KR20210122701A - Photosensitive resin composition, cured product thereof, and color filter with that - Google Patents

Abstract

An objective of the present invention is to provide a photosensitive resin composition and a cured film thereof, capable of reducing a reflectance by a simple scheme, and achieving both a high light-shielding property and highly fine pattern formation. According to the present invention, the photosensitive resin composition includes an alkali-soluble resin (i) containing a polymerizable unsaturated group, having a weight average molecular weight of 2500 or more, and obtained by reacting dicarboxylic acid, tricarboxylic acid, or acid monohydride thereof, and tetracarboxylic acid or acid dianhydride thereof with respect to a reaction product of an epoxy compound having at least two phenylglycidyl ether groups in a molecule, and monocarboxylic acid containing an unsaturated group, and a (meth)acrylate resin (ii) having a weight average molecular weight of 6000 or more and including a carboxyl group and a polymerizable unsaturated group in a side chain as resin components, and includes a light-shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment, and a mixed color organic pigment as an essential component.

Description

A photosensitive resin composition, its cured film, and the color filter which has this cured film TECHNICAL FIELD

This invention relates to the photosensitive resin composition, its cured film, and the color filter which has the said cured film.

In general, a flat panel display such as a liquid crystal display is provided with an antireflection layer in order to reduce reflection of light incident from the outside. The anti-reflection layer mainly includes Anti-Glare (AG) film (anti-glare film) and Anti-Reflection (AR) film (anti-reflection film). The AG film can prevent glare by forming irregularities on the surface of the hard coat resin layer to scatter reflected light, and also using internal scattering due to the difference in refractive index between the hard coat resin and the particles. However, it causes a decrease in contrast due to scattering of reflected light on the surface and a decrease in resolution due to internal scattering of transmitted light from the backlight. On the other hand, in the AR film, two types of layers having mainly different refractive indices are alternately laminated, and reflected light can be reduced by using interference of light. Also, recently, there is a moth-eye method that forms fine irregularities in which the refractive index continuously changes on the surface of an AR film in nanoimprint or the like. AR films can suppress a decrease in contrast due to surface scattered light or a decrease in resolution due to internal scattering, and are mainstream as an antireflection layer.

Moreover, high contrast and high fineness are calculated|required by miniaturization and high resolution of a display in recent years, and reduction of reflectance and improvement of surface smoothness are calculated|required also in an antireflection layer. In particular, since a portable information terminal, a digital signage, an in-vehicle display, etc. which are supposed to be used outdoors greatly affect visibility, the required characteristic of an antireflection layer is high. Although the visibility of the display has been greatly improved by the improvement of the antireflection layer, a reduction in reflectance is also required for each component other than the antireflection layer.

As for each component other than an antireflection layer, the color filter used for a liquid crystal display is mentioned, for example. A color filter includes a colorant constituting a pixel, a black matrix dividing the pixel, and a protective film protecting the pixel. In particular, the colorant used for a black matrix has many high refractive indexes, and the influence on the reflectance of a color filter is large. Although reduction of the amount of a coloring material is mentioned as a method of reducing the reflectance of a black matrix, since the fall of light-shielding property is caused, the contrast of an image falls easily.

In addition, organic electroluminescence displays have been released as self-luminous displays that do not use color filters, and recently, displays using micro LEDs or quantum dots for pixels are also being developed. Although these self-luminous displays generally do not use a color filter, when the reflectance of the barrier rib which partitions a pixel is high, visibility will fall easily.

Patent Document 1, Patent Document 2, and Patent Document 3 disclose a black matrix in which two layers having different optical densities (a layer having a high light-shielding property on a layer having a low light-shielding property) are laminated.

Patent Document 4 discloses a colored cured film having a low reflectance (reflectance on the surface side of the colored cured film) on the opposite side to the substrate.

Japanese Patent Laid-Open No. 2014-157179 Japanese Patent Laid-Open No. 2014-130368 International Publication No. 2014/136738 Japanese Patent Laid-Open No. 2018-141849

According to the knowledge of the present inventors, since the refractive index of the black matrix with respect to the light which penetrates from the board|substrate side with a color filter is low in the method disclosed by patent document 1, patent document 2, and patent document 3, the improvement of visibility can be anticipated. However, in order to laminate a layer with a high light-shielding property after forming a layer with a low light-shielding property on a substrate, the manufacturing process of a color filter becomes complicated, and there exists a possibility that productivity may result.

Moreover, in the colored cured film disclosed by patent document 4, since a silica particle is made to exist on the surface of a colored cured film, unevenness|corrugation may generate|occur|produce on the surface of a colored cured film. Therefore, instead of reducing the specular reflection due to the unevenness of the surface, the diffuse reflection increases, and whitening and dullness occur due to the increase of the diffuse reflection, which may lead to a decrease in the texture.

The present invention has been made in view of this, and it is possible to reduce the reflectance by a simple method, and to provide a photosensitive resin composition capable of both high light-shielding properties and high-definition pattern formation, a cured film thereof, and a color filter having the cured film aim to

As a result of intensive studies to solve the above problems, the present inventors have found that the reflectance can be reduced by a simple method by using two types of resins having a specific structure, and a photosensitive resin composition capable of coexistence of high light-shielding properties and high-definition pattern formation found

That is, the photosensitive resin composition of the present invention is a reaction product of an epoxy compound having two or more phenylglycidyl ether groups in a molecule and a monocarboxylic acid containing an unsaturated group, dicarboxylic acid or tricarboxylic acid or their acid monoanhydride; Alkali-soluble resin (i) containing a polymerizable unsaturated group having a weight average molecular weight of 2500 or more obtained by reacting tetracarboxylic acid or an acid dianhydride thereof, and a weight average molecular weight having a carboxy group and a polymerizable unsaturated group in a side chain of 6000 or more (meth) The acrylate resin (ii) is included as a resin component, and the light-shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment, or a mixed color organic pigment is included as an essential component.

Moreover, the cured film of this invention is made by hardening the said photosensitive resin composition.

Moreover, the color filter of this invention has the said cured film as a black matrix.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, a reflectance can be reduced by a simple method, and the photosensitive resin composition which can be compatible with high light-shielding property and highly detailed pattern formation, its cured film, and the color filter which has the said cured film can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment. In addition, in this invention, when a decimal 1st position is 0 with respect to content of each component, the description below a decimal point may be abbreviate|omitted.

The photosensitive resin composition according to one embodiment of the present invention is a dicarboxylic acid or tricarboxylic acid or an acid thereof with respect to a reaction product of an epoxy compound having two or more phenylglycidyl ether groups in a molecule and a monocarboxylic acid containing an unsaturated group. Alkali-soluble resin (i) containing a polymerizable unsaturated group having a weight average molecular weight of 2500 or more obtained by reacting a monoanhydride and a tetracarboxylic acid or an acid dianhydride thereof, and a carboxyl group and a polymerizable unsaturated group in the side chain have a weight average molecular weight of 6000 The above (meth)acrylate resin (ii) is included as a resin component, and the light-shielding material (iii) selected from the group which consists of a black organic pigment, a black inorganic pigment, or a mixed color organic pigment is included as an essential component.

Hereinafter, (i)-(iii) component is demonstrated.

(Alkali-soluble resin containing polymerizable unsaturated group)

The polymerizable unsaturated group-containing alkali-soluble resin having a weight average molecular weight of 2500 or more as the component (i) according to one embodiment of the present invention is represented by the following general formula (1).

(In formula (1), R ₁ is independently a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is independently a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is independently a hydrogen atom or a methyl group, and X is independently A divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ - , -Si(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a single bond represented by the general formula (2), Y is a tetravalent carboxylic acid residue, and Z is independently a hydrogen atom or a substituent represented by the general formula (3), with the proviso that at least one of Z is a substituent represented by the general formula (3), and G is independently a hydrogen atom or a substituent represented by the general formula (4), a is independently a number from 0 to 10, the average value of a in one molecule is also a number from 0 to 10, and the average value of a in the composition is also a number from 0 to 10. b is independently a number from 0 to 4; , the average value of b in one molecule is also a number of 0 to 4, and the average value of b in the composition is also a number of 0 to 4. n is an integer whose average value is 1 to 20)

(in formulas (3) and (4), R ₄ and R ₆ are a hydrogen atom or a methyl group, R ₅ and R ₇ are a hydrocarbon group having 2 to 4 carbon atoms, L is a di or trivalent carboxylic acid residue; c, f is the number of 0 or 1, d and e are the number of 0, 1 or 2, and d+e is the number of 1 or 2)

In a method for producing an alkali-soluble resin (i) containing a polymerizable unsaturated group having a weight average molecular weight of 2500 or more represented by the general formula (1) (hereinafter also simply referred to as “alkali-soluble resin represented by general formula (1)”) explain about

First, a bisphenol-type epoxy compound (a-1) having two or more phenylglycidyl ether groups in one molecule represented by the following general formula (8) (hereinafter simply referred to as “epoxy compound represented by general formula (8)”) ) and an unsaturated group-containing monocarboxylic acid (for example, (meth)acrylic acid) are reacted to obtain diol containing a polymerizable unsaturated group. In addition, "(meth)acrylic acid" is a generic term for acrylic acid and methacrylic acid, and means one or both of these.

(in formula (8), R ₁ is independently a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is independently a hydrocarbon group having 1 to 3 carbon atoms, and X is independently a hydrocarbon group having 1 to 3 carbon atoms which may contain a hetero element therein. -20 divalent organic groups, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, - O-, a fluorene-9,9-diyl group or a single bond represented by the general formula (2), a is independently a number from 0 to 10, and b is independently a number from 0 to 4)

The epoxy compound represented by General formula (8) is an epoxy compound which has two phenylglycidyl ether groups in 1 molecule obtained by making bisphenol and epichlorohydrin react. Since this reaction generally involves oligomerization of a diglycidyl ether compound, an epoxy compound containing two or more bisphenol skeletons is included.

Examples of the bisphenols 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)hexafluoro Ropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethyl Silane, 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-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane , 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxyl) Roxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis( 4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-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' -Biphenols, etc. are included.

Examples of the unsaturated group-containing monocarboxylic acid to be reacted with the epoxy compound represented by the general formula (8) include acrylic acid or methacrylic acid in addition to acrylic acid and methacrylic acid, and acid monoanhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride. The reacted compound and the like are included.

A well-known method can be used for reaction of the epoxy compound represented by General formula (8), and the said unsaturated group containing monocarboxylic acid. For example, Japanese Patent Laid-Open No. 4-355450 describes that a diol containing a polymerizable unsaturated group is obtained by using about 2 moles of (meth)acrylic acid with respect to 1 mole of an epoxy compound having two epoxy groups. In the present invention, the reactant obtained in the above reaction is a diol (d) containing a polymerizable unsaturated group represented by the general formula (9) (hereinafter also simply referred to as “a diol represented by the general formula (9)”).

(in formula (9), R ₁ is independently a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is independently a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is independently a hydrogen atom or a methyl group, and X is independently A divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ - , -Si(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a single bond represented by the general formula (2), a is independently a number from 0 to 10, and b is independently is a number from 0 to 4)

Examples of the divalent organic group having 1 to 20 carbon atoms include a divalent hydrocarbon group, a divalent group having one or two carboxyl groups in the side chain of the hydrocarbon group, and the like. Moreover, the said hydrocarbon group may have an ether bond oxygen atom or an ester bond inside.

Further, examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a sec-butylene group, a methylisobutylene group, a hexylene group, a decylene group, a dodecylene group, etc. straight or branched. hydrocarbon groups having a chain are included. In addition, the divalent organic group represented by General formula (10)-(12) is contained in the example of the divalent group which has an ester bond in the inside of a hydrocarbon group.

(in formula (10), h is an integer of 1-20)

(in formula (11), i is an integer of 2-20, and j is an integer of 0-10)

(in formula (12), k is an integer from 0 to 18, and l is independently an integer from 1 to 10)

Further, (a) dicarboxylic acid or tri, which is reacted with the hydroxyl group in the molecule of the diol represented by the general formula (9), which is a reaction product of the epoxy compound represented by the general formula (8) and the monocarboxylic acid containing an unsaturated group Examples of carboxylic acids or their acid monoanhydrides include chain hydrocarbon dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, alicyclic dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, aromatic dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides.

Examples of the chain hydrocarbon dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid , tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and their acid monoanhydrides. Also included are dicarboxylic acids or tricarboxylic acids into which any of these substituents have been introduced, and their acid monoanhydrides and the like.

Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or their acid monoanhydride include acids such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid and norbornanedicarboxylic acid. 1 Contains an anhydride. Also included are dicarboxylic acids or tricarboxylic acids, or their acid monoanhydrides, into which any of these substituents have been introduced.

Examples of the aromatic dicarboxylic acid or tricarboxylic acid or their acid monoanhydride include phthalic acid, isophthalic acid, trimellitic acid, and their acid monoanhydride. Also included are dicarboxylic acids or tricarboxylic acids into which any of their substituents have been introduced and their acid monoanhydrides.

Among the dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferable, and succinic acid, itaconic acid and tetrahydrophthalic acid are preferable. It is more preferable that Moreover, it is preferable to use these acid monoanhydrides among the said dicarboxylic acid or tricarboxylic acid. As for the acid monohydride of dicarboxylic acid or tricarboxylic acid mentioned above, only 1 type may be used independently and may use 2 or more types together.

Further, (b) tetracarboxylic acid or its (b) tetracarboxylic acid reacted with the hydroxyl group in the molecule of the diol represented by the general formula (9) which is a reaction product of the epoxy compound represented by the general formula (8) and the monocarboxylic acid containing an unsaturated group Examples of the acid dianhydride include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or acid dianhydride thereof.

Examples of the chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain hydrocarbon tetracarboxylic acid introduced with a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group. This is included.

Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and a chain hydrocarbon group; and alicyclic tetracarboxylic acid into which a substituent such as an unsaturated hydrocarbon group has been introduced.

Examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid and the like.

In the said tetracarboxylic acid, it is preferable that they are biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid, and it is more preferable that they are biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid. . Moreover, in tetracarboxylic acid or its acid dianhydride, it is preferable to use this acid dianhydride. In addition, the above-mentioned tetracarboxylic acid or its acid dianhydride may be used individually by the 1 type, and may use 2 or more types together.

(a) dicarboxylic acid or tricarboxylic acid or their acid monoanhydride, (b) tetracarboxylic acid or its acid dianhydride, It is preferable that they are 0.01 or more and 10.0 or less, and, as for the molar ratio (a)/(b), it is more preferable that they are 0.02 or more and less than 3.0. When molar ratio (a)/(b) is 0.01 or more and 10.0 or less, the optimal molecular weight for setting it as the photosensitive resin composition which has favorable optical patterning property will be obtained. In addition, as molar ratio (a)/(b) is small, molecular weight becomes large and there exists a tendency for alkali solubility to fall.

In addition, the reaction of the epoxy compound represented by the general formula (8) and the monocarboxylic acid containing an unsaturated group, and the reaction of the diol represented by the general formula (9) obtained in the above reaction and the polybasic acid or its acid anhydride are not particularly limited. Instead, a known method can be employed.

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) synthesized by the above reaction is 2500 or more, preferably 2500 or more and 100000 or less, and more preferably 2500 or more and 25000 or less. If the weight average molecular weight (Mw) is 2500 or more, phase separation is performed with a (meth)acrylate resin (described later), and a thin layer (10-100 nm) is formed on the outermost layer side of the cured film (the side not in contact with the substrate), so it is reflected Even if it does not form a prevention film etc. in the outermost layer (surface which does not contact a base material) of a cured film, a reflectance can be reduced. Moreover, while being able to suppress the adhesive fall of the pattern at the time of alkali image development as it is 100000 or less, it is easy to adjust to the solution viscosity of the photosensitive resin composition suitable for application|coating, and time does not require too much time for alkali development.

Further, the acid value of the alkali-soluble resin represented by the general formula (1) is preferably 30 mg/KOH or more and 200 mg/KOH or less, more preferably 40 mgKOH/g or more and 140 mgKOH/g or less, 80 mg It is more preferable that they are KOH/g or more and 120 mgKOH/g or less. When the acid value of the alkali-soluble resin is 30 mg/KOH or more, it becomes difficult to leave a residue at the time of alkali development. In addition, if it is 200 mgKOH/g or less, the permeation of the alkali developer does not become excessively rapid, so that the peeling phenomenon can be suppressed.

The weight average molecular weight (Mw) of alkali-soluble resin represented by General formula (1) can be measured, for example by gel permeation chromatography (GPC) "HLC-8220GPC" (made by Tosoh Corporation). In addition, the acid value of alkali-soluble resin represented by General formula (1) can be measured using potentiometric titration apparatus "COM-1600" (made by HIRANUMA Co., Ltd.), for example.

In addition, about alkali-soluble resin represented by General formula (1) of (i) component, you may use individually by 1 type, and may use 2 or more types together.

The mass of the alkali-soluble resin represented by the general formula (1) is 40 with respect to the total mass of the alkali-soluble resin represented by the general formula (1) and the (meth)acrylate resin (described later) represented by the general formula (13) It is preferable that it is -99 mass %, It is more preferable that it is 40-90 mass %, It is more preferable that it is 40-80 mass %. If the mass of the said alkali-soluble resin is 40-99 mass %, a reflectance can be reduced, maintaining high-definition pattern formation.

((meth)acrylate resin)

The (meth)acrylate resin having a weight average molecular weight of 6000 or more having a carboxyl group and a polymerizable unsaturated group in the side chain as component (ii) according to one embodiment of the present invention is, for example, represented by the following general formula (13). The general formula (13) is a random copolymer containing m, o, and p units of each unit, respectively.

(In formula (13), R ₈ , R ₁₀ , R ₁₁ are independently a hydrogen atom or a methyl group, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ is an ethereal oxygen atom or a urethane bond therein. R ₁₂ is independently a divalent hydrocarbon group having 2 to 10 carbon atoms, g is independently a number of 0 or 1, and m, o, and p are independently arbitrary integers)

A (meth)acrylate resin (ii) having a weight average molecular weight of 6000 or more having a carboxyl group and a polymerizable unsaturated group in the side chain represented by the general formula (13) (hereinafter, simply “(meth)acryl represented by the general formula (13)” rate resin") will be described.

The (meth)acrylate resin represented by General formula (13) by one Embodiment of this invention is (meth)acrylate represented by General formula (5), and (meth)acrylic acid represented by General formula (6) It is derived from a polyhydric carboxylic acid compound represented by the following general formula (14) obtained by copolymerizing The general formula (14) is a random copolymer including m and o units, respectively.

(In formula (5), R ₈ is a hydrogen atom or a methyl group, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ may contain an ethereal oxygen atom or a urethane bond therein)

(in formula (6), R ₁₀ is a hydrogen atom or a methyl group)

(In formula (14), R ₈ and R ₁₀ are a hydrogen atom or a methyl group, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ may contain an ethereal oxygen atom or a urethane bond therein. o and m are arbitrary integers)

_{Examples of the hydrocarbon group of R 9} represented by the general formula (5) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group, a dodecyl group, A cycloaliphatic hydrocarbon group such as a linear hydrocarbon group such as a tetradecyl group and an eicosyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, a tricyclodecylmethyl group, a decahydronaphthyl group, and a substituent represented by the following general formula (15) , aliphatic ethers such as methoxyethyl group and 2-(methoxyethoxy)ethyl group, and aliphatic urethanes such as 2-(ethoxycarbonylamino)ethyl group.

(in formula (15), R ₁₃ is a hydrogen atom or a methyl group)

Among the hydrocarbon groups, it is preferable that they are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, or a tricyclodecylmethyl group, and a methyl group, an ethyl group, a cyclohexyl group , a norbornyl group, an isobornyl group, and a tricyclodecylmethyl group are more preferable.

About the (meth)acrylate represented by the said General formula (5), you may use individually by 1 type, and may use 2 or more types together. In addition, about the (meth)acrylic acid represented by General formula (6), you may use individually by 1 type, and may use 2 or more types together.

The polyhydric carboxylic acid represented by the said General formula (14) is a structural component derived from the (meth)acrylate represented by the general formula (5), and the structural component derived from the (meth)acrylic acid represented by the general formula (6) This is basically a randomly bound copolymer. In addition, the method in particular to copolymerize is not restrict|limited, A well-known copolymerization method is employable.

The repeating unit (m) of the structural component derived from the (meth)acrylate represented by General formula (5) in the polyhydric carboxylic acid represented by General formula (14), and (meth) represented by General formula (6) ) The repeating unit (o) of the constituent component derived from acrylic acid is m when the sum of the numbers of m and o is 100 in consideration of reacting the (meth)acrylate having an epoxy group represented by the general formula (7). It is preferable that it is 20-70, and it is more preferable that it is 30-60. Moreover, it is preferable that it is 30-80, and, as for o, it is more preferable that it is 40-70. In addition, m and o are independently arbitrary integers. By making m into 20-70 and o into 30-80, both solubility and sclerosis|hardenability with respect to an alkali developing solution are compatible.

And by reacting (meth)acrylate which has an epoxy group represented by general formula (7) with a part of the carboxyl group of polyhydric carboxylic acid compound represented by general formula (14), general formula (13) by one Embodiment of this invention (meth)acrylate resin represented by ) is obtained. In addition, there is no particular regularity in the bonding order of the constituent components, and it is basically a copolymer bonded at random.

(in formula (7), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is a divalent hydrocarbon group having 2 to 10 carbon atoms, and g is the number of 0 or 1.)

In the general formula (13), a component derived from the (meth)acrylate compound represented by the general formula (5), a component derived from the (meth)acrylic acid compound represented by the general formula (6), and the general formula ( The binding order of the three components of the component in which (meth)acrylate having an epoxy group represented by the general formula (7) is added to a part of the carboxyl group of the component derived from (meth)acrylic acid represented by 6) is There is no particular regularity, and it is a copolymer in which three kinds of constituent components are basically randomly combined.

The solvent used when making the (meth)acrylate having an epoxy group represented by the general formula (7) react with a part of the carboxyl groups in the polyhydric carboxylic acid represented by the general formula (14) is not particularly limited, but higher than the reaction temperature It is preferable that it is a solvent which has a boiling point.

Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, acetic acid High boiling point ether or ester solvents, such as butyl, ketone solvents, such as cyclohexanone and diisobutyl ketone, etc. are contained.

The catalyst to be used is not particularly limited, and for example, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and tris(2,6- Phosphines, such as dimethoxyphenyl) phosphine, etc. are contained.

When the (meth)acrylate resin represented by the general formula (13) is produced by reacting the polyhydric carboxylic acid represented by the general formula (14) with the (meth)acrylate having an epoxy group represented by the general formula (7) It is preferable that it is 20-140 degreeC, and, as for reaction temperature, it is more preferable that it is 40-130 degreeC.

Moreover, (meth)acrylate which has an epoxy group represented by General formula (7) at the time of manufacturing (meth)acrylate resin represented by General formula (13), and polyhydric carboxyl represented by General formula (14) The acid injection ratio can be arbitrarily changed for the purpose of adjusting the acid value and curability of the (meth)acrylate resin represented by the general formula (13). At this time, the injection ratio of the epoxy group in the (meth)acrylate having the epoxy group represented by the general formula (7) to the carboxy group in the polyhydric carboxylic acid represented by the general formula (14) is preferably 10 to 50 mol%, and 30 to It is more preferable that it is 50 mol%.

In addition, when the total of the repeating units (m, o, p) in the (meth)acrylate resin represented by General formula (13) is 100, the number of each repeating unit (m, o, p) is an acid value and curability may be arbitrarily changed for the purpose of adjusting the The repeating unit (m) is preferably 20 to 70, more preferably 30 to 60, preferably 5 to 70, more preferably 10 to 50, and more preferably 30 to 60, the repeating unit (o). It is preferable that it is 10-75, and, as for (p), it is more preferable that it is 20-60. It can suppress that content of a polymeric double bond falls that m is 20-70, and the adhesiveness and hardness of a cured film fall. Moreover, since the water absorption of a cured film does not become high that o is 10-50, the solubility to an organic solvent improves. Moreover, when p is 10-40, since the volume contraction at the time of hardening does not become large too much, adhesiveness with a board|substrate and surface flatness can be improved.

The weight average molecular weight (Mw) of (meth)acrylate resin represented by General formula (13) is 6000 or more, It is preferable that they are 6000 or more and 1000000 or less, It is more preferable that they are 10000 or more and 100000 or less. When the weight average molecular weight (Mw) is 6000 or more, the above-described alkali-soluble resin and phase separation are performed, and a thin layer (10 to 100 nm) is formed on the outermost layer side of the cured film (the side not in contact with the substrate), so the anti-reflection film is cured. Even if it does not form in the outermost layer of a film|membrane (surface which does not contact a base material), a reflectance can be reduced. Moreover, the fall of adhesiveness and sclerosis|hardenability can be suppressed as it is 1000000 or less.

Moreover, it is preferable that they are 30 mg/KOH or more and 200 mg/KOH, and, as for the acid value of (meth)acrylate resin represented by General formula (13), it is more preferable that they are 40 mg/KOH or more and 140 mg/KOH or less. When the acid value of the said (meth)acrylate resin is 30 mg/KOH or more, it becomes difficult to leave a residue at the time of alkali development. In addition, if it is 200 mgKOH/g or less, the permeation of the alkali developer does not become excessively rapid, so that the peeling phenomenon can be suppressed.

The weight average molecular weight (Mw) and acid value of (meth)acrylate resin represented by the said General formula (13) can be measured with the apparatus similar to the measuring apparatus used with alkali-soluble resin represented by General formula (1).

The mass of the (meth)acrylate resin represented by the general formula (13) is based on the total mass of the alkali-soluble resin represented by the above-mentioned general formula (1) and the (meth)acrylate resin represented by the general formula (13). It is preferable that it is 1-60 mass % with respect to it, It is more preferable that it is 10-60 mass %, It is more preferable that it is 20-60 mass %. Since formation of a crosslinked structure becomes enough that the mass of the said (meth)acrylate resin is 1-60 mass %, the cured film after hardening is hard to become soft.

(Light-shielding material)

The light-shielding material as component (iii) according to an embodiment of the present invention is selected from the group consisting of a black organic pigment, a black inorganic pigment, or a mixed color organic pigment.

As the light-shielding material that can be used in the present invention, any known light-shielding component can be used without particular limitation as long as it is dispersed with an average particle diameter of 1 to 1000 nm. The average particle size of the light-shielding material can be measured, for example, by a laser diffraction/scattering method particle size distribution meter or a dynamic light scattering method particle size distribution meter.

Examples of the black organic pigment include perylene black, cyanine black, aniline black, lactam black, and the like.

Examples of the black inorganic pigment include carbon black, chromium oxide, iron oxide, and titanium black.

Examples of the mixed color organic pigment include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxadine pigments, srene pigments, perylene pigments, ferri and mixed pigments obtained by mixing at least two pigments selected from organic pigments such as non-pigments, quinophthalone pigments, diketopyrrolopyrrole pigments and thioindigo pigments to produce pseudo-blackened pigments.

The said light-shielding material may be used individually by 1 type according to the function of the photosensitive resin composition made into the objective, and may use 2 or more types together. For example, carbon black, titanium black, black organic pigment, etc. can be used as a light-shielding resist used for manufacture of the black matrix of a color filter, As a coloring resist used for manufacture of the pixel of a color filter, red, orange, yellow, Green, blue, purple organic pigments can be used, and organic pigments, inorganic pigments, inorganic fillers, etc. can be used as solder resists used for the production of the insulating film of the printed wiring board, and used for the design of the front glass of the touch panel. Carbon black, titanium black, black organic pigment, white pigment, etc. can be used as a decorative resist, and transparent fillers, such as silica, can be used as a high-hardness and high-durability transparent resist, and each can be appropriately selected and used.

In addition, in the case of using a mixed color organic pigment as the component (iii), examples of the organic pigment usable include, but are not limited to, those having the following numbers in the color index name.

Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.

Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.

Pigment green 7, 36, 58, etc.

Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.

Pigment Violet 19, 23, 37, etc.

Although content of the said light-shielding material can be arbitrarily determined by a desired light-shielding degree, it is preferable that it is 20-80 mass % with respect to the solid component in the photosensitive resin composition, and it is more preferable that it is 40-70 mass %.

When using black organic pigments, such as aniline black, cyanine black, and lactam black, or black inorganic pigments, such as carbon black and titanium black, as a light-shielding material, it is especially preferable that it is 40-60 mass % with respect to the solid component in the photosensitive resin composition. do. Light-shielding property can fully be acquired as content of a light-shielding material is 20 mass % or more with respect to the solid component in the photosensitive resin composition. Moreover, since content of the photosensitive resin used as an original binder does not decrease as content of the light-shielding material is 80 mass % or less with respect to the solid component in the photosensitive resin composition, desired developing characteristics and film-forming performance can be acquired.

The light-shielding material is a light-shielding material dispersion dispersed in a solvent, and is usually mixed with other compounding components, in which case a dispersant can be added. The dispersing agent that can be used is not particularly limited, and known compounds (compounds marketed under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) used for dispersing pigments (light-shielding materials), etc. can be used.

Examples of the dispersant include a cationic polymer-based dispersant, an anionic polymer-based dispersant, a nonionic polymer-based dispersant, and a pigment derivative-type dispersant (dispersion aid). In particular, the dispersant has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the colorant, and an amine value of 1 to 100 mgKOH/g, water It is preferable that it is a cationic polymer type dispersing agent which has an average molecular weight (Mn) in the range of 1000-100000. It is preferable that it is 1-35 mass % with respect to the total mass of a light-shielding material, and, as for content of this dispersing agent, it is more preferable that it is 2-25 mass %. In addition, high-viscosity substances such as resins generally have an action of stabilizing dispersion, but those having no dispersion promoting ability are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

(photopolymerizable monomer)

It is preferable that the photosensitive resin composition by one Embodiment of this invention contains the photopolymerizable monomer which has at least two polymerizable unsaturated groups which are component (iv).

Examples of the photopolymerizable monomer 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, glycerol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) ) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, di (meth)acrylic acid esters such as pentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate and resinous polymers having a (meth)acryl group as a compound having an ethylenic double bond. Only one type of these monomers may be used individually, and two or more types may be used together.

In addition, the photopolymerizable monomer can serve to crosslink molecules of the alkali-soluble resin, and in order to exhibit this function, it is preferable to have at least two ethylenically unsaturated bonds, and three ethylenically unsaturated bonds It is more preferable to have more than one. Moreover, it is preferable that the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acrylic groups in one molecule is 50 to 300 g/eq, and the acrylic equivalent is more preferably 80 to 200 g/eq. In addition, the photopolymerizable monomer does not have a free carboxy group.

Moreover, as a compound which has an ethylenically unsaturated bond, the resinous polymer which has a (meth)acryloyl group can be used. Examples of the resinous polymer include a resinous polymer obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bonds in the (meth)acryloyl group of the polyfunctional (meth)acrylate. Specific examples include a resinous polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the general formula (16) and a polyvalent mercapto compound represented by the general formula (17).

(In the formula (16), R ₁₄ is a hydrogen atom or a methyl group, and R ₁₅ is the remainder of supplying n hydroxyl groups within the k hydroxyl groups of _{R 16} (OH) _{k to the ester bond in the formula. Preferred R 16} ( OH) _k is a polyhydric alcohol based on a non-aromatic straight or branched hydrocarbon backbone having 2 to 8 carbon atoms, or a polyhydric alcohol ether formed by connecting multiple molecules of the polyhydric alcohol through an ether bond by dehydration condensation of the alcohol; , or esters of these polyhydric alcohols or polyhydric alcohol ethers and hydroxy acids)

(in formula (17), R ₁₇ is a single bond or a divalent to hexavalent C1 to C6 hydrocarbon group, r is _{2 when R 17} is a single bond, and an integer of 2 to 6 when _{R 17 is a divalent to hexavalent group} am)

In addition, although q represented by General formula (16) and r represented by General formula (17) independently represent the integer of 2-20, q≥r.

Examples of the polyfunctional (meth)acrylate represented by the general formula (16) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene Oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and (meth)acrylic acid esters such as caprolactone-modified pentaerythritol tri(meth)acrylate. These compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyvalent mercapto compound represented by the general formula (17) include trimethylol propane tri (mercapto acetate), trimethylol propane tri (mercapto propionate), pentaerythritol tetra (mercapto acetate), penta Erythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. are contained. These compounds may be used individually by 1 type, and may use 2 or more types together.

It is preferable that it is 50/50-90/10 in weight ratio (i)/(iv), and, as for the compounding ratio of (i) component and (iv) component, it is more preferable that it is 60/40-80/20. (i) When the mixing ratio of the component is 50/50 or more, the cured product after photocuring is difficult to become brittle, and the acid value of the coating film is difficult to decrease in an unexposed portion, so that the decrease in solubility in an alkali developer can be suppressed. Therefore, it is difficult to generate a problem that the pattern edge is not uneven or is not sharp. Moreover, since the ratio of the photoreactive functional group which occupies for resin when the compounding ratio of (i) component is 90/10 or less is enough, formation of a desired crosslinked structure can be performed. Further, since the acid value in the resin component is not too high, the solubility in the alkali developer in the exposed portion is difficult to increase, so that the formed pattern becomes thinner than the target line width and the pattern loss can be suppressed.

(Photoinitiator)

It is preferable that the photosensitive resin composition by one Embodiment of this invention contains the photoinitiator which is (v) component.

Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, etc. benzophenones such as acetophenone, benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluoro Biimidazoles such as phenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloro halomethylthiazole compounds such as romethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 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-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5- Trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1 , halomethyl-S-triazine-based compounds such as 3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime -O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-oneoxime-O -O-acyl oxime compounds, such as an acetate and 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyl oxime; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide and cumene peroxide; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photoinitiators may be used individually by the 1 type, and may use 2 or more types together.

In particular, when preparing a photosensitive resin composition containing a colorant, it is preferable to use O-acyloxime compounds (including ketoxime). Examples of the compound group that can be preferably used include O-acyloxime-based photopolymerization initiators represented by the general formulas (18) and (19). Among these compound groups, it is preferable to use an O-acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10000 or more at 365 nm when using a colorant at a high pigment concentration and when forming a cured film pattern. In addition, the "photoinitiator" as used in this invention is used in the meaning containing a sensitizer. In addition, a molar extinction coefficient can be measured using the ultraviolet-visible near-infrared spectrophotometer "UH4150" (made by Hitachi High-Tech Science Corporation), for example.

(In formula (18), R ₁₈ , R ₁₉ independently represent a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group, or a C4-C12 heterocyclic group, and R ₂₀ is a C1-C15 represents an alkyl group of may contain, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be any one of linear, branched, or cyclic alkyl groups)

(in formula (19), R ₂₁ and R ₂₂ are independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or 1 to 6 carbon atoms is a phenyl group optionally substituted with an alkyl group, R ₂₃ is each independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and a part of the -CH2- group in the alkyl group or alkenyl group is substituted with an -O- group In addition, _{some of the hydrogen atoms in these R 21} to R ₂₃ groups may be substituted with halogen atoms)

(v) It is preferable that it is 3-30 weight part on the basis of a total of 100 weight part of each component of (i) and (iv), and, as for content of the photoinitiator of component, it is more preferable that it is 5-20 weight part. (v) When the blending ratio of the component is 3 parts by weight or more, the sensitivity is good and it can have a sufficient photopolymerization rate. When the mixing ratio of the component (v) is 30 parts by weight or less, it is possible to have a suitable sensitivity, so that a desired pattern line width and a desired pattern edge can be obtained.

(Photosensitive resin composition)

The dispersion liquid used for the photosensitive resin composition can be prepared by mixing and dispersing the said (i)-(v) component by an appropriate method.

(solvent)

It is preferable to use a solvent for the photosensitive resin composition of this invention as (vi) component other than the component of (i)-(v). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; 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; Cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol glycol ethers such as monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. of acetic acid esters. By dissolving and mixing these individually or in combination of two or more types, it can be set as the uniform solution-form composition.

In addition, in the photosensitive resin composition of the present invention, if necessary, a resin other than component (i) such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent Additives, such as these, can be mix|blended.

Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based compounds, and the like.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like.

Examples of the filler include glass fiber, silica, mica, alumina, and the like.

Examples of the defoaming agent or leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like.

Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidepropyltriethoxysilane etc. are included.

The photosensitive resin composition of the present invention contains an alkali-soluble resin as (i) component and (ii) component (meta) in the solid component (the solid component includes a monomer that becomes a solid component after curing) excluding the solvent as the component (vi) ) Acrylic resin, (iii) component, light-shielding material, (iv) component, photopolymerizable monomer, and (v) component, photopolymerization initiator, are preferably contained in a total of 80% by mass or more, and 90% by mass or more It is more preferable to be Although the quantity of a solvent changes with the target viscosity, it is preferable that it is 40-90 mass % with respect to the whole quantity.

Further, the cured film formed by curing the photosensitive resin composition of the present invention is obtained by, for example, applying a solution of the photosensitive resin composition to a substrate, drying the solvent, irradiating light (including ultraviolet rays, radiation, etc.) and curing it. lose A desired pattern is obtained by forming a portion that is exposed to light and a portion that is not exposed by using a photomask or the like, curing only the portion that is exposed to light, and dissolving the other portion in an alkaline solution.

Moreover, the cured film formed by hardening|curing the photosensitive resin composition of this invention can be used for a color filter as a black matrix. For example, forming a cured film having a film thickness of 1.0 to 2.0 µm on a transparent substrate, forming each red, blue, and green pixel by photolithography after forming the cured film, and red by an inkjet process in the cured film , blue, and green inks, etc. are produced.

Moreover, the cured film formed by hardening|curing the photosensitive resin composition of this invention can also be used as a black column spacer of a liquid crystal display device. For example, a plurality of portions having different film thicknesses may be produced using a single black resist, one may function as a spacer, and the other may function as a black matrix.

Each process of the film-forming method of the cured film by application|coating and drying of the photosensitive resin composition by one Embodiment of this invention is illustrated concretely.

As a method of apply|coating the photosensitive resin composition to a board|substrate, any method, such as a method using a well-known solution immersion method, a spray method, a roller coater machine, a land coater machine, a slit coat machine, and a spinner machine, can also be employ|adopted. After coating to a desired thickness by these methods, a film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or combining these. Although the heating temperature and heating time in a pre-baking can be suitably selected according to the solvent to be used, it is preferable to carry out, for example at 80-120 degreeC for 1 to 10 minutes.

As the radiation used for exposure, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. In addition, as a developing solution suitable for this alkali development, aqueous solutions, such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, can be used, for example. These developing solutions can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The developing temperature is preferably 20 to 35° C., and a fine image can be precisely formed using a commercially available developing device, ultrasonic cleaner, or the like. In addition, after alkali development, it washes with water normally. As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method, etc. are applicable.

After developing in this way, heat treatment (post-baking) is performed at 180 to 250°C for 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesiveness of the patterned cured film (cured film) and a board|substrate. This is done by heating with an oven, a hotplate, etc. similarly to a pre-baking. The patterned cured film (cured film) of this invention is formed through each process by the photolithographic method. And the cured film which has a desired pattern can be obtained by completing superposition|polymerization or hardening (both together may be called hardening) with heat|fever. At this time, the curing temperature is preferably 160 ~ 250 ℃.

The cured film obtained by the said method forms a thin layer in the outermost layer (surface which does not contact a base material) on the side of a cured film by phase-separating a polymerizable unsaturated-group containing alkali-soluble resin and (meth)acrylate resin. As a result, a cured film having a reduced reflectance can be easily obtained without using a resin having a lowered refractive index and without separately forming an antireflection film or the like in the outermost layer (surface not in contact with the substrate) of the formed cured film.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is concretely described based on an Example and a comparative example, this invention is not limited to these.

Although it demonstrates from the synthesis example of alkali-soluble resin represented by General formula (1) which is (i) component, and (meth)acrylate resin represented by General formula (13) which is (ii) component, the resin in these synthesis examples Evaluation was performed as follows unless otherwise indicated. When the same model is used for various measuring instruments, the name of the instrument maker is omitted from the second place. In addition, all the glass substrates used for preparation of the board|substrate with a cured film for a measurement in the Example are using the glass substrate which performed the same process.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example _{was impregnated in a glass filter [weight: W 0} (g)], weighed [W ₁ (g)], and then heated at 160 ° C. for 2 hours [W ₂ (g)] from the following weight It calculated|required by Formula (1).

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

[acid value]

The resin solution was dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution was obtained using a potentiometric titrator "COM-1600" (manufactured by HIRANUMA Co., Ltd.).

[Molecular Weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH-4000 (1 piece) + TSKgelSuperH -5000 (1 piece) (made by Tosoh Corporation), temperature: 40 degreeC, speed: 0.6 ml/min), and the weight average molecular weight (Mw) as a conversion value of standard polystyrene (Tosoh Corporation, PS-oligomer kit) was calculated saved

The abbreviations used in the synthesis example are as follows.

BPFE: compound of fluorene-9,9-diyl group (reactant of 9,9-bis(4-hydroxyphenyl)fluorene and epichlorohydrin (epoxy equivalent 250 g/eq))

AA: acrylic acid

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

THPA: tetrahydrophthalic anhydride

TEAB: tetraethylammonium bromide

PGMEA: propylene glycol monomethyl ether acetate

MAA: methacrylic acid

MMA: methyl methacrylate

CHMA: cyclohexyl methacrylate

GMA: glycidyl methacrylate

AIBN: azobisisobutyronitrile

TPP: triphenylphosphine

[Synthesis Example 1]

(Alkali-soluble resin)

BPFE (224.00 g, 0.45 mol), AA (64.57 g, 0.90 mol), PGMEA (43.27 g), TEAB (0.94 g), and 2,6-di -tert-butyl-p-cresol (0.10 g) was injected, and it stirred at 100-105 degreeC for 20 hours and made it react. Next, PGMEA (246.32 g), BPDA (65.90 g, 0.225 mol) and THPA (34.08 g, 0.225 mol) were injected, stirred at 120-125 ° C. under heating for 6 hours, and alkali-soluble resin (i) (solid content) Concentration: 56.5 wt%, weight average molecular weight (Mw): 3600, acid value (in terms of solid content): 99.5 mgKOH/g) was obtained.

[Synthesis Example 2]

((meth)acrylate resin)

MAA (61.98 g, 0.72 mol), MMA (43.25 g, 0.43 mol), CHMA (48.45 g, 0.29 mol), and AIBN (7.09 g) in a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux cooling tube ) and diethylene glycol dimethyl ether (432 g) were injected, and polymerization was carried out by stirring at 80 to 85° C. under a nitrogen stream for 8 hours. In addition, GMA (73.69 g, 0.52 mol), TPP (1.76 g), and 2,6-di-tert-butyl-p-cresol (0.10 g) were injected into the four-necked flask, and at 80 to 85 ° C. It stirred for 16 hours, and obtained (meth)acrylate resin (ii) (solid content concentration: 35.5 mass %, weight average molecular weight (Mw): 21500, acid value (solid content conversion): 50 mgKOH/g).

[Synthesis Example 3]

((meth)acrylate resin)

MAA (61.98 g, 0.72 mol), MMA (43.25 g, 0.43 mol), CHMA (48.45 g, 0.29 mol), and AIBN (21.28 g) in a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux cooling tube ) and diethylene glycol dimethyl ether (458 g) were injected, and polymerization was carried out by stirring at 80 to 85° C. under a nitrogen stream for 8 hours. In addition, GMA (73.69 g, 0.52 mol), TPP (1.76 g), and 2,6-di-tert-butyl-p-cresol (0.10 g) were injected into the four-necked flask, and at 80 to 85 ° C. It stirred for 16 hours, and (meth)acrylate resin (ii)-2 (solid content concentration: 35.6 mass %, weight average molecular weight (Mw): 6500, acid value (solid content conversion): 52 mgKOH/g) was obtained.

[Comparative Synthesis Example 1]

((meth)acrylate resin)

MMA (84.10 g, 0.84 mol), CHMA (141.41 g, 0.84 mol), AIBN (8.28 g), and diethylene glycol dimethyl ether (430 g) in a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux cooling tube ) was injected and stirred at 80 to 85°C under a nitrogen stream for 8 hours to obtain (meth)acrylate resin (ii)-3 (solid content concentration: 35.3% by mass, weight average molecular weight (Mw): 19300).

Examples 1-4 and the photosensitive resin composition of a comparative example were prepared with the compounding quantity (a numerical value is mass %) of Table 1. The compounding components used in the table|surface are as follows.

(i): Alkali-soluble resin obtained in Synthesis Example 1

(ii)-1: (meth)acrylate resin obtained in Synthesis Example 2

(ii)-2: (meth)acrylate resin obtained in Synthesis Example 3

(ii)-3: (meth)acrylate resin obtained in Comparative Synthesis Example 1

(iii): PGMEA dispersion of 20.0 mass % of carbon black and 5.0 mass % of polymer dispersant (solid content 25.0%, average secondary particle size of carbon black 162 nm)

(iv): dipentaerythritol hexaacrylate

(v): Irgacure OXE02 (manufactured by BASF Japan Ltd., “Irgacure” is a registered trademark of the company)

(vi): propylene glycol monomethyl ether acetate

[evaluation]

The following evaluation was performed using the photosensitive resin composition of Examples 1-5 and Comparative Examples 1-2. In addition, all the glass substrates used for preparation of the cured film for evaluation are using the glass substrate which performed the same process.

(Creation of cured film for evaluation of adhesion and linearity)

The photosensitive resin composition shown in Table 1 was previously irradiated with ultraviolet light with a wavelength of 254 nm and an illuminance of 1000 mJ/cm 2 with a low-pressure mercury lamp, and a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as " It is called a glass substrate"), it apply|coated using the spin coater so that the film thickness after a heat hardening process might be set to 1.5 micrometers, it prebaked at 90 degreeC for 1 minute using the hotplate, and produced the cured film. Then, through the negative photomask for pattern formation, the ultraviolet-ray of wavelength 365nm was irradiated and exposed using the high-pressure mercury-vapor lamp of 30 mW/cm<2> of i line|wire illuminance.

After developing the exposed cured film using a 0.15% sodium carbonate aqueous solution at 23° C., the main curing (post-baking) was performed at 230° C. for 30 minutes using a hot air dryer, Examples 1 to 5 and Comparative Examples 1 to 2 A cured film was obtained by

[Adhesiveness evaluation]

(Assessment Methods)

The pattern line width after main hardening (post-baking) was confirmed with the optical microscope "ECLIPSE LV100" (made by NIKON CORPORATION).

(Evaluation standard)

○: L/S (line width/space width) of 20 μm/20 μm or more pattern formed without residue

×: L/S (line width/space width) of less than 20 µm/20 µm is not formed, or the hem or residue of the pattern is conspicuous

[Evaluation of linearity]

(Assessment Methods)

The thin wire pattern linearity of the cured film after main hardening (post-baking) was confirmed with the optical microscope "ECLIPSE LV100".

(Evaluation standard)

○: No peeling or defect of the thin wire pattern on the glass substrate, or unevenness of the end of the pattern

x: Peeling or defect of the thin wire pattern with respect to a glass substrate, and unevenness of the pattern edge part were confirmed

(Creation of cured film for reflectance, optical density, and appearance evaluation)

The photosensitive resin composition shown in Table 1 was apply|coated using the spin coater so that the film thickness after a heat-hardening process might be set to 1.5 micrometers on a glass substrate, and it prebaked at 90 degreeC for 1 minute using a hotplate, and produced the cured film. Next, it exposed by irradiating the ultraviolet-ray with a wavelength of 365 nm using the high-pressure mercury-vapor lamp of 30 mW/cm<2> of i line|wire irradiance without passing through the negative photomask for pattern formation.

[Evaluation of reflectance]

(Assessment Methods)

About the board|substrate with a cured film for reflectance evaluation, using the ultraviolet-visible near-infrared spectrophotometer "UH4150" (made by Hitachi High-Tech Science Corporation), the reflectance of the cured film side (opposite side to a glass substrate) was measured at 2 degrees of incidence angle. .

(Evaluation standard)

(double-circle): The reflectance of the surface of a cured film is 5.5 or less

○: The reflectance of the surface of the cured film exceeds 5.5 and 6.5 or less

(triangle|delta): The reflectance of the surface of a cured film exceeds 6.5 and 7.5 or less

x: The reflectance of the cured film surface exceeds 7.5

After developing the exposed cured film using a 0.15% sodium carbonate aqueous solution at 23° C., the main curing (post-baking) was performed at 230° C. for 30 minutes using a hot air dryer, Examples 1 to 5 and Comparative Examples 1 to 2 A cured film was obtained by

[Optical Concentration Evaluation]

(Assessment Methods)

The optical density (OD) of the cured film produced similarly to the cured film for optical density (OD) evaluation was evaluated using the Macbeth transmission densitometer. Moreover, the film thickness of the cured film formed in the board|substrate was measured, and the value which divided the value of optical density (OD) by the film thickness was made into OD/micrometer.

The optical density (OD) was calculated by the following formula (1).

Optical Density (OD)=-log10T (One)

(T represents transmittance)

[Appearance evaluation]

The nonuniformity of the surface of the cured film of the board|substrate with the cured film for external appearance evaluation, and the presence or absence of a foreign material were observed visually.

(Evaluation standard)

(double-circle): Whitening, color unevenness, or foreign matter was not confirmed at all.

○: Whitening, color unevenness, or foreign matter was observed in an area of 1/4 or less of the surface

Δ: Whitening, color unevenness, or foreign matter was observed in an area of 1/3 or less of the surface

x: Whitening, color unevenness, or foreign matter was observed in the whole

Table 2 shows the evaluation results.

By using the photosensitive resin composition containing alkali-soluble resin (i) of this invention and (meth)acrylate resin (ii) so that it is clear from the result of the said Examples 1-5 and Comparative Examples 1-2, the cured film side It turned out that a reflectance can be reduced and coexistence of high light-shielding property and high-definition pattern formation is possible.

Moreover, it turned out that the photosensitive resin composition in which a reflectance can be reduced by a simple method by using two different types of resin and coexistence of high light-shielding property and high-definition pattern formation is possible is obtained.

(industrial applicability)

ADVANTAGE OF THE INVENTION According to the photosensitive resin composition of this invention, the photosensitive resin composition which has high light-shielding property and low reflectance, and the cured film and color filter using the same can be provided. Moreover, since the cured film of this invention can contribute also to realization of the low reflection-ization of the application|coating surface side of a cured film when it forms on a transparent base material, it is useful for the cured film for sensors, such as various display devices and a solid-state image sensor, etc.

Claims (7)

With respect to the reaction product of an epoxy compound having two or more phenylglycidyl ether groups in the molecule and a monocarboxylic acid containing an unsaturated group, dicarboxylic acid or tricarboxylic acid or their acid monoanhydride, and tetracarboxylic acid or its acid 2 Alkali-soluble resin (i) containing a polymerizable unsaturated group having a weight average molecular weight of 2500 or more obtained by reacting an anhydride;
A (meth)acrylate resin (ii) having a weight average molecular weight of 6000 or more having a carboxyl group and a polymerizable unsaturated group in the side chain is included as a resin component,
A photosensitive resin composition comprising, as an essential component, a light-shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment, or a mixed color organic pigment. The method of claim 1,
The polymerizable unsaturated group-containing alkali-soluble resin (i) has a weight average molecular weight of 2500 or more and 100000 or less,
The (meth)acrylate resin (ii) has a weight average molecular weight of 6000 or more and 1000000 or less,
The mass of said (ii) with respect to the total mass of said (i) and said (ii) is 1-60 mass % of the photosensitive resin composition. 3. The method according to claim 1 or 2,
The photosensitive resin composition in which the said polymerizable unsaturated group containing alkali-soluble resin (i) has a structure represented by General formula (1).

(In formula (1), R ₁ is independently a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is independently a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is independently a hydrogen atom or a methyl group, and X is independently A divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ - , -Si(CH ₃ ) ₂ -, -O-, a fluorene-9,9-diyl group or a single bond represented by the general formula (2), Y is a tetravalent carboxylic acid residue, and Z is independently a hydrogen atom or a substituent represented by the general formula (3), with the proviso that at least one of Z is a substituent represented by the general formula (3), and G is independently a hydrogen atom or a substituent represented by the general formula (4), a is independently a number from 0 to 10, b is independently a number from 0 to 4, and n is an integer with an average value of 1 to 20)

(in formulas (3) and (4), R ₄ and R ₆ are a hydrogen atom or a methyl group, R ₅ and R ₇ are a hydrocarbon group having 2 to 4 carbon atoms, L is a di or trivalent carboxylic acid residue; c, f is the number of 0 or 1, d and e are the number of 0, 1 or 2, and d+e is the number of 1 or 2) 4. The method according to any one of claims 1 to 3,
The said (meth)acrylate resin (ii) is a part of the carboxyl group in the copolymer of (meth)acrylate represented by general formula (5) and (meth)acrylic acid represented by general formula (6) to general formula (7) The photosensitive resin composition which is a (meth)acrylate resin which has a carboxy group and a polymerizable unsaturated group in the side chain obtained by making the (meth)acrylate which has an epoxy group represented by react.

(In formula (5), R ₈ is a hydrogen atom or a methyl group, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ may contain an ethereal oxygen atom or a urethane bond therein)

(in formula (6), R ₁₀ is a hydrogen atom or a methyl group)

(in formula (7), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is a divalent hydrocarbon group having 2 to 10 carbon atoms, and g is the number of 0 or 1.) In the photosensitive resin composition of any one of Claims 1-4,
(iv) a photopolymerizable monomer having at least two polymerizable unsaturated groups;
(v) The photosensitive resin composition which further contains a photoinitiator as an essential component. The cured film formed by hardening|curing the photosensitive resin composition in any one of Claims 1-5. The color filter which has the cured film of Claim 6 as a black matrix.