclic siloxane compound having two or more epoxy groups in the molecule is blended into a photosensitive resin composition (Patent Document 3), but the purpose of the invention is only to form a cured film with a small amount of generated gas as a dam for separating the light-emitting layer in an organic EL element, and the invention discloses as an example of a multifunctional crosslinkable compound (D) having a plurality of epoxy groups or cyclohexane groups. In other words, there is no disclosure or suggestion that the blending of the siloxane compound can impart high definition or fine line adhesion to the cured film pattern formed by photolithography.

[Methods used to solve the problem]

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

[1] A photosensitive resin composition comprising:

(A) an alkali-soluble resin containing an unsaturated group;

(B) a photopolymerizable compound having at least two unsaturated bonds;

(C) a cyclic siloxane compound having two or more epoxy groups in the molecule;

(D) a photopolymerization initiator;

(G) inorganic particles; and

(H) Solvent.

[2] The photosensitive resin composition according to [1], wherein the component (C) is a cyclic siloxane compound represented by the general formula (1).

[In the general formula (1), _Ra and _Rb represent a monovalent group containing an epoxy group or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least two of n _Ra and _Rb are monovalent groups containing an epoxy group. Multiple _Ra and _Rb may be the same or different. n represents an integer of 3 or more and 10 or less.]

[3] The photosensitive resin composition as described in [1], wherein the aforementioned component (A) comprises a polymer containing a unit represented by the following general formula (2) and a unit represented by the following general formula (3), wherein the polymer is a polymer containing 5 to 90 mol% of the unit represented by the general formula (2) and 10 to 95 mol% of the unit represented by the general formula (3), having a weight average molecular weight of 3,000 to 50,000 and an acid value of 30 to 200 mg/KOH.

(However, R _c , R _f and R _h independently represent a hydrogen atom or a methyl group. R _d represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond or a urethane bond inside. In addition, 40 mol% or more of R _d in all units represented by the general formula (2) is a dicyclopentyl group or a dicyclopentenyl group. _Re represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents a number of 0 or 1. X represents a hydrogen atom or a -OC-L-(COOH) _k group (however, L is a divalent or trivalent carboxylic acid residue, and k is 1 to 2).)

[4] The photosensitive resin composition according to [1], further comprising (F) one or more light-shielding materials selected from the group consisting of black organic pigments, mixed color organic pigments, and black inorganic pigments.

[5] The photosensitive resin composition according to [1], further comprising (E) a hardener and/or a hardening accelerator.

[6] The photosensitive resin composition according to [1], wherein the component (G) has a refractive index of 1.20 to 1.50 and an average particle size of 1 to 150 nm.

[7] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [6].

[8] A substrate with a cured film, comprising the cured film according to [7] on a substrate.

[9] A method for manufacturing a substrate with a cured film, comprising forming a cured film pattern on a substrate to manufacture the substrate with a cured film, wherein:

The photosensitive resin composition described in any one of [1] to [6] is applied onto a substrate, exposed through a photomask, developed to remove unexposed portions, and heated to form a cured film pattern.

[Effects of the Invention]

The photosensitive resin composition according to the present invention can form a cured film pattern having both low reflectivity and high fineness of the film surface. In addition, a cured film pattern having excellent heat resistance and light resistance can be formed. In addition, a method for forming such a cured film pattern and manufacturing a substrate with a cured film can be provided.

DETAILED DESCRIPTION

As described above, the photosensitive resin composition of the present invention has as essential components at least (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable compound having at least two unsaturated bonds, (C) a cyclic siloxane compound having two or more epoxy groups in the molecule, (D) a photopolymerization initiator, (G) inorganic microparticles, and (H) a solvent.

The photosensitive resin composition of the present invention may optionally contain (F) one or more light-shielding materials selected from the group consisting of black organic pigments, mixed color organic pigments and black inorganic pigments, or (E) a hardener and/or a hardening accelerator.

The following is a detailed description focusing on each component used.

<(A) Alkali-soluble resin containing an unsaturated group>

The (A) unsaturated group-containing alkali-soluble resin contained in the photosensitive resin composition of the present invention will be described.

The (A) unsaturated group-containing alkali-soluble resin has an acid value for imparting alkali developability, and can be used without particular limitation as long as it can be combined with the photopolymerizable compound of the component (B) and has appropriate photocurability.

Examples of component (A) include: an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting a dicarboxylic acid or a tricarboxylic acid or a monoanhydride (b) thereof and a tetracarboxylic acid or a dianhydride (c) thereof with respect to a reaction product of an epoxy compound (a-1) having two epoxy groups in one molecule as shown in general formula (9) and a monocarboxylic acid containing an unsaturated group. Since the alkali-soluble resin shown in general formula (4) has a large number of aromatic rings, it has excellent heat resistance. In addition, a high-definition pattern can be obtained.

In addition, another example of component (A) may be a (meth)acrylate resin containing a polymer of a unit represented by the general formula (2) and a unit represented by the general formula (3) described later. In addition, "(meth)acrylate" is a collective term for acrylate and methacrylate, and refers to one or both of these. The same applies to (meth)acrylic acid, etc. described later.

First, the unsaturated group-containing alkali-soluble resin represented by the following general formula (4) will be described.

In formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, A is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl or a direct bond, Y is a tetravalent carboxylic acid residue, and Z is each independently a hydrogen atom or a substituent represented by general formula (5). However, at least one of Z is a substituent represented by general formula (5), and q is an integer from 1 to 20.

In the formula (5), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.

A method for producing an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (4) (hereinafter also simply referred to as "alkali-soluble resin represented by the general formula (4)") is described in detail.

First, an epoxy compound (a-1) having two epoxy groups in one molecule represented by the general formula (9) (hereinafter also simply referred to as "epoxy compound (a-1)") is reacted with a monocarboxylic acid containing an unsaturated group (e.g., (meth)acrylic acid) to obtain a diol compound containing a polymerizable unsaturated group.

In formula (9), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and A is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl or a direct bond.

The epoxy compound (a-1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin.

Examples of bisphenols used as a raw material for the epoxy compound (a-1) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, (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 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, -bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. These may be used alone or in combination of two or more.

Examples of the unsaturated group-containing monocarboxylic acid compound include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride.

The reaction of the epoxy compound (a-1) with the monocarboxylic acid compound containing an unsaturated group can be carried out using a well-known method. For example, Japanese Patent Publication No. 4-355450 states that about 2 moles of (meth) acrylic acid are used relative to 1 mole of an epoxy compound having two epoxy groups, thereby obtaining a diol compound containing a polymerizable unsaturated group. In the present invention, the compound obtained by the above reaction is a diol compound containing a polymerizable unsaturated group, which is a diol (d) containing a polymerizable unsaturated group as shown in the general formula (10) (hereinafter also simply referred to as "diol (d) shown in the general formula (10)").

In formula (10), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, and A is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl or a direct bond.

When the diol (d) represented by the general formula (10) is synthesized, and the subsequent addition reaction of a polycarboxylic acid or its anhydride, and the reaction with a monofunctional epoxy compound having a polymerizable unsaturated group reactive with a carboxyl group is carried out to produce the alkali-soluble resin represented by the general formula (4), the reaction is usually carried out in a solvent, optionally using a catalyst.

Examples of the solvent include: cellothioic acid solvents such as ethyl cellothioic acid acetate and butyl cellothioic acid acetate; high-boiling-point ether or ester solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone, etc. In addition, the reaction conditions regarding the solvent, catalyst, etc. used are not particularly limited, but for example, it is more preferable to use a solvent that does not contain a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

In the reaction between the carboxyl group and the epoxy group, it is more preferable to use a catalyst. Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tri(2,6-dimethoxyphenyl)phosphine.

Then, the diol (d) represented by the general formula (10) is reacted with a tetracarboxylic acid or its dianhydride (b), and a dicarboxylic acid or a tricarboxylic acid or its anhydride (c) to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (4).

The acid component used to synthesize the alkali-soluble resin represented by the general formula (4) is a polyacid component that can react with the hydroxyl group in the diol (d) molecule represented by the general formula (10), and it is necessary to use a dicarboxylic acid or a tricarboxylic acid or a monoanhydride (b) of these and a tetracarboxylic acid or a dianhydride (c) thereof. The carboxylic acid residue of the above-mentioned acid component can be any of a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may include bonds containing hetero elements such as -O-, -S-, and a carbonyl group.

As the dicarboxylic acid or tricarboxylic acid or the monoanhydride thereof (b), chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid or the monoanhydride thereof, etc. can be used.

Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxyglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituents. In addition, examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituents. In addition, examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with any substituents.

Among the acid monoanhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are more preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred. In addition, among the dicarboxylic acids or tricarboxylic acids, it is more preferred to use these acid monoanhydrides. The acid monoanhydrides of the above-mentioned dicarboxylic acids or tricarboxylic acids can be used alone or in combination of two or more.

Moreover, as the tetracarboxylic acid or its acid dianhydride (c), a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or an acid dianhydride thereof can be used.

Examples of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. In addition, examples of the above-mentioned alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups are introduced. In addition, examples of aromatic tetracarboxylic acids include pyromelitic acid, diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, etc.

Among tetracarboxylic acids or their acid dianhydrides, biphenyl tetracarboxylic acid, diphenyl ketone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid are more preferred, and biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferred. In addition, among tetracarboxylic acids or their acid dianhydrides, their acid dianhydrides are more preferably used. In addition, the above-mentioned tetracarboxylic acids or their acid dianhydrides may be used alone or in combination of two or more.

The reaction of the diol (d) represented by the general formula (10) with the acid components (b) and (c) is not particularly limited and a known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting (meth)acrylate epoxy ester with tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

Here, it is more preferred to react in such a way that the terminal of the compound becomes a carboxyl group so that the molar ratio of the diol (d) represented by the general formula (10), the dicarboxylic acid or tricarboxylic acid or the monoanhydride of these (b), and the tetracarboxylic dianhydride (c) becomes (d):(b):(c)=1:0.01 to 1.0:0.2 to 1.0.

For example, when (b) acid monoanhydride and (c) acid dianhydride are used, it is more preferred to react so that the amount of the acid component [(b)/2+(c)] relative to the molar ratio of the diol (d) represented by the general formula (5) [[(b)/2+(c)]/(d)] becomes 0.5 to 1.0. Here, when the molar ratio exceeds 0.5, the content of the unreacted diol compound containing a polymerizable unsaturated group does not increase, so the temporal stability of the photosensitive resin composition can be improved. On the other hand, when the molar ratio is 1.0 or less, the terminal of the alkali-soluble resin represented by the general formula (4) does not become an acid anhydride, so the increase in the content of the unreacted acid dianhydride can be suppressed, and the temporal stability of the photosensitive resin composition can be improved. In addition, for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (4), the molar ratio of each component of (d), (b) and (c) can be arbitrarily changed within the above range.

In addition, the acid value of the alkali-soluble resin represented by the general formula (4) is preferably in the range of 20 to 180 mgKOH/g, and more preferably in the range of 80 mgKOH/g to 120 mgKOH/g. When the acid value is 20 mgKOH/g or more, it is not easy to leave residues during alkali development, and when it is 180 mgKOH/g or less, the penetration of the alkali developer is not too fast, so the peeling development can be suppressed. In addition, the acid value can be obtained by titrating with a 1/10N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Industry Co., Ltd.).

The alkali-soluble resin represented by the general formula (4) has a polystyrene-converted weight average molecular weight (Mw) of 1,000 to 100,000, preferably 2,000 to 20,000, and more preferably 2,000 to 6,000, as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by TOSOH Co., Ltd.). When the weight average molecular weight is 1,000 or more, the decrease in the adhesion of the pattern during alkali development can be suppressed. In addition, when the weight average molecular weight is 100,000 or less, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and alkali development will not be too time-consuming.

The alkali-soluble resin represented by the general formula (4) can be used alone in the component (A), or it can be replaced by the (meth)acrylate resin described later, or they can be used in combination. The type of alkali-soluble resin used can be appropriately selected according to the desired application or characteristics, but when the content of the alkali-soluble resin represented by the general formula (4) is relatively high, the heat resistance is particularly excellent and a high-definition pattern can be formed. Therefore, from the viewpoint of imparting these characteristics, the content of the alkali-soluble resin represented by the general formula (4) is preferably high, and is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and particularly preferably 85 to 100% by mass relative to the total mass of the component (A) (for example, the total mass of the alkali-soluble resin represented by the general formula (4) and the (meth)acrylate resin described later), more preferably 75 to 100% by mass, and particularly preferably 85 to 100% by mass.

[(Meth)acrylate resin]

Next, a (meth)acrylate resin will be described as another example of the component (A).

By replacing the alkali-soluble resin represented by the general formula (4) or including a (meth)acrylate resin together with the alkali-soluble resin represented by the general formula (4), even if the aromatic ring is reduced, the degradation to light can be suppressed, so the light resistance can be improved. In addition, compared with the alkali-soluble resin represented by the general formula (4), the refractive index is lower, which is conducive to low reflectivity. When these resins are used together, light resistance or low reflectivity can be improved while having a certain degree of heat resistance and high-precision pattern formation.

Thus, the (meth)acrylate resin is a polymer containing the unit represented by the following general formula (2) and the unit represented by the general formula (3), and the side chain has a carboxyl group and a polymerizable unsaturated group. That is, the (meth)acrylate resin is a random copolymer in which the units represented by the general formula (2) and the units represented by the general formula (3) are connected to r and s units, respectively (here, r and s are arbitrary integers). In addition, it may also contain units of a third component other than these, for example, it may further contain units derived from carboxylic acids containing unsaturated groups as shown in the general formula (8) described later, styrenes in which the phenyl group may have a substituent, or monomaleimide, etc. as copolymer components. The substituents that the phenyl group of the styrene group may have include, for example, alkyl groups having 1 to 10 carbon atoms, etc. Monomaleimides include, for example, N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc. Among these third component units, styrene and N-phenylmaleimide are more preferably used.

The ratio of the unit represented by the general formula (2) and the unit represented by the general formula (3) is preferably 5 to 90 mol%, more preferably 20 to 70 mol%, when the total of the polymer composed of the unit represented by the general formula (2), the unit represented by the general formula (3), and the unit of the third component is 100 mol%. In addition, the unit represented by the general formula (3) is preferably 10 to 95 mol%, more preferably 30 to 80 mol%. The ratio of the unit of the third component other than these can be 0 to 50 mol%, when the total of the polymer is 100 mol%.

Here, in formulae (2) and (3), R _c , R _f and R _h independently represent a hydrogen atom or a methyl group. R _d represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond or a urethane bond inside. In addition, 40 mol% or more of R _d in all units represented by general formula (2) is a dicyclopentyl group or a dicyclopentenyl group. _Re represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents a number of 0 or 1. X represents a hydrogen atom or a -OC-L-(COOH) _k group (but L is a divalent or trivalent carboxylic acid residue, and k is 1 to 2). In addition, X may contain two or more types in one polymer molecule. That is, the OX group may include a -OC-L-(COOH) _k group formed by the reaction with the anhydride of a dicarboxylic acid or a tricarboxylic acid in the third step described later, and an OH group when unreacted.

The method for producing such a (meth)acrylate resin will be described.

For example, the first step is to copolymerize the compound of the following formula (6) used to form the unit represented by the general formula (2) with glycidyl (meth)acrylate in a solvent to obtain a copolymer, but the present invention is not limited thereto. At this time, the blending ratio of the compound of formula (6) is preferably 5 to 90 mol% relative to the total 100 mol% of the compound of formula (6), glycidyl (meth)acrylate, and the third component in addition. More preferably, the compound of formula (6) is 20 to 70 mol%. That is, the unit represented by the following general formula (2) is preferably 5 to 90 mol% in the total 100 mol% of the unit represented by the general formula (3) and the third component in addition, and more preferably 20 to 70 mol%.

In addition, the copolymer may contain the above-mentioned styrene components and the like and copolymerize them.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for _Rd in the above formulae (2) and (6) are not limited, and include: saturated straight-chain hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc.; unsaturated straight-chain hydrocarbon groups such as vinyl, allyl, ethynyl, etc.; cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 4-methylcyclohexyl, dicyclopent ... Cyclic aliphatic hydrocarbon groups such as cyclopentenyl, dicyclohexyl, norbornyl, isobornyl, adamantyl, tricyclodecylmethyl, and the substituents represented by the following general formula (7) (* represents the bonding portion to the ester portion of the general formula (2)); hydrocarbon groups having an aromatic ring such as phenyl, tolyl, mesityl, naphthyl, anthracenyl, phenanthryl, benzyl, 2-phenylethyl, 2-phenylvinyl, and decahydronaphthyl; aliphatic ethers such as methoxyethyl, 2-(methoxyethoxy)ethyl, and isopentyl; aliphatic ethyl carbamates such as 2-(ethoxycarbonylamino)ethyl, etc. The unit represented by the general formula (2) may contain a plurality of units having different R _d .

Among them, from the viewpoint of imparting heat resistance and light resistance, it is more preferred that R _d represents a dicyclopentyl group or a dicyclopentenyl group in an amount of 40 mol% or more of all units formed as the general formula (2).

Next, the second step is to react unsaturated carboxylic acids such as (meth) acrylic acid with the epoxy groups in the copolymer obtained above to ring-open the epoxy groups. At this time, the unsaturated carboxylic acids reacted are preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 100 mol% with respect to the epoxy groups. Increasing the reaction amount of the unsaturated carboxylic acids with respect to the epoxy groups can introduce more unsaturated groups and groups corresponding to X shown below into the obtained (meth) acrylate resin, so it is more preferred.

As the unsaturated group-containing carboxylic acid, a carboxylic acid represented by the following formula (8) can be used: _{R e} , R _f and p are the same as those described above.

The divalent hydrocarbon group having 2 to 10 carbon atoms belonging to _Re is preferably a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and may be linear, branched, or cyclic. The hydrocarbon group represented by _Re is preferably a vinyl group, a 1,2-propylene group, or a 1,4-butylene group. The unit represented by the general formula (3) may contain a plurality of units having different Re _atoms . A more preferred unsaturated group-containing carboxylic acid is (meth)acrylic acid wherein p=0.

Next, in the third step, the anhydride of a dicarboxylic acid or a tricarboxylic acid is reacted with the OH group formed by ring opening in the second step to form a unit represented by the general formula (3). The (meth)acrylate resin is an alkali-soluble resin containing a polymerizable unsaturated group obtained in this way.

The anhydride of the dicarboxylic acid or tricarboxylic acid to be reacted is not limited, but preferably the dicarboxylic acid or tricarboxylic acid or the acid monoanhydride thereof used in forming the alkali-soluble resin represented by the general formula (4) above. These can be used alone or in combination of two or more. Among them, maleic acid, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydrotrimellitic acid, chlorobridgeic acid, phthalic acid, and trimellitic acid are more preferred, and succinic acid, itaconic acid, and the acid monoanhydride of tetrahydrophthalic acid, succinic acid, and trimellitic acid are more preferred.

In the third step, the amount of the anhydride of the dicarboxylic acid or tricarboxylic acid used is appropriately adjusted relative to the OH group formed by the ring-opening in the second step, thereby adjusting the acid value to the range described below.

In addition, the synthesis method of such (meth)acrylate resin is not limited thereto. For example, the aforementioned (meth)acrylates and (meth)acrylic acid can be subjected to free radical copolymerization in a solvent, and then the carboxyl groups in the copolymer are reacted with a (meth)acrylate compound having a glycidyl group such as (meth)acrylate glycidyl, and then the generated hydroxyl group is reacted with the aforementioned dicarboxylic acid compound, tricarboxylic acid compound or their acid monoanhydrides.

The weight average molecular weight (Mw) of the (meth)acrylate resin thus obtained is preferably 3000 to 50000, and more preferably 4000 to 20000. When the weight average molecular weight is 3000 or more, the decrease in pattern adhesion during alkali development can be suppressed. In addition, when the weight average molecular weight is 50000 or less, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and alkali development will not be too time-consuming.

In addition, the acid value of the (meth)acrylate resin is preferably 30 mgKOH/g or more and 200 mgKOH/g, more preferably 40 mgKOH/g or more and 140 mgKOH/g or less, and even more preferably 50 to 150 mgKOH/g. If the acid value is 30 mgKOH/g or more, it is not easy to leave residues during alkali development. In addition, if it is 200 mgKOH/g or less, the penetration of the alkali developer will not be too fast, so stripping development can be suppressed. The acid value can be adjusted by the amount of carboxyl groups present in X in the unit represented by the general formula (3).

The weight average molecular weight (Mw) and acid value of the (meth)acrylate resin can be measured by the same method as that used for the alkali-soluble resin represented by the general formula (4).

The (meth)acrylate resin can be used alone in the component (A). In addition, it can be used in combination with the alkali-soluble resin represented by the general formula (4) as described above according to the desired use or characteristics, and can be appropriately selected. It can usually be used in an amount of 10 to 100% by mass relative to the total mass of the component (A) (for example, the total mass of the alkali-soluble resin represented by the general formula (4) and the (meth)acrylate resin). When the (meth)acrylate resin is more, it is particularly excellent in light resistance and low reflectivity. Therefore, from the perspective of imparting these characteristics, it is more preferably 50 to 100% by mass relative to the total mass of the component (A) (for example, the total mass of the alkali-soluble resin represented by the general formula (4) and the (meth)acrylate resin), more preferably 75 to 100% by mass, and particularly preferably 90 to 100% by mass.

The content of the component (A) in the photosensitive resin composition of the present invention is preferably 30 to 80% by mass relative to the total mass of the solid content when no coloring material or light-shielding material is contained, and is more preferably 2% by mass to 70% by mass when a coloring material or light-shielding material is contained.

<(B) Photopolymerizable Monomer Having at Least Two Ethylenically Unsaturated Bonds>

The function of the component (B) is to crosslink the molecules of the alkali-soluble resin of the component (A). Examples of the component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (Meth)acrylates such as oil (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene oxirane-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendrimers having (meth)acryloyl groups can be used. One or more of these can be used. Dendrimers having (meth)acryloyl groups can be exemplified by well-known dendrimers obtained by adding thiol groups in a polyvalent mercapto compound to a portion of the carbon-carbon double bonds in the (meth)acryloyl groups of a polyfunctional (meth)acrylate compound.

The component (B) has the aforementioned function, and therefore, in order to exert its function, a monomer having two or more ethylenically unsaturated bonds is used. In addition, the acrylic acid equivalent of the molecular weight of the monomer divided by the number of (meth)acryloyl groups in one molecule may be 50 to 300.

The amount of the (B) component is preferably 30/70 to 90/10, and more preferably 35/65 to 60/40, as a blending ratio with the aforementioned (A) component in the mass ratio (A)/(B). If the blending ratio of the (A) component is less than 30/70, the cured product after photocuring becomes fragile. In addition, the acid value of the coating in the unexposed portion is low, so there is a concern that the solubility in the alkaline developer is reduced and the pattern edge is jagged and not sharp. In addition, if the blending ratio of the (A) component is higher than 90/10, the proportion of photoreactive functional groups in the resin is small, and a cross-linked structure cannot be fully formed. In addition, the acid value in the resin component is too high, and there is a concern that the solubility in the exposed portion relative to the alkaline developer becomes higher, so there is a concern that the formed pattern is thinner than the target line width and pattern defects are easily generated.

<(C) Cyclic Siloxane Compound Having Two or More Epoxy Groups in the Molecule>

The photosensitive resin composition of the present invention contains a cyclic siloxane compound having two or more epoxy groups in the (C) molecule. More preferably, it is a cyclic siloxane compound having three or more epoxy groups in the molecule. Since the (C) component has a cyclic siloxane structure, it is inferred that the rigid cyclic structure has higher resistance to the developer than the chain structure, and has excellent adhesion to the glass substrate and can improve the fine line adhesion. In addition, since there are two or more epoxy groups in the molecule, the crosslinking density will increase during curing and the curing property will be excellent. The (C) component can use only one compound or two or more compounds in combination. The (C) component is shown in the following general formula (1).

_Ra and _Rb in the general formula (1) represent a monovalent group containing an epoxy group or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least two of n _Ra and _Rb are monovalent groups containing an epoxy group. Multiple _Ra and _Rb may be the same or different. n represents an integer of 3 to 10. More preferably, n is 4 to 6.

Here, the monovalent group containing an epoxy group is not limited, but a group represented by _-Rg -Ep is more preferred. Here, _Rg represents an alkylene group which may be linked to an ether bond, an ester bond, an amine group, etc., and Ep represents a group containing an epoxy group.

Examples of R _g (the aforementioned alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, dimethylene, and trimethylene.

On the other hand, Ep (epoxy-containing group) includes, for example, epoxypropyl group, 3,4-epoxycyclohexyl group, etc. The epoxy-containing group has a high reactivity with respect to cations, so 3,4-epoxycyclohexyl group is more preferred. The presence of 3,4-epoxycyclohexyl group with high reactivity with respect to cations in the molecule can improve the solvent resistance of the cured film (coating film) by adding an amount within an appropriate range of the development speed.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group having 1 to 20 carbon atoms.

When the hydrocarbon group having 1 to 20 carbon atoms is an alkyl group, the carbon number is preferably 1 to 16, and more preferably 1 to 12. A part or all of the hydrogen atoms on the carbon of the alkyl group may be substituted with other groups that do not participate in the reaction. In addition, the alkyl group may be any of linear, branched and cyclic. Specific examples of the group that does not participate in the reaction include: alkoxy groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 6 carbon atoms, halogen atoms, etc. Specific examples of the alkyl group substituted with a group that does not participate in the reaction include: methyl, ethyl, propyl, butyl, sec-butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, 2-methoxyethyl, 3-ethoxypropyl, 2-methoxycarbonylethyl, trifluoromethyl, 3-chloropropyl, etc.

In addition, when the hydrocarbon group with a carbon number of 1 to 20 is an aryl group, a monovalent aromatic organic group of a hydrocarbon ring system or a heterocyclic system can be used. When the aryl group is a hydrocarbon ring system, the carbon number is preferably 6 to 18, and more preferably 6 to 14. Specific examples of these aryl groups include: phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, etc. In addition, when the aryl group is a heterocyclic system, the heteroatom in the heterocyclic ring is sulfur, oxygen atom, etc., and the carbon number is preferably 4 to 12, and more preferably 4 to 8. Specific examples of these aryl groups include: thienyl, benzothienyl, dibenzothienyl, furanyl, benzofuranyl, dibenzofuranyl, etc. Part or all of the hydrogen atoms of the aryl group can be replaced with a group that does not participate in the reaction. Specific examples of the group that does not participate in the reaction include: the group shown in the aforementioned alkyl group, etc. In addition, other groups that do not participate in the reaction include: oxyethylene, oxyethyleneoxy, etc., which are divalent groups bonded to 2 carbon atoms on the ring. Specific examples of the aryl group that can be substituted with a group that does not participate in the reaction include methylphenyl, ethylphenyl, hexylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, octyloxyphenyl, methyl(methoxy)phenyl, fluoro(methyl)phenyl, chloro(methoxy)phenyl, bromo(methoxy)phenyl, 2,3-dihydrobenzofuranyl, and 1,4-benzodioxanyl.

In addition, when the hydrocarbon group having 1 to 20 carbon atoms is an aralkyl group, the carbon number is preferably 7 to 19, and more preferably 7 to 15. A part or all of the hydrogen atoms on the carbon atoms of the aralkyl group may be substituted with a group that does not participate in the reaction. Specific examples of the group that does not participate in the reaction include: the group shown in the above alkyl group, etc. Specific examples of the aralkyl group that can be substituted with a group that does not participate in the reaction include: benzyl, phenethyl, 2-naphthylmethyl, 9-anthrylmethyl, (4-chlorophenyl)methyl, 1-(4-methoxyphenyl)ethyl, etc.

In addition, when the hydrocarbon group having 1 to 20 carbon atoms is an alkenyl group, the carbon number is preferably 2 to 18, and more preferably 2 to 14. A part or all of the hydrogen atoms on the carbon of the alkenyl group can be substituted with a group that does not participate in the reaction. Specific examples of the group that does not participate in the reaction include: the group shown in the above-mentioned alkyl group, etc., and further include: the aryl group shown in the above-mentioned group. Specific examples of the alkenyl group that can be substituted with a group that does not participate in the reaction include: vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 2-phenylvinyl, 2-(methoxyphenyl)vinyl, 2-naphthylvinyl, 2-anthrylvinyl, etc.

Specific examples of the component (C) satisfying the above are not limited, and examples thereof include silsesquioxanes having two or more epoxy groups in the molecule. More specifically, examples thereof include 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4,8-Tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetrakis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetrasiloxane.

For example, commercially available products such as X-40-2678 and KR-470 (both manufactured by Shin-Etsu Chemical Co., Ltd.) can be obtained and used.

Among them, those having three or more monovalent groups containing epoxy groups are suitable for expressing functions. There is no upper limit on the number of monovalent groups containing epoxy groups.

When the mass ratio of the component (A) is 1, the content of the component (C) is preferably 0.1 to 1.5, more preferably 0.28 to 1.0, and even more preferably 0.62 to 0.8.

In addition, the number average molecular weight (Mn) of component (C) is preferably 100 to 5000. The aforementioned epoxy equivalent is preferably 50 to 300 g/eq. If the number average molecular weight (Mn) is 100 to 5000, the development adhesion during development can be ensured, and a cured film with better solvent resistance can be formed. In addition, if the epoxy equivalent is 50 to 300 g/eq, a photosensitive resin composition with a development speed in an appropriate range can be designed, and the solvent resistance of the cured film can be ensured.

<(D) Photopolymerization Initiator>

Examples of the component (D) in the photosensitive resin composition of the present invention include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and diphenylethylene dimethyl ketal; diphenyl ketones such as phenyl ketone, 2-chlorophenyl ketone, p,p'-bisdimethylaminophenyl ketone, 4,4'-bisdimethylaminophenyl ketone (Michelle's ketone), 4-phenylphenyl ketone, 4,4'-dichlorophenyl ketone, hydroxyphenyl ketone, and 4,4'-diethylaminophenyl ketone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenyldiimidazole, 2-(o-chlorophenyl)-4,5-phenyldiimidazole, and 2-(o-chlorophenyl)-4,5-phenyldiimidazole. )-4,5-bis(m-methoxyphenyl)diimidazole, 2-(o-fluorophenyl)-4,5-diphenyldiimidazole, 2-(o-methoxyphenyl)-4,5-diphenyldiimidazole, 2,4,5-triaryldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-diimidazole and other diimidazole compounds; 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxyphenylvinyl)-1,3,4-oxadiazole and other halomethyldiazole compounds; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl -4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and other halomethyl-s-triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl] -,2-(O-benzoyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-one oxime-O-acetate, 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane -1-ketoximine-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-ketoximine-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-furinylmethane-1-ketoximine-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-furinylmethane-1-ketoximine-O-benzoate -9H-carbazol-3-yl]-furinylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-tricyclodecanecarboxylate, 9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethanone-O-acetyl oxime, (2-methylphenyl)(7-nitro-9 ,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethyl ketone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyl oxime), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyl oxime, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)- O-acyl oxime compounds such as 9H-carbazole-3-yl]-, 1-(O-acetyl oxime); sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone; 2-ethylanthraquinone, octamethylanthraquinone , anthraquinones such as 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide and isopropyl benzene peroxide; 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, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid and other thiol compounds, etc. Among them, O-acyl oxime compounds are more preferably used from the viewpoint of easily obtaining high sensitivity. In addition, two or more of these photopolymerization initiators may be used. In addition, the photopolymerization initiator of the present invention includes a sensitizer.

In addition, a compound that does not act as a photopolymerization initiator or sensitizer by itself but can increase the ability of the photopolymerization initiator or sensitizer by being used in combination with the above-mentioned compound can also be added. Examples of such compounds include: amine compounds that are effective when used in combination with diphenyl ketone. Examples of the above-mentioned amine compounds include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethylmethylamino)diphenyl ketone, etc.

The amount of component (D) is more preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). It is more preferably 0.1 to 1% by mass in the photosensitive resin composition.

<(G) Inorganic microparticles>

The photosensitive resin composition of the present invention may contain (G) inorganic microparticles. Inorganic microparticles having a refractive index of 1.20 to 1.50 are more preferably inorganic microparticles, such as silicon oxide. The inorganic microparticles belonging to the component (G) are well-known inorganic microparticles that meet the aforementioned refractive index range and can be used without particular restrictions. The manufacturing method of gas phase reaction or liquid phase reaction and the shape (spherical, non-spherical) are not particularly limited. Inorganic microparticles surface-treated with silane coupling agent treatment or the like can also be used without particular restrictions.

The refractive index of the inorganic fine particles is more preferably 1.33 to 1.48. By using inorganic fine particles having the above refractive index, the refractive index of the surface of the cured film (coating film) can be lowered, and reflection can be suppressed without separately providing an antireflection film or the like.

In addition, the refractive index of the inorganic microparticles can be obtained by mixing the above-mentioned inorganic microparticles into a transparent mixed solution obtained by mixing a substance in a powdered state and a standard refractive liquid with a known refractive index. At this time, the refractive index of the standard refractive liquid of the above-mentioned mixed solution is used as the refractive index of the inorganic microparticles. In addition, the refractive index of the above-mentioned inorganic microparticles can be measured using an Abbe refractometer.

By using the above-mentioned inorganic microparticles, the reflectivity of the light-shielding film containing the inorganic microparticles can be reduced. In the present invention, when such a (G) component is contained, a light-shielding film with a low reflectivity can be obtained even with high light shielding, so it is more preferred. A suitable example is a cured film (or light-shielding film) using a light-shielding material as the (F) component described later, and a photosensitive resin composition using the (F) component, when the OD is 1/μm or more, the reflectivity is preferably less than 10%, more preferably less than 5%, and even more preferably less than 4%.

The average particle size of the inorganic microparticles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and more preferably 1 to 50 nm, particularly preferably 1 to 30 nm, and most preferably 1 to 10 nm. When using inorganic microparticles with an average particle size in this range, inorganic microparticles can be effectively present on the film surface, so it is conducive to low reflectivity. In addition, the change of the side of the fine line pattern can be suppressed. In addition, there is an effect of reducing the concavo-convexity of the surface of the hardened film (coating), which can suppress the inconsistent reflectivity within the hardened film (coating) surface.

In addition, relative to the total mass of the photosensitive resin composition, the content of the above-mentioned inorganic microparticles is preferably 0.1 to 5 mass parts, more preferably 0.1 to 2 mass parts. In addition, relative to the total solids in the photosensitive resin composition, it is more preferably 1 to 20 mass%. If the content of the inorganic microparticles is within the above range, low reflectivity can be achieved, and good patternability can be ensured.

The average particle size of the inorganic fine particles can be measured by an electron microscope as described in the examples below, but is not limited thereto.

The inorganic fine particles can be mixed with other ingredients as an inorganic fine particle dispersion dispersed in a solvent. The dispersant can be a well-known compound used for pigment dispersion (compounds sold under the names of dispersants, dispersing wetting agents, dispersion accelerators, etc.) without particular limitation.

<(H) Solvent>

Examples of the (H) solvent in the photosensitive resin composition of the present invention include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosol, ethyl cellosol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monobutyl ether, Glycol ethers such as methyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellothioate acetate, ethyl cellothioate acetate, butyl cellothioate acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. can be used, dissolved, and mixed to form a uniform solution composition.

<(E) Hardener and/or Hardening Accelerator>

In addition to other components, the photosensitive resin composition of the present invention may also use (E) a hardener and/or a hardening accelerator relative to the aforementioned (C) component. Examples of the hardener of the (E) component include: amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid complexes, etc. In the present invention, polyvalent carboxylic acid compounds can be preferably used.

Examples of polyvalent carboxylic acid compounds include polycarboxylic acids, polycarboxylic acid anhydrides, and thermally decomposable esters of polycarboxylic acids. Polycarboxylic acids refer to compounds having two or more carboxyl groups in one molecule, and examples thereof include succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, etc. Examples of polycarboxylic acid anhydrides include anhydrides of the above compounds. They may be intermolecular anhydrides, but are generally used as anhydrides that are ring-closed within the molecule. Examples of thermally decomposable esters of polycarboxylic acids include: tert-butyl esters, 1-(alkyloxy)ethyl esters, 1-(alkylmercapto)ethyl esters of the above compounds (but the alkyl group is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group may have a branched structure or a ring structure, and may be substituted with any substituent), etc. In addition, the polycarboxylic acid compound may also use a polymer or copolymer having two or more carboxyl groups, and the carboxyl group may be an anhydride or a thermally decomposable ester. In addition, the acid component used to synthesize the alkali-soluble resin may also be used.

The curing accelerator can be a well-known compound known as a curing accelerator, a curing catalyst, a latent curing agent, etc. for epoxy compounds. Examples of the curing accelerator for epoxy compounds include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organic metal compounds, imidazoles, etc. Among the above-mentioned curing accelerators, 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene or salts thereof are more preferably used.

The mass ratio of the component (C) to the component (E) is preferably 90:10 to 40:60. By containing the components (C) and (E) that satisfy the above conditions, the solvent resistance of the formed cured film can be sufficiently improved.

In addition, the ratio of the total number of moles Ea of the epoxy group of the component (C) to the number of moles Eb of the reactive functional group in the curing agent of the component (E) that reacts with the epoxy group (Eb/Ea) is preferably Eb/Ea=0.5 to 1.0. When Eb/Ea is 0.5 or more, the epoxy compound can be sufficiently cured, so that the unreacted epoxy compound can be suppressed from remaining in the photosensitive resin composition. In addition, when Eb/Ea is 1.0 or less, the adhesion and linear reproducibility of the cured film can be sufficiently improved.

<(F) Light-shielding material>

In addition to other components, the photosensitive resin composition of the present invention can use a light-shielding material belonging to the component (F). The light-shielding material is more preferably one or more light-shielding materials selected from the group consisting of black organic pigments, mixed color organic pigments and black inorganic pigments. Here, examples of black organic pigments include: perylene black, aniline black, cyanine black, lactam black, etc. Mixed color organic pigments include: mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. and simulating blackening. Black inorganic pigments include: carbon black, chromium oxide, iron oxide, titanium black, etc. These coloring components can be used alone or in combination of two or more. It can be appropriately selected for use according to the purpose of the photosensitive resin composition of the present invention.

Among these shading materials, from the viewpoint of shading property, surface smoothness, dispersion stability, and affinity with resin, carbon black is more preferably used. In addition, when requiring the low dielectric constant characteristic of the coating film, the shading material can be black organic pigment and/or mixed color organic pigment. On the other hand, in attaching importance to the shading property of visible light and the purposes of infrared penetration, for example, carbon black and lactam black etc. can be used together and carbon black and black organic pigment are used together appropriately.

Carbon black is preferably untreated or oxidized carbon black. Here, untreated means that no special surface treatment such as oxidation treatment or resin coating treatment has been performed, and oxidation treatment means that the surface of carbon black is treated with a certain oxidant before the dispersion step. Such untreated or oxidized carbon black has a large number of acidic functional groups on the surface, so when it is to be used, it is more preferable to use untreated or oxidized carbon black. In addition, when using carbon black to further increase the resistance value of the cured film, the surface of the carbon black can be coated with a dye, pigment, resin, etc.

When such a component (F) is used, the amount can be appropriately set according to the purpose or application of the present invention. For example, it can be arbitrarily determined so as to achieve a desired light shielding degree, but is more preferably 20 to 80% by mass based on the solid content in the photosensitive resin composition.

The component (F) is usually mixed with other ingredients as a dispersion dispersed in a solvent, and a dispersant may be added at this time. The dispersant may be a well-known compound used for dispersing light-shielding materials (compounds sold under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.), etc., without particular limitation.

Examples of dispersants include: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersing aids). In particular, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrol group, a pyridine group, a primary amine group, a secondary amine group, or a tertiary amine group as an adsorption point for the colorant, and an amine value of 1 to 100 mgKOH/g, and a number average molecular weight (Mn) in the range of 1000 to 100000. The blending amount of the dispersant is preferably 1 to 35 parts by mass, and more preferably 2 to 25 parts by mass relative to 100 parts by mass of the light-shielding material component. In addition, high-viscosity substances such as resins generally have the effect of stabilizing dispersion, and substances that do not have the ability to promote dispersion are not used as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

<Other components other than components (E) to (F)>

In addition, in the photosensitive resin composition of the present invention, in addition to the aforementioned components (E) to (F), other epoxy resins other than the aforementioned component (C), other coloring materials other than the aforementioned component (F), thermal polymerization inhibitors, antioxidants, plasticizers, leveling agents, defoamers, surfactants, coupling agents, viscosity modifiers and other additives may be optionally blended. Epoxy resins other than the aforementioned component (C) may use well-known epoxy resins without particular restrictions. In addition, coloring materials other than the aforementioned component (F) may use well-known organic pigments or inorganic pigments or dyes, etc., without particular restrictions. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc., and examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. In addition, examples of defoamers or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, etc. Examples of the coupling agent include silane coupling agents such as 3-(epoxypropyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

<Solid content>

The photosensitive resin composition of the present invention contains the above-mentioned (A) to (D) and (G) components as main components. When the solid content (including the monomer that becomes the solid content after curing) excluding the solvent does not contain the light-shielding material of the (F) component or the hardener and/or hardening accelerator of the (E) component, the total of the components (A) to (D) and (G) is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. When the light-shielding material of the (F) component or the hardener and/or hardening accelerator of the (E) component is contained, the total of the components (A) to (D) and (G) components and the (F) component and the (E) component is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. The amount of the solvent belonging to the (H) component varies depending on the target viscosity, but can be contained in the photosensitive resin composition of the present invention in the range of 60 to 90% by mass.

<Method for Forming Cured Product (Cured Film, Matrix Pattern)>

The photosensitive resin composition of the present invention is excellent as a composition for forming a color filter cured film (protective film, light shielding film), and the method for forming the cured film is as follows. For example, the photosensitive resin composition is first applied to a transparent substrate, and then the solvent is dried (pre-baked), and a photomask is placed on the film thus obtained, and ultraviolet rays are irradiated to cure the exposed part, and an alkaline aqueous solution is used to dissolve and develop the unexposed part to form a pattern, and a post-baking (heat firing) method of post-drying is further performed.

In addition to glass substrates, transparent substrates for coating compositions may include: transparent electrodes such as ITO or gold deposited or patterned on transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.). In addition, examples of other substrates used in the method for manufacturing a cured film of the present invention include: substrates such as glass substrates, silicon wafers, and polyimide films, which have high heat resistance in themselves, but thin films with low heat resistance are formed on the substrates. Specific examples include: substrates with organic devices such as OLEDs or organic thin film transistors (TFTs) formed thereon, and substances with protective films formed after the organic devices are formed. The heat-resistant temperature of such substrates with low heat resistance varies depending on the type of resin or the device, but is preferably below 100°C, and more preferably 80 to 100°C. In addition, substrates with organic devices also include: substances with protective films formed after the organic devices are formed. The reason is that even if the heat resistance of these protective films themselves is above 100°C, when the heat resistance is only below 100°C in order to substantially ensure the function of the organic device, it is also a substrate with an organic device. The present invention is also an effective technology for substrates with low heat resistance, but compared with the conventional process of post-baking at a temperature of more than 200°C, it can also be post-baked at a low temperature, which can reduce the process cost, so it is also an effective technology for this purpose.

In addition to the well-known solution dipping method and spraying method, the method of coating the solution of the composition on the transparent substrate can also adopt any method such as the method using a roll coater, a knife coater, a slit coater or a rotary machine. After coating the desired thickness by these methods, the solvent is removed (pre-baked) to form a film. Pre-baking is carried out by heating with an oven, a hot plate, etc. The heating temperature and heating time in the pre-baking can be appropriately selected according to the solvent used, for example, at a temperature of 60 to 100° C. for 1 to 3 minutes.

The exposure after pre-baking is performed by an ultraviolet exposure device, and the exposure is performed through a photomask, thereby only the photoresist corresponding to the pattern is sensitized. The exposure device and its exposure irradiation conditions can be appropriately selected, and exposure using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a far ultraviolet lamp is performed to photoharden the composition in the coating film.

The purpose of the alkali development after exposure is to remove the photoresist of the unexposed part, and the desired pattern is formed by this development. Examples of the developer suitable for the alkali development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, etc., and it is particularly preferred to use a weak alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate for development at a temperature of 23 to 28° C. Using a commercially available developer or ultrasonic washing machine, etc., a fine image can be precisely formed.

After development, for substrates with high heat resistance, post-baking is preferably performed at about 120 to 250° C., more preferably 140 to 240° C., and even more preferably 150 to 230° C. The heating time is not limited, but it can be performed usually under the condition of 20 to 60 minutes per 1 μm of film thickness.

On the other hand, if the substrate has a low heat resistance, it is more preferably post-baked at a temperature below 100°C, more preferably at a temperature of 80 to 100°C and for 20 to 60 minutes. The purpose of the post-baking is to improve the adhesion between the patterned cured film and the substrate. It can be carried out by heating with an oven, a heating plate, etc. in the same way as the pre-baking. The patterned cured film of the present invention is formed by passing through the above steps of the photolithography method. The obtained cured film can then be used to obtain the desired matrix pattern.

As mentioned above, the photoresist composition of the present invention is suitable for forming fine patterns by exposure, alkali development, etc. In addition, the cured film (light shielding film) of the present invention can be used for black matrices used in color filters or touch panels, or partitioning materials or pixel definition layers for color separation or light shielding in various multicolor display bodies such as electroluminescent devices represented by organic EL elements, color liquid crystal display devices, or image sensors, and display components such as bezels surrounding the display portion of the display.

[Example]

Hereinafter, the embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

First, synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resins that are the component (A) are described. The evaluation of the resins in these synthesis examples was performed in the following manner unless otherwise specified.

[Solid content]

The following formula was used to determine the weight of a glass filter impregnated with 1 g of the resin solution obtained in the synthesis example [weight: W ₀ (g)] [W ₁ (g)] and the weight after heating at 160°C for 2 hours [W ₂ (g)].

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

[Acid value]

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

[Molecular weight]

The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) "HLC-8320GPC" (developing solvent: tetrahydrofuran, manufactured by TOSOH Co., Ltd., column: PL1110-6540 (1 piece) + PL1110-6530 (1 piece) + PL1110-6525 (1 piece) + PL1110-6520 (1 piece), column temperature: 40°C, flow rate: 1.0 mL/min) and the weight average molecular weight (Mw) was determined as a value converted to standard polystyrene (polystyrene set manufactured by SAS Co., Ltd.).

[Average primary particle size]

The solution containing inorganic microparticles was diluted with a solvent to a particle concentration of about 0.1 wt%, and the obtained dispersion was dropped onto a metal mesh with a carbon support film, and the prepared measurement sample was observed with a transmission electron microscope "JEM-2100 Plus" (manufactured by JEOL Ltd.). The number of measurements was n=3.

The abbreviations used in the synthesis examples and the like are as follows.

AA: Acrylic acid

BPFE: a reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. In the compound of the general formula (9), A is fluorene-9,9-diyl, and _R1 to _R4 are hydrogen atoms.

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

THPA: 1,2,3,6-Tetrahydrophthalic anhydride

TPP: triphenylphosphine

PGMEA: Propylene glycol monomethyl ether acetate

TEAB: Tetraethylammonium bromide

DCPMA: Dicyclopentyl Methacrylate

GMA: Glycidyl Methacrylate

St：Styrene

SA: Succinic anhydride

AIBN: Azobisisobutyronitrile

TDMAMP: tris(dimethylaminomethyl)phenol

TEA: triethylamine

PTMA: Pentaerythritol tetrakis(thioglycolate)

DPHA: mixture of dipentaerythritol pentaacrylate and hexaacrylate

HQ: Hydroquinone

BzDMA: benzyl dimethylamine

[Synthesis Example 1]

BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) were added to a 500 ml four-necked flask with a reflux cooler, and stirred at 100 to 105°C for 20 hours to react. Then, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were added to the flask, and stirred at 120 to 125°C for 6 hours to obtain an alkali-soluble resin solution (A)-1 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw of the GPC analysis was 3600.

[Synthesis Example 2]

300.0 g of PGMEA was added to a 1 L four-necked flask with a reflux cooler, and the flask system was replaced with nitrogen and then heated to 120° C. A monomer mixture (a mixture of 10 g of AIBN dissolved in 66.1 g (0.3 mol) of DCPMA, 85.3 g (0.6 mol) of GMA, and 10.4 g (0.10 mol) of St) was dropped into the flask from a dropping funnel over 2 hours, and the mixture was further stirred at 120° C. for 2 hours to obtain a copolymer solution.

After the inside of the flask was replaced with air, 43.2 g (0.6 mol) of AA, 0.8 g of TDMAMP and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was stirred at 120° C. for 6 hours to obtain a copolymer solution containing a polymerizable unsaturated group.

THPA59.3g (0.39 mol) and TEA0.5g were further added to the obtained copolymer solution containing polymerizable unsaturated groups, and the mixture was reacted at 120°C for 4 hours to obtain an alkali-soluble copolymer resin solution (A)-2 containing polymerizable unsaturated groups. The solid content concentration of the resin solution was 48% by mass, the acid value (solid content conversion) was 79 mgKOH/g, and the Mw of the GPC analysis was 8500.

In addition, a synthesis example (Synthesis Example 3) of the component (B)-2 described later is shown.

[Synthesis Example 3]

PTMA (20 g, 0.19 mol of mercapto group), DPHA (212 g (2.12 mol of acryloyl group)), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) were added to a 1 L four-necked flask and reacted at 60° C. for 12 hours to obtain a dendritic polymer solution (H)-3. The solid content concentration of the dendritic polymer solution was 80% by mass, and the Mw of the GPC analysis was 10000. In addition, the disappearance of the mercapto group of the obtained dendritic polymer was confirmed by iodine titration.

[Modulation Example F]

1000 g of carbon black (TPX-1099: manufactured by Cabot) was mixed with water to prepare 10 L of slurry, stirred at 95°C for 1 hour, cooled and then washed with water. It was mixed with water again to prepare 10 L of slurry, 42.9 g of 70% nitric acid was added and stirred at 40°C for 4 hours. It was cooled and washed with water, mixed with water again to prepare 10 L of slurry, 769.2 g of 13% sodium hypochlorite aqueous solution was added, and stirred at 40°C for 6 hours. It was cooled and washed with water, mixed with water again to prepare 10 L of slurry, 38.1 g of dye (Direct Deep BLACK) with a purity of 38.4% was added, and stirred at 40°C for 1 hour, and then 10.1 g of aluminum sulfate was further added and stirred at 40°C for 1 hour. It was cooled and then washed with water, filtered and dried to obtain dye-coated carbon black.

The dye-coated carbon black, polymer dispersant, alkali-soluble resin obtained in the above-mentioned Synthesis Example 1 (hereinafter referred to as (A)-1), and PGMEA are mixed and dispersed in a bead mill to obtain a carbon black dispersion (F) having a dye-coated carbon black concentration of 25.0 mass %, a polymer dispersant concentration of 2.0 mass %, and a resin concentration of (A)-1 of 8.0 mass %.

The photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 4 were prepared in the blending amounts (unit: parts by mass) described in Tables 1 and 2. The blending components used in Tables 1 and 2 are as follows.

(Alkali-soluble resin containing unsaturated groups)

(A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1 above

(A)-2: Alkali-soluble resin solution obtained in Synthesis Example 2 above

(Photopolymerizable compound)

(B)-1: 50% PGMEA solution of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by Toagosei Co., Ltd.; "Aronix" is a registered trademark of the same company)

(B)-2: Resin-like polymer solution obtained in the above-mentioned Synthesis Example 3

(Epoxy-containing cyclic siloxane)

(C)-1: KR-470, manufactured by Shin-Etsu Chemical Co., Ltd.

(C)-2:X-40-2678, manufactured by Shin-Etsu Chemical Co., Ltd.

(Epoxy-containing chain siloxane)

(C)-3:X-40-2669, manufactured by Shin-Etsu Chemical Co., Ltd.

(Other epoxy compounds)

(C')-4: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE-3150, epoxy+cyclohexane equivalent: 180, manufactured by Daicel Co., Ltd.)

(C')-5: 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (Celloxide 2021P, epoxy + cyclohexane equivalent: 126, manufactured by Daicel Co., Ltd.)

(Photopolymerization Initiator)

(D): ADEKA ARKLS NCI-831E, manufactured by ADEKA Co., Ltd., "ADEKA ARKLS" is a registered trademark of the same company

(Hardener)

(E)-1: trimellitic anhydride (TMA, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

(Hardening Aid)

(E)-2: U-CAT SA102, manufactured by San-Apro Co., Ltd.

(Carbon black dispersion)

(F)-1: Pigment dispersion (solid content 35.0% by mass) of a PGMEA solvent having a concentration of 25.0% by mass of the dye-coated carbon black obtained in Preparation Example F, a concentration of 2.0% by mass of a polymer dispersant, and a concentration of 8.0% by mass of the resin of (A)-1

(F)-2: PGMEA dispersion having a carbon black concentration of 20.0 mass % and a polymer dispersant concentration of 5.0 mass % (solid content of 25.0 mass %)

(Inorganic microparticle dispersion)

(G)-1: Silica PGMEA dispersion "YA010C" (manufactured by Admatechs Co., Ltd., silica concentration 20% by mass, PGMEA concentration 80% by mass, refractive index: 1.46, average primary particle size 10 nm)

(G)-2: Silica PGMEA dispersion (silica concentration 30% by mass, PGMEA concentration 70% by mass, refractive index: 1.46, average primary particle size 70 nm)

(Solvent)

(H)-1: Propylene glycol monomethyl ether acetate (PGMEA)

(H)-2: Diethylene glycol dimethyl ether (DMDG)

(H)-3:Diethylene glycol methyl ethyl ether (EDM)

(Other ingredients): DOWSIL SH3775M, manufactured by Dow Chemical Japan Co., Ltd. “DOWSIL” is a trademark of the same company

[Table 1]

Blending Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Embodiment 11 Example 12 Example 13 Embodiment 14 (A)-1 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 - - - - - - (A)-2 - - - - - - - - 0.6 0.6 0.6 0.6 0.6 0.6 (B)-1 1.6 2.5 2.7 1.6 1.6 2.5 2.7 1.6 1.6 2.5 2.7 1.6 1.6 2.5 (B)-2 1.6 2.5 2.7 1.6 1.6 2.5 2.7 1.6 1.6 2.5 2.7 1.6 1.6 2.5 (C)-1 1.7 0.8 0.6 - 1.7 0.8 0.6 - 1.7 0.8 0.6 - 1.7 0.8 (C)-2 - - - 1.7 - - - 1.7 - - - 1.7 - - (C)-3 - - - - - - - - - - - - - - (C′)-4 - - - - - - - - - - - - - - (C′)-5 - - - - - - - - - - - - - - (D) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E)-1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E)-2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F)-1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 (F)-2 - - - - - - - - - - - - - - (G)-1 2.0 2.0 2.0 2.0 - - - - 2.0 2.0 2.0 2.0 - - (G)-2 - - - - 2.0 2.0 2.0 2.0 - - - - 2.0 2.0 (H)-1 32.4 31.5 31.3 32.4 32.4 31.5 31.3 32.4 32.4 31.5 31.3 32.4 32.4 31.5 (H)-2 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 (H)-3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 (Other ingredients) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

[Table 2]

Blending Embodiment 15 Example 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A)-1 - - - - - - - - - - 0.6 - 0.6 - (A)-2 0.6 0.6 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 - 0.6 - 4.4 (B)-1 2.7 1.6 1.3 2.0 2.2 1.3 1.3 2.0 2.2 1.3 1.6 1.6 1.6 1.3 (B)-2 2.7 1.6 1.3 2.0 2.2 1.3 1.3 2.0 2.2 1.3 1.6 1.6 1.6 1.3 (C)-1 0.6 - 1.3 0.6 0.4 - 1.3 0.6 0.4 - - - - - (C)-2 - 1.7 - - - 1.3 - - - 1.3 - - - - (C)-3 - - - - - - - - - - 1.7 1.7 - - (C’)-4 - - - - - - - - - - - - 0.8 0.7 (C′)-5 - - - - - - - - - - - - 0.8 0.7 (D) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E)-1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E)-2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F)-1 24.1 24.1 - - - - - - - - 24.1 24.1 24.1 - (F)-2 - - 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 - - - 30.0 (G)-1 - - 2.0 2.0 2.0 2.0 - - - - 2.0 2.0 2.0 2.0 (G)-2 2.0 2.0 - - - - 2.0 2.0 2.0 2.0 - - - - (H)-1 31.3 32.4 23.5 22.8 22.6 23.5 23.5 22.8 22.6 23.5 32.4 32.4 32.4 23.5 (H)-2 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 (H)-3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 (Other ingredients) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

[assessment]

The following evaluations were performed using the photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 4. The evaluation results are shown in Tables 3 and 4.

<Evaluation of Patternability>

Each of the compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.0 μm, and pre-baked at 85°C for 1 minute. A negative photomask having a line pattern with an opening width of 1 to 20 μm was then adhered to the dried coating film, and ultraviolet rays of 40 mJ/cm ² were irradiated from an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/cm ² to perform a photohardening reaction on the photosensitive portion.

Then, the exposed coated plate was developed at 23°C, 0.04% potassium hydroxide aqueous solution at a shower development pressure of 1kgf/ ^cm2 for 20 seconds from the development time (film breaking time = BT) when the pattern began to appear, and then sprayed with water at a pressure of 5kgf/ ^cm2 to remove the unexposed part of the coating and form a line pattern on the glass substrate. After that, a hot air dryer was used to heat and bake at 85°C for 60 minutes, and the minimum opening line in the obtained line pattern without pattern peeling was taken as the minimum resolution line width. In addition, 0 or more is a pass line.

(Evaluation criteria for fine line adhesion)

◎: Less than 3μm

○: 3 μm or more and less than 10 μm

×: 10 μm or more

In addition, an optical microscope was used to observe the 10 μm mask pattern that was actually cured (post-baked). In addition, 0 or more was a pass line.

(Evaluation criteria for pattern linearity)

⊚: The jagged shape of the pattern edge portion was confirmed to be less than 1% of a 0.5 μm protrusion with respect to a line width of 10 μm, when the pattern length was 100%.

◯: The jagged shape of the pattern edge portion was confirmed to be 1% or more and less than 25% with respect to the line width of 10 μm, when the pattern length was 100%.

×: The jagged shape of the pattern edge portion was confirmed to be 25% or more in proportion to protrusions of 0.5 μm with respect to a line width of 10 μm, when the pattern length was 100%.

<Reflectivity Evaluation>

Each of the compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.0 μm, and pre-baked at 85° C. for 1 minute. Thereafter, ultraviolet rays of 50 mJ/cm ² were irradiated by an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² to perform a photocuring reaction.

Next, the exposed coated plate was developed at 23°C and 0.04% potassium hydroxide aqueous solution at a shower pressure of 1kgf/ ^cm2 for 20 seconds from the development time (film breaking time = BT) when the pattern began to appear, and then sprayed with water at a pressure of 5kgf/ ^cm2 , and then hot-air dried at 85°C for 60 minutes. The coated plate was measured for reflectivity on the film side at an incident angle of 2° using an ultraviolet visible near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Technologies Co., Ltd.). In addition, △ or above is a pass line.

(Reflectivity evaluation criteria)

◎: Reflectivity less than 4%

○: Reflectivity is 4% or more and less than 5%

△: Reflectivity is 5% or more and less than 10%

×: Reflectivity is 10% or more

<Heat resistance evaluation>

The coated plate obtained after post-baking was further heat treated at 230°C for 3 hours, and the b* value was measured by a spectrophotometer.

(Evaluation criteria for heat resistance)

◎: △b* less than 0.2

○: △b* is 0.2 or more and less than 0.5

△: △b* is 0.5 or more and less than 1

×: △b* is 1 or more

<Lightfastness Evaluation>

The coated plate obtained after post-baking was further irradiated with ultraviolet light at a wavelength of 254 nm and an illumination of 130 W/cm ² for 2 hours using a low-pressure mercury lamp, and the b* value was measured by a spectrophotometer. △ or above was a pass line.

(Evaluation criteria for light resistance)

◎: △b* less than 0.5

○: △b* is 0.5 or more and less than 1

△: △b* is 1 or more and less than 1.5

×: △b* is 1.5 or more

[Table 3]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Embodiment 11 Example 12 Example 13 Embodiment 14 Fine line adhesion ◎ ○ ○ ○ ◎ ○ ○ ○ ◎ ○ ○ ○ ◎ ○ Pattern linearity ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ◎ ◎ Film surface reflectivity ○ ◎ ◎ △ △ △ △ △ ○ ◎ ◎ △ △ △ Heat resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ Lightfastness △ △ △ △ △ △ △ △ ○ ○ ○ ○ ○ ○

[Table 4]

Embodiment 15 Example 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Fine line adhesion ○ ○ ◎ ○ ○ ○ ◎ ○ ○ ○ × × × × Pattern linearity ○ ◎ ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ × × ◎ ◎ Film surface reflectivity △ △ ◎ ◎ ◎ △ △ △ △ △ × × ○ ○ Heat resistance ○ ○ △ △ △ △ △ △ △ △ × × ◎ △ Lightfastness ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ × × △ ◎

From the results of Examples 1 to 24 and Comparative Examples 1 to 4, it can be confirmed that by adding the epoxy group-containing cyclic siloxane as the component (C) and the silica dispersion as the inorganic microparticles (G) to the photosensitive resin composition, both the formation of a high-definition pattern and the reduction of the reflectivity of the coating surface can be achieved. In addition, it was confirmed that by using the alkali-soluble resin (A)-1 of Synthesis Example 1 and using the aforementioned component (C) and the aforementioned component, heat resistance can be achieved, and in addition, by using the alkali-soluble resin (A)-2 of Synthesis Example 2 and using the aforementioned component (C) and the aforementioned component, light resistance can be achieved.

Claims (9)

1. A photosensitive resin composition comprising:

(A) An alkali-soluble resin containing an unsaturated group;

(B) A photopolymerizable compound having at least 2 or more unsaturated bonds;

(C) A cyclic siloxane compound having 2 or more epoxy groups in the molecule;

(D) A photopolymerization initiator;

(G) Inorganic microparticles; and

(H) And (3) a solvent.

2. The photosensitive resin composition according to claim 1, wherein the component (C) is a cyclic siloxane compound represented by the general formula (1),

[ R _a and R _b in the general formula (1) represent an epoxy group-containing 1-valent group or a C1-20 1-valent hydrocarbon group, at least 2 of n R _a and R _b are epoxy group-containing 1-valent groups, the R _a and R _b may be the same or different, and n represents an integer of 3 to 10 inclusive ].

3. The photosensitive resin composition according to claim 1, wherein,

The component (A) comprises a polymer comprising a unit represented by the following general formula (2) and a unit represented by the general formula (3), wherein the polymer comprises 5 to 90 mol% of the unit represented by the general formula (2) and 10 to 95 mol% of the unit represented by the general formula (3), has a weight average molecular weight of 3000 to 50000, has an acid value of 30 to 200mg/KOH,

(However, R _c、R_f and R _h independently represent a hydrogen atom or a methyl group, R _d represents a 1-valent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond, an ester bond or a urethane bond in the interior thereof, and R _d is dicyclopentyl or dicyclopentadienyl in an amount of 40 mol% or more of all the units represented by the general formula (2), R _e represents a 2-valent hydrocarbon group having 2 to 10 carbon atoms, p represents a number of 0 or 1, and X represents a hydrogen atom or a-OC-L- (COOH) _k group (wherein L is a 2-valent or 3-valent carboxylic acid residue, and k is 1 to 2)).

4. The photosensitive resin composition according to claim 1, which contains (F) at least 1 light-shielding material selected from the group consisting of black organic pigments, mixed-color organic pigments and black inorganic pigments.

5. The photosensitive resin composition according to claim 1, which contains (E) a curing agent and/or a curing accelerator.

6. The photosensitive resin composition according to claim 1, wherein the refractive index of the component (G) is 1.20 to 1.50 and the average particle diameter is 1 to 150nm.

7. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.

8. A substrate with a cured film, wherein the cured film according to claim 7 is provided on the substrate.

9. A method for manufacturing a substrate with a hardening film, which is to form a hardening film pattern on the substrate to manufacture the substrate with the hardening film,

A method of forming a cured film pattern comprising applying the photosensitive resin composition according to any one of claims 1 to 6 to a substrate, exposing the substrate to light through a photomask, removing the unexposed portion by development, and heating the exposed portion.