JP7250591B2 - A method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the same, a cured product obtained by curing the same, and a touch panel containing the cured product as a constituent component and color filters - Google Patents

Description

The present invention comprises a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the same, a cured product obtained by curing the same, and a cured product thereof. It relates to touch panels and color filters that are included as components.

In recent years, with the development of mobile terminals, the number of display devices such as touch panels and liquid crystal panels used outdoors or in vehicles is increasing. In the display device, the outer frame of the touch panel is provided with a light-shielding film to block light leakage around the liquid crystal panel on the back, and the liquid crystal panel is provided with a light-shielding film to suppress light from leaking from the screen during black display, and A black matrix is provided to suppress color mixture between adjacent color resists.

In a display device or the like, in order to suppress light leakage or the like and improve the visibility of the screen of the display device or the like, the black pigment concentration in the light shielding film is increased to increase the light shielding property of the light shielding film (light shielding film (lower the light transmittance of the material). Since the refractive index of the black pigment is higher than the refractive index of the transparent base material and the curable resin, increasing the black pigment concentration in the light-shielding film causes the surface of the transparent base material on which the light-shielding film is formed, And the reflectance when viewed from the side opposite to the side on which the light shielding film is formed becomes high. As a result, reflection at the interface between the light-shielding film formed on the transparent base material and the transparent base material increases, resulting in reflections on the light-shielding film and the difference in reflectance between the colored portion of the color filter and the black matrix boundary. occurs. Moreover, the resin used for the high-definition black matrix forming resist has a high refractive index. Therefore, it is difficult to achieve both light-shielding properties and low reflectivity only by adjusting the density of the black pigment.

Therefore, there is a demand for a photosensitive resin composition for black resists having a low refractive index.

For example, in Patent Document 1, a resin film containing at least two kinds of resins, a colorant, and a photoacid generator is used. A resin film having a peak where the value of A1/A2 is more than 0.1 and 2.5 or less, where A1 is the half-value width of the peak in the spectrum plotting the light intensity, and A2 is the scattering angle of the maximum light intensity of the peak. is disclosed. The resin film is said to be excellent in low reflectivity because a phase separation structure can be formed by two or more kinds of resins.

WO2017/057192

However, as a result of investigation by the present inventors, it was not possible to obtain a refractive index for achieving a desired reflectance with the resin film described in Patent Document 1.

The present invention has been made in view of the above points, and includes a method for producing an unsaturated group-containing alkali-soluble resin capable of obtaining a photosensitive resin composition having excellent developing properties, the unsaturated group-containing alkali-soluble resin, An object of the present invention is to provide a photosensitive resin composition containing the unsaturated group-containing alkali-soluble resin, a cured product obtained by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured product as a component. .

In the method for producing a polymerizable unsaturated group-containing alkali-soluble resin of the present invention, a reaction product of an epoxy compound (a) having a structure represented by formula (1) and an unsaturated group-containing monocarboxylic acid is , a dicarboxylic acid or tricarboxylic acid or their acid unihydride (b), and a tetracarboxylic acid or their acid dianhydride (c) are reacted.

（式（１）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合であり、ａは平均値が０～１０であり、ｂは０～４である。）

(In formula (1), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, and X is a carbon atom which may contain a hetero element therein.) a divalent organic group having a number of 1 to 20, —CO—, —SO ₂ —, —Si(CH ₃ ) ₂ —, —O—, or a single bond, a having an average value of 0 to 10, and b is 0 to 4.)

The polymerizable unsaturated group-containing alkali-soluble resin of the present invention has a structure represented by Formula (2).

（式（２）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｒ_３は水素原子またはメチル基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合であり、Ｙは４価のカルボン酸残基であり、Ｚは水素原子または式（３）で示される置換基であり、ただし、Ｚの少なくとも１つは式（３）で表される置換基であり、Ｇは水素原子または式（４）で表される置換基であり、ａは平均値が０～１０であり、ｂは０～４であり、ｎは平均値が１～２０である。）

(In formula (2), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and X is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom inside, —CO—, —SO ₂ —, —Si(CH ₃ ) ₂ —, —O— or a single bond; is a tetravalent carboxylic acid residue, Z is a hydrogen atom or a substituent represented by formula (3), provided that at least one of Z is a substituent represented by formula (3), G is a hydrogen atom or a substituent represented by formula (4), a has an average value of 0 to 10, b has an average value of 0 to 4, and n has an average value of 1 to 20.)

（式（３）、（４）中、Ｒ_４は水素原子またはメチル基であり、Ｒ_５は炭素数２～４の炭化水素基であり、Ｌは２または３価のカルボン酸残基であり、ｃは０または１であり、ｄおよびｅは０、１または２であり、ｄ＋ｅは１または２である。）

(In formulas (3) and (4), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrocarbon group having 2 to 4 carbon atoms, and L is a divalent or trivalent carboxylic acid residue. , c is 0 or 1, d and e are 0, 1 or 2, and d+e is 1 or 2.)

The photosensitive resin composition of the present invention contains (A) a polymerizable unsaturated group-containing alkali-soluble resin represented by formula (2) and (B) a photopolymerization initiator.

The cured product of the present invention is obtained by curing the photosensitive resin composition obtained by patterning the photosensitive resin composition by photolithography.

The touch panel of the present invention contains the cured product as a constituent.

The color filter of the present invention contains the cured product as a constituent.

According to the present invention, there is provided a method for producing an unsaturated group-containing alkali-soluble resin capable of obtaining a photosensitive resin composition having excellent development properties, the unsaturated group-containing alkali-soluble resin, and the unsaturated group-containing alkali-soluble resin. It is possible to provide a photosensitive resin composition containing the composition, a cured product obtained by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured product as a component.

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

The alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by the formula (2) of the present invention is an epoxy compound (a) having two epoxy groups in one molecule and an unsaturated group It is obtained by reacting a dicarboxylic acid or tricarboxylic acid or their acid dianhydride (b) and a tetracarboxylic acid or their acid dianhydride (c) with a reactant with a contained monocarboxylic acid. In addition, the polymerizable unsaturated group-containing alkali-soluble resin contains several oxyalkylene groups and an epoxy compound (a-1) having two cycloalkyl groups in one molecule as an epoxy compound serving as a raw material. It is characterized by using

（式（２）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｒ_３は水素原子またはメチル基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合であり、Ｙは４価のカルボン酸残基であり、Ｚは水素原子または式（３）で示される置換基であり、ただし、Ｚの少なくとも１つは式（３）で表される置換基であり、Ｇは水素原子または式（４）で表される置換基であり、ａは平均値が０～１０であり、ｂは０～４であり、ｎは平均値が１～２０である。）

(In formula (2), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and X is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom inside, —CO—, —SO ₂ —, —Si(CH ₃ ) ₂ —, —O— or a single bond; is a tetravalent carboxylic acid residue, Z is a hydrogen atom or a substituent represented by formula (3), provided that at least one of Z is a substituent represented by formula (3), G is a hydrogen atom or a substituent represented by formula (4), a has an average value of 0 to 10, b has an average value of 0 to 4, and n has an average value of 1 to 20.)

（式（３）、（４）中、Ｒ_４は水素原子またはメチル基であり、Ｒ_５は炭素数２～４の炭化水素基であり、Ｌは２または３価のカルボン酸残基であり、ｃは０または１であり、ｄおよびｅは０、１または２であり、ｄ＋ｅは１または２である。）

(In formulas (3) and (4), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrocarbon group having 2 to 4 carbon atoms, and L is a divalent or trivalent carboxylic acid residue. , c is 0 or 1, d and e are 0, 1 or 2, and d+e is 1 or 2.)

A method for producing an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter also simply referred to as "polymerizable unsaturated group-containing alkali-soluble resin") represented by the following formula (2): I will explain in detail.

First, an unsaturated group is added to an epoxy compound (a-1) having two epoxycycloalkyl groups in one molecule represented by formula (1) (hereinafter also simply referred to as "epoxy compound (a-1)"). The contained monocarboxylic acid (for example, (meth)acrylic acid) is reacted to obtain an epoxy (meth)acrylate.

（式（１）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合である。ただし、ａは平均値が０～１０であり、ｂは０～４である。）

(In formula (1), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, and X is a carbon atom which may contain a hetero element therein.) a divalent organic group of numbers 1 to 20, -CO-, -SO ₂ -, -Si(CH ₃ ) ₂ -, -O- or a single bond, provided that a has an average value of 0 to 10; , b is 0 to 4.)

Examples of the unsaturated group-containing monocarboxylic acid compounds include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with succinic anhydride, maleic anhydride, phthalic anhydride and the like. and so on.

A known method can be used for the reaction between the epoxy compound (a-1) and (meth)acrylic acid. For example, Japanese Patent Laid-Open No. 4-355450 discloses a diol compound containing a polymerizable unsaturated group by using about 2 mol of (meth)acrylic acid per 1 mol of an epoxy compound having two epoxy groups. is obtained. In the present invention, the compound obtained by the above reaction is a diol compound containing a polymerizable unsaturated group, which is the diol (d) represented by formula (6).

（式（６）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｒ_３は水素原子またはメチル基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合である。ただし、ａは平均値が０～１０であり、ｂは０～４である。）

(In formula (6), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and X is It is a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside, -CO-, -SO ₂ -, -Si(CH ₃ ) ₂ -, -O- or a single bond. , a has an average value of 0 to 10, and b has an average value of 0 to 4.)

X in the epoxy compound (a-1) represented by the formula (1) is a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, -CO-, -SO ₂ -, —Si(CH ₃ ) ₂ —, —O— or a single bond. Examples of the divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside include a divalent hydrocarbon group, a 2 having a carboxy group at one or two ends of the hydrocarbon group. Valence groups and the like are included. The hydrocarbon group may have an ether oxygen atom or an ester bond inside.

Examples of divalent hydrocarbon groups include linear or branched chains such as methylene group, ethylene group, propylene group, isopropylidene group, sec-butylene group, methylisobutylene group, hexylene group, decylene group and dodecylene group. including hydrocarbon groups with Examples of divalent groups having an ester group at the end of a hydrocarbon group include divalent organic groups represented by formulas (7) to (10).

（式（７）中、ｇは１～２０の整数である。）

(In formula (7), g is an integer of 1 to 20.)

（式（８）中、ｈは２～２０の整数であり、ｉは０～１０の整数である。）

(In formula (8), h is an integer of 2 to 20, and i is an integer of 0 to 10.)

（式（９）中、ｊは１～２０の整数である。）

(In formula (9), j is an integer of 1 to 20.)

（式（１０）中、ｋは０～１８の整数であり、ｌは１～１０の整数である。）

(In formula (10), k is an integer of 0 to 18 and l is an integer of 1 to 10.)

Two cyclohexane rings in the above formula (1) are bonded via X. The cyclohexane ring is bonded to oxygen atoms at the 1- and 2-positions, respectively, and to X at the 4- or 5-position. The bonding position of X may be either 4-position or 5-position, and may be randomly bonded at 4-position and 5-position.

Specific examples of the epoxy compound (a-1) represented by formula (1) include epoxy compounds represented by formulas (11) to (17).

（式（１１）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０である。）

(In formula (11), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, and a has an average value of 0 to 10.)

（式（１２）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０である。）

(In formula (12), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, and a has an average value of 0 to 10.)

（式（１３）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０である。）

(In formula (13), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, and a has an average value of 0 to 10.)

（式（１４）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０であり、ｇは１～２０の整数である。）

(In formula (14), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, a has an average value of 0 to 10, and g is an integer of 1 to 20.)

（式（１５）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０であり、ｈは２～２０の整数であり、ｉは０～１０の整数である。）

(In formula (15), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, a has an average value of 0 to 10, h is an integer of 2 to 20, and i is an integer of 0 to 10. is.)

（式（１６）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０であり、ｊは１～２０の整数である。）

(In formula (16), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, a has an average value of 0 to 10, and j is an integer of 1 to 20.)

（式（１７）中、Ｒ_１は炭素数２～４の炭化水素基であり、ａは平均値が０～１０であり、ｋは０～１８の整数であり、ｌは１～１０の整数である。）

(In formula (17), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, a has an average value of 0 to 10, k is an integer of 0 to 18, and l is an integer of 1 to 10. is.)

Synthesis of diol (d) represented by general formula (6), subsequent addition reaction of polyvalent carboxylic acid or its anhydride, monofunctional epoxy having polymerizable unsaturated group reactive with carboxy group In the production of the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (2) by reacting compounds and the like, the reaction is usually carried out in a solvent using a catalyst if necessary.

Examples of solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate; Ketone solvents such as diisobutyl ketone and the like are included. Although there are no particular restrictions on the reaction conditions such as the solvent and catalyst used, it is preferable to use, as the reaction solvent, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature.

Further, it is preferable to use a catalyst in the reaction between the carboxyl group and the epoxy group. ,6-dimethoxyphenyl)phosphine and other phosphines.

Next, the diol (d) represented by the formula (6) obtained by the reaction of the epoxy compound and (meth)acrylic acid is reacted with the acid components (b) and (c) to obtain the formula (18). It is possible to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter referred to as "alkali-soluble resin represented by formula (18)").

（式（１８）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｒ_３は水素原子またはメチル基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合であり、Ｙは４価のカルボン酸残基であり、Ｚ’は水素原子または式（１９）で表される置換基である。ただし、ａは平均値が０～１０であり、ｂは０～４であり、ｎは平均値が１～２０である。）

(In formula (18), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and X is a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element therein, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ , -Si(CH ₃ ) ₂ -, -O - or a single bond, Y is a tetravalent carboxylic acid residue, Z' is a hydrogen atom or a substituent represented by formula (19), provided that a has an average value of 0 to 10 , b is 0 to 4, and n has an average value of 1 to 20.)

（式（１９）中、Ｌは２または３価のカルボン酸残基であり、ｒは１または２である。）

(In formula (19), L is a divalent or trivalent carboxylic acid residue, and r is 1 or 2.)

The acid component used to synthesize the alkali-soluble resin represented by formula (18) is a polyvalent acid component capable of reacting with hydroxyl groups in the diol (d) molecule represented by formula (6). , a dicarboxylic acid or tricarboxylic acid or their monoanhydride (b) and a tetracarboxylic acid or their dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may contain a bond containing a heteroatom such as —O—, —S—, or a carbonyl group.

Dicarboxylic or tricarboxylic acids or their monoanhydrides (b) include chain hydrocarbon dicarboxylic or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic or tricarboxylic acids, aromatic hydrocarbon dicarboxylic or tricarboxylic acids, or Their acid monoanhydrides and the like can be used.

Examples of monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, Acid unianhydrides such as tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid and diglycolic acid, and dicarboxylic or tricarboxylic acid unianhydrides introduced with optional substituents are included. Examples of acid unianhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid unianhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and any dicarboxylic acid or tricarboxylic acid monoanhydride into which a substituent of is introduced. In addition, examples of acid unihydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid unihydrides such as phthalic acid, isophthalic acid and trimellitic acid, and dicarboxylic acids or tricarboxylic acids into which optional substituents have been introduced. Contains monoanhydride.

Among the monoanhydrides of dicarboxylic or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid are preferred, and succinic acid, itaconic acid, tetrahydrophthalic acid. is more preferable. Moreover, it is preferable to use those acid monoanhydrides in dicarboxylic acid or tricarboxylic acid. The acid 1 anhydrides of dicarboxylic acids or tricarboxylic acids described above may be used alone or in combination of two or more thereof.

In addition, as the tetracarboxylic acid or its acid dianhydride (c), chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or acid dianhydride thereof, etc. can be used.

Examples of chain hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain chains into which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. Hydrocarbon tetracarboxylic acids and the like are included. Examples of the alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, chain hydrocarbon groups, Alicyclic tetracarboxylic acids into which substituents such as saturated hydrocarbon groups have been introduced are included. Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid and the like.

Among tetracarboxylic acids or acid dianhydrides thereof, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and diphenylethertetracarboxylic acid are preferable, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferable. Moreover, in tetracarboxylic acid or its acid dianhydride, it is preferable to use the acid dianhydride. In addition, the tetracarboxylic acid or its acid dianhydride mentioned above may be used individually by 1 type, and may use 2 or more types together.

The reaction between the diol (d) represented by formula (6) and the acid components (b) and (c) is not particularly limited, and known methods can be employed. For example, JP-A-9-325494 describes a method of reacting epoxy (meth)acrylate and tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

Here, epoxy (meth)acrylate (d), dicarboxylic acid or tricarboxylic acid or their acid unihydride (b), tetracarboxylic dianhydride (c) so that the terminal of the compound is a carboxy group It is preferable to carry out the reaction so that the molar ratio (d):(b):(c)=1:0.01-1.0:0.2-1.0.

For example, when using (b) an acid dianhydride and (c) an acid dianhydride, the amount of the acid component with respect to the diol compound containing a polymerizable unsaturated group (epoxy (meth) acrylate) (d) [( It is preferable to carry out the reaction so that the molar ratio [(d)/[(b)/2+(c)]] of b)/2+(c)] is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the diol compound containing an unreacted polymerizable unsaturated group is not increased, so the aging stability of the alkali-soluble resin composition is enhanced. be able to. On the other hand, when the molar ratio exceeds 0.5, the end of the alkali-soluble resin represented by formula (2) does not become an acid anhydride, so the content of unreacted acid dianhydride is suppressed from increasing. Therefore, the stability over time of the alkali-soluble resin composition can be enhanced. For the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the above formula (2), the molar ratio of each component of (d), (b) and (c) is arbitrarily within the above range. can be changed.

The alkali-soluble resin obtained by the reaction of the diol (d) represented by the formula (6) with the acid components (b) and (c) is represented by the formula (18), wherein all G in the formula (2) are hydrogen atoms. ). In this embodiment, the unsaturated group-containing epoxy compound represented by formula (20) is reacted with the carboxy group of formula (18). A known method can be used for the reaction of the unsaturated group-containing epoxy compound represented by Formula (18) and Formula (20). Methods for making acrylates can be used. Thereby, the polymerizable unsaturated group-containing alkali-soluble resin represented by formula (2) can be obtained. Furthermore, the hydroxyl group of the polymerizable unsaturated group-containing alkali-soluble resin may be reacted with a dicarboxylic acid, tricarboxylic acid, or acid unihydride thereof.

（式（２０）中、Ｒ_４は水素原子またはメチル基であり、Ｒ_５は炭素数２～４の炭化水素基であり、ｃは０または１である。）

(In formula (20), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrocarbon group having 2 to 4 carbon atoms, and c is 0 or 1.)

The molar ratio of the epoxy group of the unsaturated group-containing epoxy compound represented by formula (20) to the carboxy group of formula (18) is determined by the photoreaction sensitivity of the alkali-soluble resin represented by formula (2). It can be arbitrarily changed for the purpose of adjusting the amount of heavy bonds) and acid value. Further, if the number of moles of the formula (20) is 90% or less of the total number of moles of the number of moles of the component (b) and twice the number of moles of the component (c), alkali developability can be imparted. and can be used for a photosensitive resin composition having photopatternability. Further, when the effect of improving the sensitivity of the photoreaction is to be imparted, it is necessary to make it 10% or more. The acid value of the alkali-soluble resin represented by formula (2) to be used is preferably 20-180, more preferably 30-120.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) of the alkali-soluble resin represented by the formula (2) of the present invention is usually 1000 to 100000. and preferably from 2000 to 20000. When the weight-average molecular weight is 1,000 or more, it is possible to suppress deterioration of pattern adhesion during alkali development. Moreover, when the weight average molecular weight is less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and alkali development does not take too much time. Gel permeation chromatography (GPC) measurement of the alkali-soluble resin can be performed using "HLC-8220GPC" (manufactured by Tosoh Corporation).

Next, the unsaturated group-containing alkali-soluble resin of formula (21) (hereinafter referred to as "alkali-soluble resin represented by formula (21)") will be described. The unsaturated group-containing alkali-soluble resin represented by formula (21) is a mixture with the polymerizable unsaturated group-containing alkali-soluble resin represented by formulas (2) and (5).

The method for producing an alkali-soluble resin represented by formula (21) can be carried out in the method for producing an alkali-soluble resin represented by formula (2), but in the first step, two epoxy When the epoxy compound (a) having a group and the unsaturated group-containing monocarboxylic acid are reacted, the epoxy compound (a-1) and the epoxy resin (a-2) derived from bisphenols are used as components (a). used together.

（式（２１）中、Ｙは４価のカルボン酸残基であり、Ｚは水素原子または式（３）で示される置換基である。ただし、Ｚの少なくとも１つは式（３）で表される置換基であり、Ｇは水素原子または式（４）で表される置換基であり、ＷおよびＷ’は、後述する式（２４）で表される２価の有機基Ｐおよび／または後述する式（２５）で表される２価の有機基Ｑで表される２価の有機基を示す。ただし、ｆは平均値が１～２０である。）

(In formula (21), Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or a substituent represented by formula (3). However, at least one of Z is represented by formula (3) G is a hydrogen atom or a substituent represented by formula (4), and W and W′ are divalent organic groups P represented by formula (24) described later and / or represents a divalent organic group represented by a divalent organic group Q represented by formula (25) described later, provided that f has an average value of 1 to 20.)

Epoxy resin (a-2) derived from bisphenols is represented by formula (22).

（式（２２）中、Ｒ_６、Ｒ_７、Ｒ_８、およびＲ_９は、それぞれ独立に水素原子、炭素数１～５のアルキル基、ハロゲン原子またはフェニル基であり、Ｒ_１０は炭素数２～４の炭化水素基である。また、Ｍは－ＣＯ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、－Ｓｉ（ＣＨ_３）_２－、－ＣＨ_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、フルオレン－９，９－ジイル基または単結合を示し、ｄは０～１０の平均値（但し０は含まず）を示す。）

(In formula (22), R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₁₀ is a is a hydrocarbon group of -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) represents _{a 2-} , -O-, fluorene-9,9-diyl group or a single bond, and d represents an average value of 0 to 10 (excluding 0).)

The above component (a-2) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. Since this reaction generally involves oligomerization of the diglycidyl ether compound, an oligomer as shown in formula (21) is formed, but each molecule has a different value of m, and as described above, the average value of m is is more than 0 and 10 or less, preferably 0.05 or more and 5 or less.

Examples of bisphenols used as starting materials for component (a-2) above 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-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-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-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl) ) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl ) fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)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 and the like, and derivatives thereof. Among the above bisphenols, 2,2-bis(4-hydroxyphenyl)propane is preferred. The bisphenols used as raw materials for component (a-2) may be used singly or in combination of two or more.

In the first step of producing the compound represented by formula (21), (a-1) component and (a-2) component are combined with (a-2 ) component is added so as to be 10 to 100 parts by mass (preferably 30 to 60 parts by mass), and the total number of moles of epoxy compounds (a-1) and (a-2) having two epoxy groups Epoxy (meth)acrylate (d') is obtained by reacting twice as much (meth)acrylic acid. The reaction is preferably carried out catalyzed in a solvent, as described above. In addition, epoxy acrylate obtained by reacting 2 mol (meth)acrylic acid with respect to 1 mol of (a-1) and separately 2 mol of (meth)acrylic acid with respect to 1 mol of (a-2) Epoxy (meth)acrylate (d') may be obtained by mixing with reacted epoxy acrylate.

In the second step, the epoxy (meth)acrylate (d') obtained in the first step is combined with a dicarboxylic acid or tricarboxylic acid or their unianhydride (b) and a tetracarboxylic acid or their dianhydride (c). to obtain an alkali-soluble resin of formula (23) having a carboxyl group and a polymerizable unsaturated group in one molecule (hereinafter referred to as "alkali-soluble resin of formula (22)").

（式（２３）中、Ｙは４価のカルボン酸残基であり、Ｚ’は水素原子または式（１９）で表される置換基であり、ＷおよびＷ’は、後述する式（２４）で表される２価の有機基Ｐおよび／または後述する式（２５）で表される２価の有機基Ｑで表される２価の有機基を示す。ただし、ｆは平均値が１～２０である。）

(In formula (23), Y is a tetravalent carboxylic acid residue, Z' is a hydrogen atom or a substituent represented by formula (19), and W and W' are formula (24) described later. Represents a divalent organic group P represented by and / or a divalent organic group represented by a divalent organic group Q represented by the formula (25) described later, provided that f has an average value of 1 to 20.)

Here, f is an integer in each molecule of the alkali-soluble resin represented by formula (23), and the number of units represented by P and Q in the molecule is fP and fQ, respectively. f=fP+fQ. When W'=P, fQ≠0; when W'=Q, fP≠0; when W' is P, W always includes Q; means that W always contains P.

（式（２４）中、Ｒ_１は炭素数２～４の炭化水素基であり、Ｒ_２は炭素数１～３の炭化水素基であり、Ｒ_３は水素原子またはメチル基であり、Ｘは内部にヘテロ元素を含んでいてもよい炭素数１～２０の２価の有機基、－ＣＯ－、－ＳＯ_２－、－Ｓｉ（ＣＨ_３）_２－、－Ｏ－または単結合である。ただし、ａは平均値が０～１０であり、ｂは０～４である。）

(In formula (24), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and X is It is a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside, -CO-, -SO ₂ -, -Si(CH ₃ ) ₂ -, -O- or a single bond. , a has an average value of 0 to 10, and b has an average value of 0 to 4.)

（式（２５）中、Ｒ_６、Ｒ_７、Ｒ_８、およびＲ_９は、独立に水素原子、炭素数１～５のアルキル基、ハロゲン原子又はフェニル基であり、Ｒ_１０は炭素数２～４の炭化水素基であり、Ｒ_１１は水素原子またはメチル基である。また、Ｍは－ＣＯ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、－Ｓｉ（ＣＨ_３）_２－、－ＣＨ_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、９，９－フルオレニレン基または直結合である。ただし、ｄは平均値が０～１０である。）

(In formula (25), R ₆ , R ₇ , R ₈ and R ₉ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₁₀ is a 4, R ₁₁ is a hydrogen atom or a methyl group, and M is —CO—, —SO ₂ —, —C(CF ₃ ) ₂ —, —Si(CH ₃ ) ₂ —, —CH ₂ —, —C(CH ₃ ) ₂ —, —O—, 9,9-fluorenylene group or direct bond, provided that d has an average value of 0 to 10.)

In the second step, the type, addition amount, reaction conditions, etc. of the acid components (b) and (c) used in producing the alkali-soluble resin of formula (23) are as follows: It is the same as when manufacturing resin.

In the third step, the unsaturated group-containing epoxy compound represented by Formula (20) is reacted with the alkali-soluble resin represented by Formula (23). For this reaction, the alkali-soluble resin represented by formula (23) is converted to formula (21) in the same manner as in the case of producing the alkali-soluble resin represented by formula (2) from the alkali-soluble resin represented by formula (18). An alkali-soluble resin represented by is obtained. If the number of moles of the formula (20) is 90% or less of the total number of moles, which is twice the number of moles of the component (b) and the number of moles of the component (c), alkali developability can be imparted. , can be used in a photosensitive resin composition having photopatternability. Further, when the effect of improving the sensitivity of the photoreaction is to be imparted, it is necessary to make it 10% or more.

The weight average molecular weight of the alkali-soluble resin represented by formula (21) is preferably 1,000 to 100,000, preferably 2,000 to 30,000. The acid value of the alkali-soluble resin of formula (21) is preferably 20-180, preferably 30-120.

Next, the photosensitive resin composition using the alkali-soluble resin represented by the formula (2) and/or the alkali-soluble resin represented by the formula (21) of the present invention will be described. Although the preferred photosensitive resin composition component ratio differs depending on whether (E) dispersoid is included or not, the case of (E) not including dispersoid will be described first.

(A) an alkali-soluble resin represented by formula (2) and / or formula (21), (B) a photopolymerization initiator is added, and a solution viscosity suitable for forming a coating film using a solvent to obtain a photosensitive resin composition.

In the photosensitive resin composition of the present invention, the component (A) is 1 to 55% by mass in the solid content of the photosensitive resin composition, and the component (C) is 100 parts by mass of the component (A). is 0 to 100 parts by mass, component (B) is 0.1 to 40 parts by mass per 100 parts by mass of the total amount of component (A) and component (C), and component (E) is 1 to 95% by mass.

Further, the component (A) includes a polymerizable unsaturated group-containing alkali-soluble resin represented by formula (2) and a resin represented by formula (5), and is represented by formula (2) The ratio between the mass m _A-1 of the polymerizable unsaturated group-containing alkali-soluble resin and the mass m _A-2 of the resin represented by formula (5) is m _A-1 /m _A-2 =75/25. ~25/75.

（式（５）中、Ｒ_６、Ｒ_７、Ｒ_８、およびＲ_９は、独立に水素原子、炭素数１～５のアルキル基、ハロゲン原子またはフェニル基であり、Ｒ_１０は炭素数２～４の炭化水素基であり、Ｒ_１１は水素原子またはメチル基である。また、Ｍは－ＣＯ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、－Ｓｉ（ＣＨ_３）_２－、－ＣＨ_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、９，９－フルオレニレン基または直結合であり、Ｙは４価のカルボン酸残基であり、Ｚは水素原子または式（３）で表される置換基である。ただし、Ｚの少なくとも１つは式（３）で表される置換基であり、Ｇは水素原子または式（４）で表される置換基を示す。ｄは平均値が０～１０であり、ｍは平均値が１～２０である。）

(In formula (5), R ₆ , R ₇ , R ₈ and R ₉ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₁₀ is a 4, R ₁₁ is a hydrogen atom or a methyl group, and M is —CO—, —SO ₂ —, —C(CF ₃ ) ₂ —, —Si(CH ₃ ) ₂ —, —CH ₂ —, —C(CH ₃ ) ₂ —, —O—, 9,9-fluorenylene group or a direct bond, Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or the ), wherein at least one of Z is a substituent represented by formula (3), and G represents a hydrogen atom or a substituent represented by formula (4).d has an average value of 0 to 10, and m has an average value of 1 to 20.)

Examples of the (B) photopolymerization initiator in the photosensitive resin composition of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, Acetophenones such as p-tert-butylacetophenone; Benzophenones such as benzophenone, 2-chlorobenzophenone and p,p'-bisdimethylaminobenzophenone; Benzoins such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether Ethers; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)- Biimidazole compounds such as 4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 2-trichloromethyl-5- Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)- Halomethyldiazole compounds such as 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-trimethoxy styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. -s-triazine compounds; 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)butane-1 O-acyl oxime compounds such as -one oxime-O-acetate; sulfur compounds such as; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone and other anthraquinones; azobisisobutylnitrile, benzoyl peroxide, cumene peroxide and other organic peroxides thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. In addition, these photoinitiators may be used individually by 1 type, and may use 2 or more types together.

In particular, O-acyloxime compounds (including ketoximes) are preferably used when a photosensitive resin composition containing a dispersoid such as a coloring agent, which will be described later, is used. A specific group of compounds includes O-acyloxime-based photopolymerization initiators represented by formula (26) or (27). Among them, when using a colorant at a high pigment concentration and when forming a light-shielding film pattern, an O-acyloxime-based photopolymerization initiator having a molar absorption coefficient at 365 nm of 10000 L/mol cm or more should be used. is preferred. In addition, the "photopolymerization initiator" as used in the field of this invention is used in the meaning containing a sensitizer.

（式（２６）中、Ｒ_１２、Ｒ_１３は、それぞれ独立にＣ１～Ｃ１５のアルキル基、Ｃ６～Ｃ１８のアリール基、Ｃ７～Ｃ２０のアリールアルキル基またはＣ４～Ｃ１２の複素環基を表し、Ｒ_１４はＣ１～Ｃ１５のアルキル基、Ｃ６～Ｃ１８のアリール基、Ｃ７～Ｃ２０のアリールアルキル基を表す。ここで、アルキル基およびアリール基はＣ１～Ｃ１０のアルキル基、Ｃ１～Ｃ１０のアルコキシ基、Ｃ１～Ｃ１０のアルカノイル基、ハロゲンで置換されていてもよく、アルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合を含んでいてもよい。また、アルキル基は直鎖、分岐、または環状のいずれのアルキル基であってもよい。）

(In formula (26), R ₁₂ and R ₁₃ each 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 ₁₄ represents a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group, wherein the alkyl group and the aryl group are a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1 ~C10 alkanoyl group, optionally substituted with halogen, alkylene moiety may contain unsaturated bond, ether bond, thioether bond, ester bond, and alkyl group is linear, branched or cyclic may be any alkyl group.)

（式（２７）中、Ｒ_１５およびＲ_１６はそれぞれ独立に、炭素数１～１０の直鎖状もしくは分岐状のアルキル基であるか、炭素数４～１０のシクロアルキル基、シクロアルキルアルキル基もしくはアルキルシクロアルキル基であるか、または炭素数１～６のアルキル基で置換されていてもよいフェニル基である。Ｒ_１７は独立して炭素数２～１０の直鎖状もしくは分岐状のアルキル基またはアルケニル基であり、当該アルキル基またはアルケニル基中の－ＣＨ_２－基の一部が－Ｏ－基で置換されていてもよい。さらに、これらＲ_１５～Ｒ_１７の基中の水素原子の一部がハロゲン原子で置換されていてもよい。）

(In formula (27), R ₁₅ and R ₁₆ are each 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 a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms, and R ₁₇ is independently a linear or branched alkyl group having 2 to 10 carbon atoms. or an alkenyl group, some of the —CH ₂ — groups in the alkyl or alkenyl group may be substituted with —O— groups, and hydrogen atoms in these groups R ₁₅ to R ₁₇ may be partially substituted with halogen atoms.)

Examples of solvents contained in the photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone. , N-methyl-2-pyrrolidone and other ketones; toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol , diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers; 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, and propylene glycol monoethyl ether acetate. By dissolving and mixing these alone or in combination of two or more, a uniform solution composition can be obtained. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 60 to 90% by mass in the photosensitive resin composition solution.

In the photosensitive resin composition of the present invention, in addition to (A) an alkali-soluble resin having a specific structure and (B) a photopolymerization initiator as described above, if necessary, (C) at least one ethylenic A photopolymerizable monomer having an unsaturated bond, or (D) an epoxy compound or epoxy resin containing two or more epoxy groups can be added, and these components (C) and (D) can be used in combination. can be done.

(C) Examples of photopolymerizable monomers include (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; 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)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa( (Meth)acrylic acid esters such as meth)acrylates; dendrimer-type polyfunctional acrylates are included. These photopolymerizable monomers may be used alone or in combination of two or more.

The photopolymerizable monomer having at least one ethylenically unsaturated bond is a photopolymerizable monomer having two or more photopolymerizable groups and capable of cross-linking the molecules of the unsaturated group-containing alkali-soluble resin. is preferred. In addition, (C) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxy group.

(D) Examples of epoxy resins or epoxy compounds having two or more epoxy groups include 3,3′,5,5′-tetramethyl-4,4′-biphenol type epoxy resins, bisphenol A type epoxy resins, Bisphenol fluorene type epoxy resin, phenol novolak type epoxy resin, 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexene carboxylate, 2,2-bis(hydroxymethyl)-1-butanol 1,2- Epoxy-4-(2-oxiranyl)cyclohexane adducts, epoxy silicone resins and the like are included. These compounds may be used alone or in combination.

In a photosensitive resin composition that does not contain component (E), the preferred blending ratio when using component (C) and/or component (D) is component (C) per 100 parts by mass of component (A). It is preferably 0 to 100 parts by mass, and when component (D) is used, it is preferably 5 to 30 parts by mass per 100 parts by mass of the total amount of components (A) and (C). The purpose of using component (C) is to improve the sensitivity of the photocuring reaction of the photosensitive resin composition, and the sensitivity increases as the amount added increases. However, if it is added in an amount larger than that of the component (A), the alkali solubility of the photosensitive resin composition becomes insufficient, resulting in a decrease in developability. On the other hand, the purpose of adding the component (D) is to improve the physical properties of the photo-patterned film by heat curing following the photo-curing reaction and alkali development. When used, the surface hardness and the like can be improved by cross-linking the resin component. However, if the amount is too large relative to the photocurable component, the photopatternability will be adversely affected.

The above photosensitive resin composition can also be used as (E) a photosensitive resin composition to which a dispersoid is added. A preferable blending ratio when used as a photosensitive resin composition containing dispersoids is that the content of component (A) in the solid content including the component that solidifies by photocuring is 1 to 55% by mass, and (C ) component is 0 to 100 parts by mass per 100 parts by mass of component (A), and component (B) is 0.1 to 40 parts by mass per 100 parts by mass of the total amount of components (A) and (C). parts by mass, (E) is 1 to 95% by mass of the solid content, and when component (D) is used, 5 to 30 mass parts per 100 parts by mass of the total amount of components (A) and (C) It is preferable that it is a part.

The (E) dispersoid that can be used in the present invention is dispersed with an average particle size of 1 to 1000 nm (average particle size measured by a laser diffraction/scattering method particle size distribution analyzer or a dynamic light scattering method particle size distribution analyzer). Known dispersoids that have been used in conventional photosensitive resin compositions can be used without any particular restrictions, as long as they are the same.

Here, examples of black pigments include perylene black, cyanine black, aniline black, carbon black, titanium black and the like. Examples of mixed color organic pigments include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketo Pigments in which at least two colors selected from organic pigments such as pyrrolopyrrole pigments and thioindigo pigments are mixed are included. Examples of white pigments include titanium oxide pigments, composite oxide pigments; inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate and barium sulfate. These (E) components may be used alone or in combination of two or more depending on the intended function of the photosensitive resin composition.

In addition, the dispersoid (E) can be used alone or in combination according to the intended function of the photosensitive resin composition. For example, carbon black, titanium black, black organic pigments, etc. can be used as light-shielding resists used for manufacturing the black matrix of color filters, and red and orange resists can be used as coloring resists used for manufacturing pixels of color filters. , yellow, green, blue, purple organic pigments, etc. can be used, and organic pigments, inorganic pigments, inorganic fillers, etc. can be used as the solder resist used for manufacturing the insulating film of the printed wiring board, and the touch panel Carbon black, titanium black, black organic pigments, white pigments, etc. can be used as decorative resists used for the design of the front glass, and transparent fillers such as silica can be used as transparent resists with high hardness and high durability. , can be appropriately selected and used.

Examples of organic pigments that can be used as the component (E) include, but are not limited to, those with the following numbers in the name of the color index.
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.

The mixing ratio of the component (E) colorant can be arbitrarily determined according to the desired degree of light blocking, but it is preferably 1 to 80% by mass based on the solid components in the photosensitive resin composition.

The component (E) is usually mixed with other ingredients as a colorant dispersion dispersed in a solvent, and in this case, a dispersant (component E') can be added. As the dispersant, known compounds used for dispersing pigments (colorants) (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. .

Examples of dispersants include cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative dispersants (dispersing aids). In particular, the dispersant has a cationic functional group such as an imidazolyl group, pyrrolyl group, pyridyl group, primary, secondary or tertiary amino group as an adsorption point to the colorant, and has an amine value of 1 to 100 mgKOH/ g. It is preferably a cationic polymeric dispersant having a number average molecular weight in the range of 1,000 to 100,000. The blending amount of the dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the colorant. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those that do not have dispersion-promoting properties are not treated as dispersants. However, it does not limit its use for the purpose of stabilizing the dispersion.

As described above, the photosensitive resin composition of the present invention can be used as a photosensitive resin composition to which various (E) dispersoids are added, for applications requiring light resistance, for example.

In addition, in the present invention, if necessary, other resin components that are polymerized or cured by light or heat may be used together. Other resin components include, for example, a novolac epoxy resin derived from novolaks such as phenol novolak and cresol novolak (an alkali-soluble resin obtained by reacting methacrylic acid and an acid anhydride, (meth)acrylic acid and Alkali-soluble resins obtained by reacting epoxy group-containing (meth)acrylates with carboxy groups in copolymers with (meth)acrylic acid esters can be used.

The photosensitive resin composition of the present invention may optionally contain curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, leveling agents, antifoaming agents, surfactants, coupling agents and the like. Additives can be added. The curing agent includes amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to curing of the resin are included. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

The cured product of the present invention is formed by photolithography using the photosensitive resin composition of the present invention. As the manufacturing process, first, a photosensitive resin composition solution is applied to the surface of the substrate, and then the solvent is dried (pre-baking). A method of curing the exposed portion by irradiation, further performing development to dissolve the unexposed portion using an alkaline aqueous solution to form a pattern, and performing post-baking as post-curing can be mentioned. Here, glass, transparent films (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) and the like are used as the substrate on which the photosensitive resin composition solution is applied.

As a method for applying the photosensitive resin composition solution to the substrate, any method such as a method using a roller coater, a land coater, a slit coater, a spinner, or the like can be used in addition to the known solution dipping method and spray method. can be adopted. By these methods, a film is formed by applying a desired thickness and then removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected according to the solvent used, and are preferably carried out at 80 to 120° C. for 1 to 10 minutes, for example.

As the radiation used for exposure, for example, visible light, ultraviolet rays, deep ultraviolet rays, electron beams, X-rays, etc. can be used, and the wavelength range of the radiation is preferably 250 to 450 nm. As a developer suitable for this alkali development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like can be used. These developers can be appropriately selected according to the properties of the resin layer, and it is also effective to add a surfactant as necessary. The developing temperature is preferably 20 to 35° C., and a fine image can be precisely formed using a commercially available developing machine, ultrasonic cleaning machine, or the like. After alkali development, the film is usually washed with water. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, or the like can be applied.

Alkaline development after exposure is carried out for the purpose of removing the photosensitive resin composition from the unexposed portions, and a desired pattern is formed by this development. Examples of the developer suitable for this alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, and aqueous solutions of hydroxides of alkali metals. It is preferable to develop at a temperature of 23 to 27° C. using a weakly alkaline aqueous solution containing 0.03 to 1% by weight of carbonate. can be formed.

After development in this manner, heat treatment (post-baking) is performed at 180 to 250° C. for 20 to 100 minutes. However, if the substrate on which the film is to be formed has low heat resistance, the formulation of the composition can be designed so that post-baking conditions can be set at 80 to 180° C. for 30 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is done by heating with an oven, hot plate or the like, similar to pre-baking. The patterned cured product of the present invention is formed through each step of the photolithography method described above.

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

First, synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin containing the structure represented by the formula (2) will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows. .

[Solid content concentration]
A glass filter [mass: W ₀ (g)] was impregnated with 1 g of the resin solutions and photosensitive resin compositions obtained in Synthesis Examples and Comparative Synthesis Examples and weighed [W ₁ (g)], and the temperature was 160 ° C. It was obtained from the following formula (1) from the mass [W ₂ (g)] after heating for 2 hours at .
Solid content concentration (mass%) = 100 × (W ₂ - W ₀ )/(W ₁ - W ₀ )

[Acid value]
The resin solution is dissolved in tetrahydrofuran and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the amount of KOH required per 1 g of solid content. acid value.

[Molecular weight]
Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) conversion value weight average molecular weight (Mw ).

Abbreviations used in Synthesis Examples and Comparative Synthesis Examples are as follows.
HBPA-EA1: hydrogenated BisA epoxy (epoxy equivalent 201 g/eq) (formula (1)
skeleton) and acrylic acid reaction product (epoxy group and carbo
Equivalent reactant of oxy group)
HBPA-EA2: hydrogenated BisA epoxy (epoxy equivalent weight 265 g/eq) (formula (1)
skeleton) and acrylic acid reaction product (epoxy group and carbo
Equivalent reactant of oxy group)
BPA-EA: BisA epoxy (epoxy equivalent weight 189 g/eq) (formula (22)
skeleton) and a reaction product with acrylic acid (epoxy group and calcium
Equivalent reactant of boxy group)
BPF-EA: Bis phenol fluorene type epoxy (epoxy equivalent 250
g/eq) (having a skeleton of formula (22)) with acrylic acid
substance (equivalent reactant of epoxy group and carboxyl group)
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride THPA: 1,2,3,6-tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]
A 50% PGMEA solution of HBPA-EA1 (329.1 g), BPDA (44.1 g), THPA (22.8 g), and TEAB (0.43 g) were placed in a 1000 ml four-necked flask equipped with a reflux condenser. and PGMEA (8.5 g) were charged and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-1. The resulting resin had a solid content concentration of 61.2% by mass, an acid value (in terms of solid content) of 123.1 mgKOH/g, and a molecular weight (Mw) of 3,210.

[Synthesis Example 2]
A 50% PGMEA solution of HBPA-EA1 (340.0 g), HPMDA (34.7 g), THPA (23.6 g), and TEAB (0.43 g) were placed in a 1000 ml four-necked flask equipped with a reflux condenser. and PGMEA (8.5 g) were charged and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-2. The resulting resin had a solid content concentration of 61.1% by mass, an acid value (in terms of solid content) of 120.4 mgKOH/g, and a molecular weight (Mw) of 3,230.

[Synthesis Example 3]
A 50% PGMEA solution of HBPA-EA2 (338.2 g), BPDA (36.8 g), THPA (19.0 g), and TEAB (0.43 g) were placed in a 1000 ml four-necked flask equipped with a reflux condenser. and PGMEA (8.5 g), and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-3. The resulting resin had a solid content concentration of 73.8% by mass, an acid value (in terms of solid content) of 93.0 mgKOH/g, and a molecular weight (Mw) of 4,980.

[Synthesis Example 4]
A 50% PGMEA solution of HBPA-EA2 (338.2 g), HPMDA (28.0 g), THPA (19.0 g), and TEAB (0.43 g) were placed in a 1000 ml four-necked flask equipped with a reflux condenser. and PGMEA (8.5 g) were charged and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-4. The resulting resin had a solid content concentration of 64.2% by mass, an acid value (in terms of solid content) of 100.8 mgKOH/g, and a molecular weight (Mw) of 3,960.

[Comparative Synthesis Example 1]
50% PGMEA solution of BPA-EA (325.1 g), BPDA (45.6 g), THPA (23.6 g), and TEAB (0.43 g) in a 1000 ml four-necked flask equipped with a reflux condenser. and PGMEA (8.5 g) were charged and stirred for 6 hours while heating at 120 to 125° C. to obtain an alkali-soluble resin (i)-5. The resulting resin had a solid content concentration of 68.5% by mass, an acid value (in terms of solid content) of 113.0 mgKOH/g, and a molecular weight (Mw) of 2,080.

[Comparative Synthesis Example 2]
A 50% PGMEA solution of BPA-EA (335.6 g), HPMDA (35.9 g), THPA (24.3 g), and TEAB (0.43 g) were placed in a 1000 ml four-necked flask equipped with a reflux condenser. , PGMEA (8.5 g), and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-6. The resulting resin had a solid content concentration of 69.5% by mass, an acid value (in terms of solid content) of 116.5 mgKOH/g, and a molecular weight (Mw) of 2,630.

[Comparative Synthesis Example 3]
A 50% PGMEA solution of BPF-EA (313.7 g), BPDA (47.1 g), THPA (24.3 g), and TEAB (0.43 g) were placed in a 1000 ml four-necked flask equipped with a reflux condenser. and PGMEA (8.5 g), and stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (i)-7. The obtained resin had a solid content concentration of 56.55% by mass, an acid value (in terms of solid content) of 103.0 mgKOH/g, and a molecular weight (Mw) of 3,600.

Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the photosensitive resin composition and the cured product, but the present invention is not limited to these. Raw materials and abbreviations used in the following examples and comparative examples are as follows.

(i)-1: alkali-soluble resin obtained in Synthesis Example 1 above (i)-2: alkali-soluble resin obtained in Synthesis Example 2 above (i)-3: alkali-soluble resin obtained in Synthesis Example 3 above Resin (i)-4: alkali-soluble resin obtained in Synthesis Example 4 above (i)-5: alkali-soluble resin obtained in Comparative Synthesis Example 1 above (i)-6: obtained in Comparative Synthesis Example 2 above Alkali-soluble resin (i)-7: Alkali-soluble resin obtained in Comparative Synthesis Example 3 (ii): Dipentaerythritol hexaacrylate (iii): Irgacure 184 (manufactured by BASF, “Irgacure” is the same
company's registered trademark)
(iv): 20.0% by weight of carbon black, 5.0% by weight of polymeric dispersant P
GMEA dispersion (25.0% solids, average secondary of carbon black
particle size 162 nm)
(v): propylene glycol monomethyl ether acetate

[Evaluation of photosensitive resin composition]
Table 1 shows the content (unit: % by mass) of each component in the photosensitive resin composition solutions of Synthesis Examples 1 to 4 and Comparative Examples 1 and 2.

(Sample preparation)
The photosensitive resin composition solutions of Examples 1 to 4 and Comparative Examples 1 and 2 were coated on a glass plate using a spin coater under the conditions of a dry film thickness of 1.5 μm and dried, followed by a photomask. The film was exposed by irradiating ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW/cm ² using a 500 W high-pressure mercury lamp without passing through a filter. After the exposure, the film was processed with a developer using a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa. Thereafter, a heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film (a glass substrate having a cured film formed thereon).

The transmittance and refractive index of the glass substrate on which the cured film was formed were evaluated. Table 2 shows the results.

(Method for measuring transmittance)
Using a spectrophotometer "UH-4150" (manufactured by Hitachi High-Tech Science Co., Ltd.), the light transmittance at 400 nm was measured.

(Evaluation criteria)
Evaluation was performed according to the following criteria.
○: Light transmittance is 85% or more ×: Light transmittance is less than 85%

(Method for measuring refractive index)
Using a prism coupler film thickness/refractometer "Model 2010/M" (manufactured by Metricon), the refractive index of a light beam of 633 nm was measured. Table 2 shows the measured refractive indices.

As is clear from the results of Examples 1 to 4 and Comparative Examples 1 and 2, photosensitive resin compositions containing the alkali-soluble resins (i)-1 to (i)-4 of the formula (1) of the present invention It was found that a cured product having a high transmittance and a low refractive index can be obtained by using these.

[Evaluation of colored photosensitive resin composition]
Table 3 shows the content (unit: % by mass) of each component in the colored photosensitive resin composition solutions of Synthesis Examples 5 to 8 and Comparative Examples 3 and 4.

(Sample preparation for reflectance measurement)
The colored photosensitive resin composition solutions of Examples 5 to 8 and Comparative Examples 3 and 4 were coated on a glass plate using a spin coater under the conditions of a dry film thickness of 1.5 μm. The film was exposed by irradiating ultraviolet rays with a wavelength of 365 nm and an illuminance of 10 mW/cm ² using a 500 W high-pressure mercury lamp without a mask. After the exposure, the film was processed with a developer using a 0.4% sodium carbonate aqueous solution at 23° C. for 60 seconds under a pressure of 0.1 MPa. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a colored cured film (a glass substrate having a colored cured film formed thereon).

The reflectance was measured for the glass substrate on which the colored cured film was formed. Table 4 shows the results.

(Measurement method of reflectance)
The Y value was measured using a spectrophotometer "UH-4150" (manufactured by Hitachi High-Tech Science Co., Ltd.).

(Evaluation criteria)
The appearance of the surface of the colored cured film was visually confirmed.
◎: Color unevenness is not observed at all ○: Color unevenness is observed in an area of 1/4 or less of the surface △: Color unevenness is observed in an area of 1/3 or less of the surface ×: Color unevenness is observed throughout be done

(Sample preparation for alkali developability evaluation)
The colored photosensitive resin composition solutions of Examples 5 to 8 and Comparative Examples 3 and 4 were coated on a glass plate using a spin coater under conditions to give a dry film thickness of 1.5 μm, dried, and then patterned. Exposure was performed by irradiating ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW/cm 2 using a 500 W high-pressure mercury lamp through a mask for formation. After exposure, it was processed with a developing solution using a 0.15% sodium carbonate aqueous solution at 23°C. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a colored cured film (a glass substrate having a colored cured film formed thereon).

The alkali developability and adhesion were evaluated for the glass substrate on which the colored cured film was formed. Table 5 shows the results.

(Evaluation method: alkali developability)
At the time of development, it was visually confirmed whether or not the dried thin film of the colored photosensitive resin composition was dissolved in the developer.

(Evaluation criteria: alkali developability)
○: During development, the area not irradiated with ultraviolet rays dissolves in the developer. ×: During development, the area that is not irradiated with ultraviolet rays does not dissolve in the developer, or peels off as fragments.

(Evaluation method: adhesion)
Fine line formation of the resist film pattern was confirmed with an optical microscope "ECLIPSE LV100" (manufactured by Nikon Corporation).

(Evaluation criteria: adhesion)
○: A pattern with an L/S (line width/space width) of 20 μm/20 μm or more was formed without residue ×: A pattern with an L/S (line width/space width) of less than 20 μm/20 μm was formed There is no pattern, or the hemming or residue of the pattern is conspicuous.

As is clear from the results of Examples 5 to 8 and Comparative Examples 3 and 4, photosensitive resin compositions containing the alkali-soluble resins (i)-1 to (i)-4 of the formula (1) of the present invention It has been found that fine patterns can be formed by using this.

According to the alkali-soluble resin of the present invention, it is possible to obtain a photosensitive resin composition which enables fine pattern formation and satisfies the requirements for light resistance. Therefore, it is useful for touch panels, color filters, and the like, for example. In other words, since it can be patterned by photolithography, it has the advantage of being able to be formed by an existing photolithography process, and furthermore, since it can be formed with a thin film, it can contribute to the thinning of structures, and can be used for touch panels and color filters. Suitable for fabrication.

Claims (12)

dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) for the reactant of the epoxy compound (a) having the structure represented by formula (1) and the unsaturated group-containing monocarboxylic acid, and a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, comprising reacting a tetracarboxylic acid or its acid dianhydride (c).

(In formula (1), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, and X is a carbon atom which may contain a hetero element therein.) a divalent organic group having a number of 1 to 20, —CO—, —SO ₂ —, —Si(CH ₃ ) ₂ —, —O—, or a single bond, a having an average value of 0 to 10, and b is 0 to 4.) The carboxy group of the polymerizable unsaturated group-containing alkali-soluble resin obtained by the production method according to claim 1 is further reacted with a compound having a group that reacts with the carboxy group and a polymerizable unsaturated group. , a method for producing a polymerizable unsaturated group-containing alkali-soluble resin. Polymerizable unsaturated group-containing resin obtained by reacting the hydroxyl group of the polymerizable unsaturated group-containing alkali-soluble resin obtained by the production method according to claim 2 with a dicarboxylic acid or tricarboxylic acid or their acid unihydride. A method for producing an alkali-soluble resin. A polymerizable unsaturated group-containing alkali-soluble resin having a structure represented by formula (2).

(In formula (2), R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, R ₂ is a hydrocarbon group having 1 to 3 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and X is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom inside, —CO—, —SO ₂ —, —Si(CH ₃ ) ₂ —, —O— or a single bond; is a tetravalent carboxylic acid residue, Z is a hydrogen atom or a substituent represented by formula (3), provided that at least one of Z is a substituent represented by formula (3), G is a hydrogen atom or a substituent represented by formula (4), a has an average value of 0 to 10, b has an average value of 0 to 4, and n has an average value of 1 to 20.)

(In formulas (3) and (4), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrocarbon group having 2 to 4 carbon atoms, and L is a divalent or trivalent carboxylic acid residue. , c is 0 or 1, d and e are 0, 1 or 2, and d+e is 1 or 2.) (A) a polymerizable unsaturated group-containing alkali-soluble resin containing the polymerizable unsaturated group-containing alkali-soluble resin according to claim 4;
(B) a photoinitiator;
A photosensitive resin composition comprising: (C) a photopolymerizable monomer having at least one polymerizable unsaturated group;
(D) an epoxy compound or epoxy resin having two or more epoxy groups, which is an optional component;
The photosensitive resin composition according to claim 5, comprising: 7. The photosensitive resin composition according to claim 5, which contains (E) a dispersoid. In the solid content of the photosensitive resin composition, component (A) is 1 to 55% by mass, component (C) is 0 to 100 parts by mass with respect to 100 parts by mass of component (A), and (B ) component is 0.1 to 40 parts by mass per 100 parts by mass of the total amount of component (A) and component (C), and component (E) is 1 to 95 mass %. The photosensitive resin composition according to . The component (A) is
A polymerizable unsaturated group-containing alkali-soluble resin represented by the formula (2);
a resin represented by formula (5);
including
The ratio between the mass m _A-1 of the polymerizable unsaturated group-containing alkali-soluble resin represented by the formula (2) and the mass m _A-2 of the resin represented by the formula (5) is m _A- 9. The photosensitive resin composition according to any one of claims 5 to 8, wherein ₁ /m _A-2 =75/25 to 25/75.

(In formula (5), R ₆ , R ₇ , R ₈ and R ₉ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₁₀ is a 4, R ₁₁ is a hydrogen atom or a methyl group, and M is —CO—, —SO ₂ —, —C(CF ₃ ) ₂ —, —Si(CH ₃ ) ₂ —, —CH ₂ —, —C(CH ₃ ) ₂ —, —O—, 9,9-fluorenylene group or single bond, Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or ), wherein at least one of Z is a substituent represented by formula (3), G is a hydrogen atom or a substituent represented by formula (4), and d is The average value is 0 to 10, and the average value of m is 1 to 20.) A cured product obtained by patterning the photosensitive resin composition according to any one of claims 5 to 9 by photolithography, and curing the patterned photosensitive resin composition. A touch panel comprising the cured product according to claim 10 as a component. A color filter comprising the cured product according to claim 10 as a constituent.