JP2022063336A - Photosensitive resin composition and method of producing resin-coated substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is suitable for forming a resin film pattern on a plastic substrate having a heat resistance of 140°C or higher, and a method of producing a resin-coated substrate by curing the photosensitive resin composition on a substrate at a low temperature.

SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) an epoxy compound, (D) a curing agent and/or a curing accelerator for the epoxy compound, (E) a photopolymerization initiator, and (F) a solvent; and the total amount of the component (C) and the component (D) is 6 mass% to 24 mass% in the solid components excluding the component (F).

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention forms a resin film pattern on a substrate having a heat resistant temperature of 140 ° C. or lower (a plastic substrate, a glass substrate, a substrate with an organic device equipped with an organic EL, an organic TFT, etc. on a silicon wafer, etc.) by a photolithography method. It relates to a photosensitive resin composition having a specific composition used for the purpose, and also relates to a method for manufacturing a substrate with a resin film.

Recently, for the purpose of making devices flexible and one-chip, for example, a resin film (transparent insulation) is directly applied to a plastic substrate (plastic film, resin film) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate). (Film, etc.) pattern, colored film pattern, light-shielding film pattern can be formed, or resin film pattern, colored film pattern, light-shielding film pattern can be formed directly on a substrate with an organic device equipped with an organic EL, organic TFT, etc. on a glass substrate or silicon wafer. There is a demand to form. However, in many cases, the heat resistance temperature of the plastic substrate itself is generally only about 140 ° C., the heat resistance of the substrate with an organic device is at most 120 ° C, and the heat resistance in the actual manufacturing process is preferably 100 ° C or less. Is the reality. Therefore, when forming a resin film pattern, a colored film pattern, and a light-shielding film pattern on a plastic substrate or device, the film strength of the formed pattern becomes insufficient at a heat firing temperature of 140 ° C. or lower, and a subsequent subsequent step (for example, light-shielding). In the case of a film pattern, there is a problem that the film of the coating film is reduced, the surface is roughened, the pattern is peeled off, and the like in the solvent resistance at the time of applying each RGB resist and the alkali resistance at the time of alkaline development. Further, at a thermal firing temperature of 120 ° C. or lower, it is extremely difficult to form a resin film pattern, a colored film pattern, and a light-shielding film pattern having a desired film strength.

Therefore, for example, Japanese Patent Application Laid-Open No. 2003-15288 (Patent Document 1) describes a photosensitive resin composition containing an alkali-soluble resin of an acrylic copolymer as a base and a thermal polymerization initiator in addition to a photopolymerization initiator. The substrate used, coated, exposed, patterned, and heat-baked at 150 ° C. is disclosed. Although the residue and adhesion to the substrate (peeling test) are ensured, the pattern line width, development margin, There is no description of reliability (solvent resistance, alkali resistance), etc., and these are not yet sufficient.
Japanese Unexamined Patent Publication No. 2017-181976 (Patent Document 2) describes an unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer having at least three ethylenically unsaturated bonds, an oxime ester-based polymerization initiator, and an azo-based polymerization initiator. A photosensitive resin composition for a light-shielding film containing an agent and a light-shielding component is disclosed. However, when a resin film pattern is formed on a plastic substrate having low heat resistance or a substrate with an organic device at a low temperature, it is still insufficient, and it is more excellent in development adhesion and linearity, and also has solvent resistance and alkali resistance. There is a demand for a photosensitive resin composition capable of forming an excellent resin film pattern.

Japanese Patent Application Laid-Open No. 2003-15288 Japanese Unexamined Patent Publication No. 2017-181976

The present invention has been made in view of the above problems, and an object thereof is a resin film (transparent insulating film, etc.) pattern on a plastic substrate or a substrate with an organic device having a heat resistance of at most 140 ° C. It is suitable for forming colored film patterns and light-shielding film patterns, and when applied to these plastic substrates and substrates with organic devices that have low heat resistance, resin film patterns and colored films with excellent solvent resistance and alkali resistance, etc. It is an object of the present invention to provide a photosensitive resin composition suitable for obtaining a pattern, a light-shielding film pattern, and the like, and a method for producing a obtained substrate with a resin film. These resin film patterns, colored film patterns, light-shielding film patterns and the like can be applied as constituent members of various displays, touch panel sensors, image sensors and the like.

Therefore, the present inventors obtain a resin film pattern, a colored film pattern, a light-shielding film pattern, etc., which are excellent in solvent resistance, etc., while obtaining good development adhesion and pattern linearity by thermal curing at 140 ° C. or lower. As a result of diligent studies on a production method for forming a pattern using a specific photosensitive resin composition capable of forming a predetermined polymerizable unsaturated group-containing alkali-soluble resin, photopolymerizable monomer, epoxy compound, and epoxy compound. In the composition containing the curing agent and / or the curing accelerator and the photopolymerization initiator, the above-mentioned problems are solved by using the composition containing the curing agent and / or the curing accelerator of the epoxy compound and the epoxy compound in a specific range. We have found that we can solve the problem and completed the present invention.

In the present invention, a photosensitive resin composition is applied onto a substrate having a heat resistant temperature of 140 ° C. or lower, exposed through a photomask, an unexposed portion is removed by development, and then heated at 140 ° C. or lower. A photosensitive resin composition used for forming a substrate with a resin film by forming a predetermined resin film pattern.
(A) Unsaturated group-containing alkali-soluble resin,
(B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds,
(C) Epoxy compound,
(D) Epoxy compound curing agent and / or curing accelerator,
(E) Photopolymerization initiator,
(F) Solvent,
The photosensitive resin composition is characterized in that the total amount of the C component and the D component is 6 to 24% by mass in the solid content excluding the F component.
In particular, in the present invention
The epoxy compound of the C component has an epoxy equivalent of 100 to 300 g / eq.
The curing agent for component D is a polyvalent carboxylic acid compound,
The photopolymerization initiator of the E component is an acyloxime-based photopolymerization initiator.

Ｒ^１、Ｒ^２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又はＣ４～Ｃ１２の複素環基を表し、Ｒ^３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、又は環状のいずれのアルキル基であってもよい。
Ａ成分の不飽和基含有アルカリ可溶性樹脂が一般式（２）で表される不飽和基含有アルカリ可溶性樹脂であることが好ましい。

（式中、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立して水素原子、炭素数１～５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ^８は、水素原子又はメチル基を表し、Ａ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－ジイル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ_１及びＹ_２は、それぞれ独立して水素原子又は－ＯＣ－Ｚ－（ＣＯＯＨ）ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１又は２の数を表す）を表し、ｎは１～２０の整数を表す。） The photosensitive resin composition of the present invention may further contain a colorant consisting of (G) an organic pigment or an inorganic pigment.
It is preferable that the colorant of the G component is a light-shielding material made of an organic black pigment or an inorganic black pigment.
As the photopolymerization initiator of the E component, it is preferable to use an acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10,000 or more at 365 nm.
It is preferable that the photopolymerization initiator of the component E is the acyloxime-based photopolymerization initiator of the general formula (1).

R ¹ and R ² independently represent an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20 or a heterocyclic group of C4 to C12, and R ³ is an alkyl of C1 to C15. Represents a group, an aryl group of C6 to C18, and an arylalkyl group of C7 to C20. Here, the alkyl group and the aryl group may be substituted with an alkyl group of C1 to C10, an alkoxy group of C1 to C10, an alkanoyl group of C1 to C10, or a halogen, and the alkylene moiety may be substituted with an unsaturated bond or an ether bond. It may contain a thioether bond and an ester bond. Further, the alkyl group may be a linear, branched, or cyclic alkyl group.
The unsaturated group-containing alkali-soluble resin of the component A is preferably an unsaturated group-containing alkali-soluble resin represented by the general formula (2).

(In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ⁸ is a hydrogen atom or a methyl group. , A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- , Fluolene-9,9-diyl group or direct bond, X represents _a tetravalent carboxylic _acid residue, Y1 and Y2 are independently hydrogen atoms or -OC-Z- (COOH) m, respectively. (However, Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20.)

Another aspect of the present invention is a method of forming a resin film pattern on a substrate having a heat resistant temperature of 140 ° C. or lower to manufacture a substrate with a resin film, and is a photosensitive resin used for forming the resin film pattern. As the composition, the above-mentioned photosensitive resin composition is used, the photosensitive resin composition is applied onto a substrate, exposed through a photomask, the unexposed portion is removed by development, and then at 140 ° C. or lower. It is a method for manufacturing a substrate with a resin film, which comprises heating to form a predetermined resin film pattern.

The photosensitive resin composition of the present invention can form a resin film pattern having a line width of 5 to 50 μm with a resolution without including a step of thermosetting at a temperature exceeding 140 ° C. in the process of producing the resin film pattern. It is possible to form a resin film pattern that is excellent in developability and linearity and has good solvent resistance. Therefore, a substrate with an organic device provided with a resin film such as PET or PEN having a heat resistant temperature of 140 ° C. or less, an organic EL formed on a glass substrate or a silicon wafer, an organic TFT, or the like (a protective film is formed and protected after the formation of the organic device). A desired resin film pattern can be formed on a substrate (including a substrate such as a film bonded).

Hereinafter, the present invention will be described in detail.
The present invention relates to a photosensitive resin composition used for forming a resin film pattern on a substrate having a heat resistant temperature of 140 ° C. or lower, and the resin film pattern is applied by applying an optical processing technique such as a photolithography method. This is a method for manufacturing a low heat resistant substrate with a resin film, and is characterized by the photosensitive resin composition used. Therefore, first, each component of the photosensitive resin composition and its constituent ratio will be described.

The polymerizable unsaturated group-containing alkali-soluble resin which is the component (A) in the photosensitive resin composition can be used without particular limitation as long as it is a resin having a polymerizable unsaturated group and an acidic group in the molecule. A typical example of the polymerizable unsaturated group is an acrylic group or a methacrylic group, and a carboxyl group can be typically exemplified as the acidic group.

The range of preferable weight average molecular weight (Mw) and acid value of this polymerizable unsaturated group-containing alkali-soluble resin varies depending on the skeleton of the resin, but usually Mw is 2000 to 50,000 and the acid value is 60 to 120 mgKOH / g. If Mw is less than 2000, the adhesion of the pattern during alkaline development may decrease, and if it exceeds Mw50000, the developability is significantly reduced, and it becomes impossible to obtain a photosensitive resin composition having an appropriate development time. There is a risk. Further, when the acid value value is smaller than 60, a residue tends to remain during alkaline development, and when the acid value value is larger than 120, the penetration of the alkaline developer becomes too fast, resulting in unfavorable dissolution development and peeling development. Neither is preferable because it ends up. As the unsaturated group-containing alkali-soluble resin of the component (A), only one kind may be used, or a mixture of two or more kinds may be used.

As the first example of the unsaturated group-containing alkali-soluble resin of the component (A) which can be preferably applied, a compound having two or more epoxy groups and (meth) acrylic acid (which is "acrylic acid and / or methacrylic acid"). (Meaning), and the obtained epoxy (meth) acrylate compound having a hydroxy group is reacted with (a) an acid monoanhydride of a dicarboxylic acid or a tricarboxylic acid and / or (b) a tetracarboxylic acid dianhydride. It is an epoxy (meth) acrylate acid adduct obtained by the above-mentioned. Examples of the compound having two or more epoxy groups induced to the epoxy (meth) acrylate adduct include a bisphenol type epoxy compound and a novolak type epoxy compound.

The bisphenol type epoxy compound is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin, and since this reaction generally involves oligomerization of the diglycidyl ether compound, the bisphenol skeleton Contains an epoxy compound containing two or more of. The bisphenols used in this reaction include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and 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 (4,9-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 (4,9-bis) 4-Hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. Be done. Among these, bisphenols having a fluorene-9,9-diyl group can be particularly preferably used.

(A) Acid monoanhydride of dicarboxylic acid or tricarboxylic acid to be reacted with epoxy (meth) acrylate includes acid monoanhydride of chain hydrocarbon dicarboxylic acid or tricarboxylic acid, or acid monoanoxide of alicyclic dicarboxylic acid or tricarboxylic acid. Acidic anhydrides, aromatic dicarboxylic acids or tricarboxylic acid monoanhydrides are used. Here, examples of the acid monoanhydride of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, and glutaric acid. There are acid monoanhydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and even dicarboxylic acid or tricarboxylic acid monoanhydride in which any substituent is introduced. good. Examples of the acid monoanhydride of the alicyclic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornandicarboxylic acid. Further, an acid monoanhydride of a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent is introduced may be used. Further, examples of the acid monoanhydride of the aromatic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as phthalic acid, isophthalic acid and trimellitic acid, and further, dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced. It may be an acid monoanhydride of an acid.

The acid dianhydride of (b) tetracarboxylic acid to be reacted with epoxy (meth) acrylate includes acid dianhydride of chain hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, or acid dianhydride. , Acid dianhydride of aromatic tetracarboxylic acid is used. Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid and hexanetetracarboxylic acid, and further, any substituent can be used. It may be an acid dianhydride of the introduced tetracarboxylic acid. Examples of the acid dianhydride of the alicyclic tetracarboxylic acid include acid dianhydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid and norbornantetracarboxylic acid. It may be an acid dianhydride of a tetracarboxylic acid having an arbitrary substituent introduced therein. Further, examples of the acid dianhydride of the aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid and biphenyl ether tetracarboxylic acid, and further, any arbitrary acid dianhydride. It may be an acid dianhydride of a tetracarboxylic acid having a substituent introduced therein.

The molar ratio (a) / (b) of (a) an acid anhydride of a dicarboxylic acid or a tricarboxylic acid to be reacted with an epoxy (meth) acrylate and (b) an acid dianhydride of a tetracarboxylic acid is 0.01 to 10. It is often 0.0, more preferably 0.02 or more and less than 3.0. If the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight for obtaining a photosensitive resin composition having good photopatterning property cannot be obtained, which is not preferable. The smaller the molar ratio (a) / (b), the larger the molecular weight and the tendency for the alkali solubility to decrease.

The epoxy (meth) acrylate adduct can be produced by a known method, for example, the method described in JP-A-8-278629, JP-A-2008-9401, and the like. First, as a method of reacting an epoxy compound with (meth) acrylic acid, for example, an equimolar (meth) acrylic acid with an epoxy group of the epoxy compound is added to a solvent, and a catalyst (triethylbenzylammonium chloride, 2,6) is added. -In the presence of (diisobutylphenol, etc.), there is a method of heating and stirring at 90 to 120 ° C. while blowing air to react. Next, as a method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound which is a reaction product, a predetermined amount of the epoxy acrylate compound, the acid dianhydride and the acid anhydride are added to the solvent, and a catalyst (odor) is added. In the presence of tetraethylammonium oxide, triphenylphosphine, etc.), there is a method of heating and stirring at 90 to 130 ° C. for reaction. The epoxy acrylate adduct obtained by this method has the skeleton of the general formula (2).

Another example of a resin that can be preferably used as a polymerizable unsaturated group-containing alkali-soluble resin as a component (A) is a copolymer such as (meth) acrylic acid or (meth) acrylic acid ester (meth). Examples thereof include resins having an acrylic group and a carboxyl group. For example, as a first step, a copolymer obtained by copolymerizing (meth) acrylic acid esters containing glycidyl (meth) acrylate in a solvent is reacted with (meth) acrylic acid as a second step, and the third step is carried out. It is a polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting an anhydride of a dicarboxylic acid or a tricarboxylic acid in a step. As an example of these copolymers that can be preferably used, those specifically shown in Japanese Patent Application No. 2017-33662 can be referred to.

As another example, a polyol compound having an ethylenically unsaturated bond in the molecule as the first component, a diol compound having a carboxyl group in the molecule as the second component, and a diisocyanate compound as the third component are reacted. Examples thereof include the obtained urethane compounds. As the resin of this system, those shown in JP-A-2017-76071 can be referred to.

Examples of the photopolymerizable monomer having at least two ethylenically unsaturated bonds in (B) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene. Glycoldi (meth) acrylate, tetramethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, penta Elythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa (meth) acrylate and other (meth) acrylic acid esters, ethylenic double bond Examples of the compound to have include a dendritic polymer having a (meth) acrylic group, and one or more of these can be used. Further, the photopolymerizable monomer having at least two ethylenically unsaturated bonds can play a role of cross-linking the molecules of the contained alkali-soluble resin, and in order to exert this function, it is photopolymerizable. It is preferable to use one having three or more groups. Further, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth) acrylic groups in one molecule may be 50 to 300, but a more preferable acrylic equivalent is 80 to 200. The component (B) does not have a free carboxy group.

ここで、Ｒ^８は水素原子またはメチル基を表し、Ｒ^９はＲ^１０（ＯＨ）ｋのｋ個のヒドロキシル基の内ｌ個のヒドロキシル基を式中のエステル結合に供与した残り部分を表し、ｋおよびｌは独立に２～２０の整数を表すが、ｋ≧ｌである。また、Ｒ^１１は単結合又は２～６価のＣ１～Ｃ６の炭化水素基であり、ｍはＲ^１１が単結合であるときは２であり、Ｒ^１１が２～６価の基であるときは２～６の整数を表す。
一般式（３）で示される多官能（メタ）アクリレート化合物の具体例としては、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールトリ（メタ）アクリレート等の（メタ）アクリル酸エステルを挙げることができる。これらの化合物は、その１種のみを単独で使用してもよく、２種以上を併用してもよい。
一般式（４）で示される多価メルカプト化合物の具体例としては、トリメチロールプロパントリ（メルカプトアセテート）、トリメチロールプロパントリ（メルカプトプロピオネート）、ペンタエリスリトールテトラ（メルカプトアセテート）、ペンタエリスリトールトリ（メルカプトアセテート）、ペンタエリスリトールテトラ（メルカプトプロピオネート）、ジペンタエリスリトールヘキサ（メルカプトアセテート）、ジペンタエリスリトールヘキサ（メルカプトプロピオネート）等が挙げることができる。これらの化合物は、その１種のみを単独で使用してもよく、２種以上を併用してもよい。 As a dendritic polymer having a (meth) acrylic group as a compound having an ethylenic double bond that can be contained in the composition as a component (B), for example, a (meth) acrylate group of a polyfunctional (meth) acrylate compound. A dendritic polymer obtained by adding a polyvalent mercapto compound to a part of a carbon-carbon double bond in the above can be exemplified. Specifically, a dendritic polymer obtained by reacting the (meth) acrylate of the polyfunctional (meth) acrylate compound of the general formula (3) with the polyvalent mercapto compound of the general formula (4) can be exemplified.

Here, R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents the rest of the k hydroxyl groups of R ¹⁰ (OH) k donated to the ester bond in the formula. k and l independently represent an integer of 2 to 20, but k ≧ l. Further, R ¹¹ is a single bond or a 2- to 6-valent C1 to C6 hydrocarbon group, m is 2 when R ¹¹ is a single bond, and R ¹¹ is a 2- to 6-valent group. Represents an integer from 2 to 6.
Specific examples of the polyfunctional (meth) acrylate compound represented by the general formula (3) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethyl propanthry (meth) acrylate, and ethylene oxide-modified trimethylol. Propanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate Etc. (meth) acrylic acid esters can be mentioned. As for these compounds, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.
Specific examples of the polyvalent mercapto compound represented by the general formula (4) include trimethylolpropane tri (mercaptoacetate), trimethylolpropane tri (mercaptopropionate), pentaerythritol tetra (mercaptoacetate), and pentaerythritol tri (mercaptoacetate). (Mercaptoacetate), pentaerythritol tetra (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate) and the like can be mentioned. As for these compounds, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

The epoxy compound (C) includes, for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol fluorene type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a phenol aralkyl type epoxy compound, and a naphthalene skeleton. Phenol novolak compound (for example, NC-7000L manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, trisphenol methane type epoxy compound, tetrakisphenol ethane type epoxy compound, polyhydric alcohol glycidyl ether, polyhydric carboxylic acid glycidyl ester, A copolymer of a monomer having a (meth) acrylic group containing glycidyl (meth) acrylate represented by a copolymer of methacrylic acid and glycidyl methacrylate as a unit, 3', 4'-epoxycyclohexylmethyl 3,4- An alicyclic epoxy compound typified by epoxycyclohexanecarboxylate, a polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series manufactured by DIC), 1,2-bis (hydroxymethyl) -1-butanol 1,2. -Epoxy-4- (2-oxylanyl) cyclohexane adduct (for example, "EHPE3150" manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (for example, "NISSO-PB / JP-100" manufactured by Nippon Soda Co., Ltd.), epoxy compound having a silicone skeleton, etc. Can be mentioned. As these components, a compound having an epoxy equivalent of 100 to 300 g / eq and a number average molecular weight of 100 to 5000 is preferable. Further, it is more preferable to use an epoxy compound having three or more epoxy groups in one molecule. As the component (C), only one kind of compound may be used, or a plurality of compounds may be used in combination.

Among the components (D), as the curing agent for the epoxy compound, any compound used as a curing agent for the epoxy compound can be used, and an amine compound, a polyvalent carboxylic acid compound, a phenol resin, an amino resin, a dicyandiamide, etc. can be used. Although Lewis acid complex compounds and the like can be exemplified, polyvalent carboxylic acid compounds can be preferably used in the present invention. Examples of the polyvalent carboxylic acid compound include a polyvalent carboxylic acid, an anhydride of the polyvalent carboxylic acid, and a thermodegradable ester of the polyvalent carboxylic acid. The polyvalent carboxylic acid refers to a compound having two or more carboxy groups in one molecule, for example, succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4. , 5-dicarboxylic acid, norbornan-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4 -Tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, butane-1,2,3 , 4-Tetracarboxylic acid and the like can be mentioned.
Examples of the anhydride of the polyvalent carboxylic acid include acid anhydrides of the compounds exemplified above, which may be intermolecular acid anhydrides, but generally, acid anhydrides having a closed ring in the molecule are used. Examples of the thermally decomposable ester of the polyvalent carboxylic acid include t-butyl ester, 1- (alkyloxy) ethyl ester, and 1- (alkylsulfanyl) ethyl ester of the compounds exemplified above (however, the alkyl referred to here has a carbon number of carbons). It represents 1 to 20 saturated or unsaturated hydrocarbon groups, and the hydrocarbon group may have a branched structure or a ring structure, or may be substituted with an arbitrary substituent). can. Further, as the polyvalent carboxylic acid compound, a polymer or a copolymer having two or more carboxy groups can also be used, and the carboxy group may be an anhydrate or a pyrolytic ester. Examples of such polymers or copolymers include polymers or copolymers containing (meth) acrylic acid as a constituent, copolymers containing maleic anhydride as a constituent, and tetracarboxylic dianhydrides. Examples thereof include a compound obtained by reacting with a diamine or a diol to open a ring of an acid anhydride. Of these, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid anhydrides are more preferably used. be able to.
When the polyvalent carboxylic acid compound is used as a curing agent for the epoxy compound, the compounding ratio is 0.5 to 1.0 mol of the carboxyl group of the polyvalent carboxylic acid compound with respect to 1 mol of the epoxy group of the epoxy compound. , More preferably 0.6 to 0.95 mol.

As the curing accelerator of the epoxy compound among the components (D), known compounds known as the curing accelerator of the epoxy compound, the curing catalyst, the latent curing agent and the like can be used, for example, a tertiary amine, a quaternary ammonium salt, and the like. Examples thereof include tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles, etc., but in particular 1,8-diazabicyclo [5.4.0] undec-7-ene or 1 , 5-Diazabicyclo [4.3.0] nona-5-ene or salts thereof are suitable.
The amount of the curing accelerator added is usually 0.05 to 2 parts by mass with respect to 100 parts by mass of the epoxy compound, but the amount added should be adjusted according to the state of development of chemical resistance of the resin film pattern after heat curing. Can be done.

Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone and the like. , Benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-chlorophenyl). ) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2 -(O-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-stylyl-1,3,4-oxa Diazol, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Halomethylthiazole compounds such as 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, etc. 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 (trichloro) Methyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyl-S-triazine compounds 1, 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- O-acyloxime compounds such as (4-methylsulfanylphenyl) butane-2-oneoxime-o-acetate, benzyldimethylketal, thioxanson, 2-chlorothioxanson, 2,4-diethylthioxanson, 2- Sulfur compounds such as methylthioxanson and 2-isopropylthioxanson, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobisisobutylnitrile and benzoyl peroxide. , Organic peroxides such as cumemperoxide, thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, tertiary amines such as triethanolamine and triethylamine.
Among these, particularly in the case of a photosensitive resin composition containing a colorant, it is preferable to use o-acyloxime compounds (including ketooxime). Among them, when a colorant is used at a high pigment concentration or when a light-shielding film pattern is to be formed, it is preferable to use an o-acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10,000 or more at 365 nm. As the specific compound group, the o-acyloxime-based photopolymerization initiator of the general formula (1) can be mentioned. Further, two or more kinds of these photopolymerization initiators can also be used. The photopolymerization initiator referred to in the present invention is used in the sense of including a sensitizer.

(F) 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, acetone, methyl ethyl ketone, cyclohexanone and N-methyl. -2-Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl. Glycol ethers such as ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve. Examples thereof include acetates such as acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, which are used for dissolution and mixing. Therefore, a uniform solution-like composition can be obtained, and the composition can be prepared and used with a desired solution viscosity.

As the colorant (G), known organic pigments, inorganic pigments, carbon black, titanium black and the like can be used without particular limitation, but if it is an organic pigment, fine dispersion with an average particle size of 50 nm or less can be achieved. Therefore, those that have been atomized (those having a specific surface area of 50 m2 / g or more by the BET method) are particularly preferable. Specifically, azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindrin pigments, dioxazine pigments, slen pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, Examples include thioindigo pigments.

Among the colorants, black organic pigments, mixed color organic pigments, inorganic pigments and the like can be used without particular limitation as the light-shielding materials such as organic black pigments and inorganic black pigments used for light-shielding film applications. Examples of the black organic pigment include perylene black, cyanine black, aniline black, lactam black and the like. Examples of the mixed color organic pigment include those obtained by mixing at least two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like to make a pseudo-black color. Examples of the inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride and the like. These light-shielding materials may be used alone or by appropriately selecting two or more types, but carbon black is particularly good in light-shielding property, surface smoothness, dispersion stability, and affinity with resin. preferable.

Additives such as a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, and a surfactant can be added to the photosensitive resin composition of the present invention, if necessary. .. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like, and examples of the plasticizer include dibutylphthalate, dioctylphthalate, tricresyl phosphate and the like, which can be filled. Examples of the material include glass fiber, silica, mica, alumina and the like, and examples of the leveling agent and defoaming agent include silicone-based, fluorine-based and acrylic compounds. Examples of the silane coupling agent include 3- (glycidyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like, and examples of the surfactant include a fluorine-based surfactant. Examples thereof include an activator and a silicone-based surfactant.

Regarding the preferable composition ratio of each component (A) to (E) and (G) in the solid content of the photosensitive resin composition of the present invention (the solid content includes a monomer component that becomes a solid content after curing), The total amount of the component (C) and the component (D) is preferably 6 to 24% by mass, and particularly preferably 10 to 20% by mass. Further, the component (B) is 10 to 60 parts by mass and 10 to 80 parts by mass with respect to 100 parts by mass of the component (A), and the component (E) is the total amount of the component (A) and the component (B) 100. It is 2 to 40 parts by mass with respect to the mass part. More preferably, the component (B) is 30 to 50 parts by mass with respect to 100 parts by mass of the component (A), and the component (E) is based on 100 parts by mass of the total amount of the component (A) and the component (B). It is 3 to 30 parts by mass. When a colorant is used, the preferred content range of the component (G) in the solid content is 20 to 60% by mass.

The colorant of the component (G) is preferably dispersed in a solvent together with the dispersant to prepare a colorant dispersion liquid, and then blended as a photosensitive resin composition for a color film. Here, the solvent described above can be used as the solvent to be dispersed, and for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and the like are preferably used. As the dispersant to be used, known dispersants such as various polymer dispersants can be used. As a specific example of the dispersant, a known compound (a compound commercially available under the names of a dispersant, a dispersion wetting agent, a dispersion accelerator, etc.) conventionally used for dispersion of pigments may be used without particular limitation. However, for example, a cationic polymer-based dispersant, an anionic polymer-based dispersant, a nonionic polymer-based dispersant, a pigment derivative-type dispersant (dispersion aid), and the like can be mentioned. In particular, it 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 a pigment, has an amine value of 1 to 100 mgKOH / g, and has a number average molecular weight. A cationic polymer dispersant having a value in the range of 1,000 to 100,000 is suitable. The blending amount of this dispersant is preferably 1 to 30% by mass, preferably 2 to 25% by mass with respect to the colorant.

Further, when preparing the colorant dispersion liquid, a photosensitive resin composition for a colored film is prepared by covariating a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in addition to the above-mentioned dispersant. In this case, it is possible to obtain a photosensitive resin composition which makes it easy to maintain high exposure sensitivity, has good adhesion during development, and is less likely to cause a problem of residue. At that time, the blending amount of the component (A) is preferably 2 to 20% by mass, more preferably 5 to 15% by mass in the colorant dispersion liquid. If the component (A) is less than 2% by mass, the effects of covariance, sensitivity improvement, adhesion improvement, and residue reduction cannot be obtained. If it exceeds 20% by mass, the viscosity of the colorant dispersion is high, and it is difficult or very time-consuming to uniformly disperse the colorant, especially when the content of the colorant is large. Then, the obtained colorant dispersion is mixed with the components (A) to (F), and if necessary, other components are added to adjust the viscosity to be suitable for the film forming conditions, thereby producing the present invention. It can be a photosensitive resin composition used in the method.

The photosensitive resin composition of the present invention contains the above components (A) to (E) and / or (G) as main components. A total of 80% by mass, preferably 90% by mass, of the components (A) to (E) and / or (G) in the solid content excluding the solvent (the solid content includes a monomer component that becomes a solid content after curing). It is desirable to include% or more. The amount of the solvent varies depending on the target viscosity, but it is preferable that the amount of the solvent is contained in the photosensitive resin composition in the range of 60 to 90% by mass.

The method for forming the resin film pattern in the present invention is a normal photolithography method, which will be described in detail below. First, the photosensitive resin composition is applied onto a plastic substrate or a substrate with an organic device, and then the solvent is dried (prebaked), and then the obtained coating film is irradiated with ultraviolet rays through a photomask to cure the exposed portion. Further, it is a method of developing to elute the unexposed portion using an alkaline aqueous solution to form a pattern, and further performing post-baking (heat firing) as post-curing.

Examples of the substrate used in the production method of the present invention, that is, the substrate to which the photosensitive resin composition having a specific composition composition is applied, include resin films (plastic substrates) such as PET and PEN having a heat resistant temperature of 140 ° C. or lower. Can be done. Here, the heat-resistant temperature is a temperature at which problems such as deformation do not occur even if the substrate is exposed in a processing process such as forming a pattern of a resin film on the substrate, and for a resin film, it depends on the degree of stretching treatment. Although it varies, it is necessary that at least the glass transition temperature (Tg) is not exceeded. Further, a substrate in which electrodes such as ITO and gold are vapor-deposited or patterned on a resin film can be exemplified.

In addition, as an example of another substrate used in the manufacturing method of the present invention, a thin film having high heat resistance but low heat resistance is formed on the substrate itself, such as a glass substrate, a silicon wafer, or a polyimide film. I can mention things. Specific examples include a substrate with an organic device in which an organic EL (OLED) or an organic thin film transistor (TFT) is formed on a glass, a silicon wafer, or a polyimide film. The heat-resistant temperature of a substrate having low heat resistance, such as a resin film or a substrate with an organic device, varies depending on the type of resin and the device, but the heat-resistant temperature of a preferably used substrate is 80 to 140. ℃. The substrate with an organic device includes a substrate on which a protective film, a protective film, etc. are formed after the formation of the organic device. This is because even if the heat resistance of these protective films and the protective film itself is 150 ° C or higher, if the heat resistance is substantially 140 ° C or lower in order to ensure the function of the organic device, the organic device is attached. This is because it corresponds to a substrate.

As a method of applying the solution of the photosensitive resin composition on these substrates, any of a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coater machine, a spinner machine, and the like can be used. Method can also be adopted. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and are performed at a temperature of, for example, 60 to 110 ° C. (set so as not to exceed the heat resistant temperature of the substrate) for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an ultraviolet exposure apparatus, and by exposing through a photomask, only the resist of the portion corresponding to the pattern is exposed. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far-ultraviolet lamp to photocure the photosensitive resin composition in the coating film. Preferably, it is photocured by irradiating a certain amount of light having a wavelength of 365 nm.

Alkaline development after exposure is performed for the purpose of removing the resist in the unexposed portion, and this development forms a desired pattern. Examples of the developing solution suitable for this alkaline development include an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and in particular, sodium carbonate, potassium carbonate, and lithium carbonate. It is preferable to develop at a temperature of 23 to 28 ° C. using a weak alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as, and to obtain a fine image using a commercially available developer or an ultrasonic cleaning machine. Can be formed precisely.

After development, heat treatment (post-baking) is preferably performed under the conditions of a temperature of 80 to 140 ° C. (set so as not to exceed the heat resistant temperature of the substrate) and 20 to 90 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned resin film and the substrate. This is done by heating in an oven, hot plate, etc., similar to pre-baking. A more preferable range of heat treatment conditions for post-baking is a temperature of 90 to 120 ° C. and a heating time of 30 to 60 minutes. The patterned resin film of the present invention is formed through each step by the above photolithography method.

As described above, the method for producing a resin film pattern of the present invention is suitably used for forming a resin film pattern on a substrate having a low heat resistant temperature by operations such as exposure and alkaline development. It is also suitable when a fine resin film pattern is required. Specifically, when using a substrate having a low heat resistant temperature, various insulating films, colored films for color filters, partition materials for forming organic EL pixels (for the case of forming RGB by the inkjet method, etc.), and insulation for touch panels. It is useful for forming films and light-shielding films, and these resin film-patterned substrates are used for display devices such as liquid crystals and organic EL, for photographing elements, and for touch panel members (main applications are for displays and touch panels). It is possible to use a substrate).

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The preparation of the photosensitive resin composition used in the method for producing a resin film pattern formation of the present invention will be described, and the evaluation results of the characteristics of the cured product of the photosensitive resin composition will be described.

First, an example of synthesizing (A) a polymerizable unsaturated group-containing alkali-soluble resin is shown. The evaluation of the resin in the synthetic example was performed as follows.
[Solid content concentration]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)], weighed [W1 (g)], and heated at 160 ° C. for 2 hours, and then weight [W2 (g)]. It was calculated from the following equation.
Solid content concentration (% by weight) = 100 × (W2-W0) / (W1-W0).

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator [manufactured by Hiranuma Sangyo Co., Ltd., trade name COM-1600].

[Molecular weight]
Gel Permeation Chromatography (GPC) [Product name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 (1) [manufactured by Tosoh Corporation], temperature: 40 ° C, rate: 0.6 ml / min], and the weight average molecular weight (Mw) as a conversion value of standard polystyrene [PS-oligoform kit manufactured by Tosoh Corporation]. I asked.

The abbreviations used in the synthetic example and the comparative synthetic example are as follows.
DCPMA: Dicyclopentanyl methacrylate GMA: Glycydyl methacrylate St: Styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (9,9-bis (4-hydroxyphenyl) Reaction of fluorene with chloromethyloxylan Stuff.)
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride THPA: tetrahydrophthalic anhydride DMPA: dimethylol propionic acid IDICA: isophorone diisocyanate PTMA: pentaerythritol tetra (mercaptoacetate)
DPHA: Mix of dipentaerythritol pentaacrylate and hexaacrylate AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine TPP: Triphenylfuphosphine BzDMA: benzyldimethylamine PGMEA: Propylene glycol monomethyl Ether acetate

[Synthesis Example 1]
300 g of PGMEA was placed in a 1 L four-necked flask equipped with a return condenser, the inside of the flask system was replaced with nitrogen, and then the temperature was raised to 120 ° C. In this flask, a monomer mixture (a mixture of 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 10 g of AIBN in 31.2 g (0.30 mol) of St) was added dropwise from the funnel for 2 hours. The mixture was added dropwise and stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Then, after replacing the inside of the flask with air, 24.0 g of AA (95% of glycidyl group), 0.8 g of TDMP and 0.15 g of HQ were added to the obtained copolymer solution, and 6 hr under heating at 120 ° C. The mixture was stirred to obtain a polymerizable unsaturated group-containing copolymer solution.
Further, 30.0 g of SA (90% of the number of moles added with AA) and 0.5 g of TEA were added to the obtained polymerizable unsaturated group-containing copolymer solution and reacted at 120 ° C. for 4 hours to obtain a polymerizable unsaturated group-containing alkali. A soluble copolymer resin solution (A) -1 was obtained. The solid content concentration of the resin solution was 46% by mass, the acid value (in terms of solid content) was 76 mgKOH / g, and the Mw by GPC analysis was 5300.

[Synthesis Example 2]
114.4 g (0.23 mol) of BPFE in a 500 ml four-necked flask with a return condenser,
33.2 g (0.46 mol) of AA, 157 g of PGMEA and 0.48 g of TEAB were charged, and the mixture was reacted by stirring at 100 to 105 ° C. under heating for 20 hours. Next, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were charged in a flask, and the mixture was stirred under heating at 120 to 125 ° C. for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin. (A) -2 was obtained. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (in terms of solid content) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

[Synthesis Example 3]
In a 500 mL four-necked flask with a return cooler, 104.2 g (0.29 mol) of bisphenol A type epoxy compound (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name YD-128, epoxy equivalent = 182), AA41. 2 g (0.57 mol), 1.50 g of TPP, and 40.0 g of PGMEA were charged and stirred for 12 hours under heating at 100 to 105 ° C. to obtain a reaction product.
Then, 17.4 g (0.13 mol) of DMPA and 84 g of PGMEA were charged into the obtained reaction product, and the temperature was raised to 45 ° C. Next, 61.8 g (0.28 mol) of IDICA was added dropwise, paying attention to the temperature inside the flask. After completion of the dropping, the mixture was stirred for 6 hours under heating at 75 to 80 ° C. Further, 21.0 g (0.14 mol) of THPA was charged and stirred for 6 hours under heating at 90 to 95 ° C. to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -3. The solid content concentration of the obtained resin solution was 66.6% by mass, the acid value (in terms of solid content) was 61 mgKOH / g, and the Mw by GPC analysis was 11860.

[Synthesis Example 4]
20 g of PTMA (0.19 mol of mercapto group), 212 g of DPHA (2.12 mol of acrylic group), 58 g of PGMEA, 0.1 g of HQ, and 0.01 g of BzDMA were added to a 1 L 4-necked flask and reacted at 60 ° C. for 12 hours. , Dendrite polymer solution (B) -3 The solid content concentration was 80% by mass. The disappearance of the mercapto group was confirmed by the iodometry method for the obtained dendritic polymer. The Mw of the obtained dendritic polymer was 10,000.

［評価］
実施例１～５６及び比較例１～５６の感光性樹脂組成物を用いて、以下に記す評価を行った。実施例１～１４および比較例１～１４の結果を表９に、実施例１５～２８および比較例１５～２８の結果を表１０に、実施例２９～４２および比較例２９～４２の結果を表１１に、実施例４３～５６および比較例４３～５６の結果を表１２に示す。 (Preparation of photosensitive resin composition)
Regarding the formulation of the photosensitive resin composition when the colorant concentration (Pcon) is 0%, Examples 1 to 14 are shown in Table 1, Comparative Examples 1 to 14 are shown in Table 2, and the photosensitive resin composition when Pcon is 20%. About the formulation Examples 15 to 28 are shown in Table 3, Comparative Examples 15 to 28 are shown in Table 4, and Examples 29 to 42 are shown in Table 5 regarding the formulation of the photosensitive resin composition in the case of Pcon 40%, and Comparative Examples 29 to 42. In Table 6, Examples 43 to 56 were prepared as shown in Table 7, and Comparative Examples 43 to 56 were prepared as shown in Table 8 regarding the formulation of the photosensitive resin composition in the case of Pcon 60%. Each component used in the formulation is as follows, and all the values in the table are parts by mass.
(A) Polymerizable unsaturated group-containing alkali-soluble resin:
(A) -1: Resin solution obtained in Synthesis Example 1 (solid content concentration 46.0% by mass)
(A) -2: Resin solution obtained in the above synthesis example 2 (solid content concentration 56.1% by mass)
(A) -3: Resin solution obtained in Synthetic Example 3 (solid content concentration 66.6% by mass)
(B) Photopolymerizable monomer:
(B) -1: Mixture of pentaerythritol triacrylate and tetraacrylate (trade name M-450 manufactured by Toagosei Co., Ltd., acrylic equivalent 88)
(B) -2: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent 96-115)
(B) -3: Dendrite polymer solution obtained in Synthesis Example 4 (solid content concentration 80.0% by mass)
(C) Epoxy compound:
(C) -1: 3,4-Epoxycyclohexanecarboxylic acid (3', 4'-epoxycyclohexyl) methyl (Seroxide 2021P manufactured by Daicel, Epoxy equivalent 135)
(C) -2: Triphenylmethane type epoxy resin (EPPN-501H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 160)
(C) -3: 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct (Daicel's "EHPE3150", epoxy equivalent 180)
(D) Epoxy compound curing agent and curing accelerator:
(D) -1: Phthalic anhydride (D) -2: Benzene-1,2,4-tricarboxylic acid-1,2-anhydride (D) -3: 1,8-diazabicyclo [5.4.0] PGMEA solution containing 2% by mass of undeca-7-ene (manufactured by San-Apro, DBU (R))
(E) Photopolymerization Initiator: Oxime Ester-based Photopolymerization Initiator (ADEKA Cools NCI-831)
(F) Solvent:
(F) -1: PGMEA
(F) -2: Diethylene glycol methyl ethyl ether (EDM)
(G) Colorant:
(G) -1: Pigment dispersion of PGMEA solvent with 25% by mass of resin-coated carbon black and 5% by mass of polymer dispersant (solid content concentration 30% by mass)
(G) -2: Pigment dispersion of PGMEA solvent containing 20% by mass of titanium black and 5% by mass of polymer dispersant (solid content concentration 25% by mass)
(H) Surfactant: Megafuck 475 (manufactured by DIC Corporation)

[evaluation]
The evaluations described below were performed using the photosensitive resin compositions of Examples 1 to 56 and Comparative Examples 1 to 56. The results of Examples 1 to 14 and Comparative Examples 1 to 14 are shown in Table 9, the results of Examples 15 to 28 and Comparative Examples 15 to 28 are shown in Table 10, and the results of Examples 29 to 42 and Comparative Examples 29 to 42 are shown. Table 11 shows the results of Examples 43 to 56 and Comparative Examples 43 to 56.

<Evaluation of development characteristics (pattern line width / pattern linearity)>
Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.2 μm, and at 90 ° C. Prebaked for 1 minute. After that, the exposure gap was adjusted to 100 μm, a negative photomask with a line / space of 10 μm / 50 μm was placed on the dry coating film, and an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² was used to generate 50 mJ / cm ² ultraviolet rays. Was irradiated, and a photocuring reaction of the photosensitive portion was carried out.

Next, the exposed coating film was subjected to +10 seconds and +20 seconds from the development time (break time = BT) at which the pattern began to appear at a shower pressure of 1 kgf / cm ² with a 0.04% potassium hydroxide aqueous solution at 25 ° C. After development, a 5 kgf / cm ² pressure spray water wash was performed to remove the unexposed portion of the coating film to form a resin film pattern on the glass substrate, and then a heat post was performed at 100 ° C. for 60 minutes using a hot air dryer. Bake. The line width and pattern linearity of the obtained resin film pattern with respect to the mask width of the 10 μm line were evaluated.

Pattern line width: Measure the pattern line width with a mask width of 10 μm using a length measuring microscope (“XD-20” manufactured by Nikon Corporation). bottom.
Pattern linearity: Observe the 10 μm mask pattern after post-baking with an optical microscope. Was evaluated as ×.
The pattern line width and the pattern linearity were evaluated in the case of BT + 10 seconds and the case of BT + 20 seconds.

<Evaluation of OD / μm>
Each photosensitive resin composition containing the colorant obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm. , Prebaked at 90 ° C. for 1 minute. Then, without covering with a negative photomask, an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW / cm ² was irradiated with ultraviolet rays of 80 mJ / cm ² , and a photocuring reaction was carried out.

Next, this exposed coated plate was developed at 25 ° C. using a 0.05% potassium hydroxide aqueous solution at a shower pressure of 1 kgf / cm ² for 60 seconds, then washed with spray water at 5 kgf / cm ² pressure, and then hot air was washed. It was heat post-baked at 120 ° C. for 60 minutes using a dryer. The OD value of this coated plate was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the colored film formed on the coated plate was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD / μm.

<Evaluation of solvent resistance>
The solvent resistance of the formed coating film (light-shielding film) was evaluated using the coated plate (glass plate with light-shielding film) prepared in the same manner as in the OD evaluation. Rub continuously 20 times with a waste cloth soaked in PGMEA, observe the surface condition, and if the surface of the coating film is not dissolved and is not scratched, it is solvent resistant ○, and the surface of the coating film is dissolved or softened. When it was scratched, it was rated as solvent resistance x. In addition, when dissolution and scratches were limited to a small part, it was marked as Δ.

The photosensitive resin composition of the present invention has a line width of 3 to 15 μm, particularly development adhesion and straight line at a line width of 3 to 15 μm or less, even if the process of forming a resin film pattern does not include a step of thermosetting at a temperature exceeding 140 ° C. It is possible to form a resin film pattern having excellent properties and good solvent resistance. Therefore, for resin films such as PET and PEN having a heat resistant temperature of 140 ° C. or lower, or for a substrate with an organic device provided with an organic EL or an organic TFT on a glass substrate or a silicon wafer, the above-mentioned It is possible to form a resin film pattern having such characteristics.
The photosensitive resin composition of the present invention has a heat-resistant temperature of a resin film such as a transparent film pattern, an insulating film pattern, a black matrix, a partition wall pattern, etc., which are required for forming a color filter, an organic EL pixel, or a touch panel, for example. It is suitable for being provided on a low substrate, and these substrates with a resin film can be used for manufacturing display devices such as liquid crystals and organic EL, and for manufacturing solid-state photographing elements such as CMOS and touch panels. It will be like.

Claims (7)

A photosensitive resin composition is applied onto a substrate having a heat resistant temperature of 140 ° C. or lower, exposed through a photomask, an unexposed portion is removed by development, and then heated at 140 ° C. or lower to obtain a predetermined resin film. A photosensitive resin composition used for forming a pattern to produce a substrate with a resin film.
(A) Unsaturated group-containing alkali-soluble resin,
(B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds,
(C) Epoxy compound,
(D) Epoxy compound curing agent and / or curing accelerator,
(E) Photopolymerization initiator,
(F) Solvent,
Including
The epoxy compound of the C component has an epoxy equivalent of 100 to 300 g / eq.
The curing agent for component D is a polyvalent carboxylic acid compound,
The photopolymerization initiator of the E component is an acyloxime-based photopolymerization initiator.
A photosensitive resin composition characterized in that the total amount of the C component and the D component is 6 to 24% by mass in the solid content excluding the F component. (G) The photosensitive resin composition according to claim 1, further comprising a colorant composed of an organic pigment or an inorganic pigment. The photosensitive resin composition according to claim 2, wherein the colorant of the G component is a light-shielding material composed of an organic black pigment or an inorganic black pigment. The photosensitive resin composition according to any one of claims 1 to 5, wherein an acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10,000 or more at 365 nm is used as the photopolymerization initiator of the E component. The photosensitive resin composition according to claim 6, wherein the photopolymerization initiator of the component E is an acyloxime-based photopolymerization initiator of the general formula (1).

R ¹ and R ² independently represent an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20 or a heterocyclic group of C4 to C12, and R ³ is an alkyl of C1 to C15. Represents a group, an aryl group of C6 to C18, and an arylalkyl group of C7 to C20. Here, the alkyl group and the aryl group may be substituted with an alkyl group of C1 to C10, an alkoxy group of C1 to C10, an alkanoyl group of C1 to C10, or a halogen, and the alkylene moiety may be substituted with an unsaturated bond or an ether bond. It may contain a thioether bond and an ester bond. Further, the alkyl group may be a linear, branched, or cyclic alkyl group. The photosensitive resin composition according to any one of claims 1 to 7, wherein the unsaturated group-containing alkali-soluble resin of the component A is an unsaturated group-containing alkali-soluble resin represented by the general formula (2).

(In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ⁸ is a hydrogen atom or a methyl group. , A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- , Fluolene-9,9-diyl group or direct bond, X represents _a tetravalent carboxylic _acid residue, Y1 and Y2 are independently hydrogen atoms or -OC-Z- (COOH) m, respectively. (However, Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20.) It is a method of manufacturing a substrate with a resin film by forming a resin film pattern on a substrate having a heat resistant temperature of 140 ° C. or lower.
As the photosensitive resin composition used for forming the resin film pattern, the photosensitive resin composition according to claim 1 is used, the photosensitive resin composition is applied onto a substrate, and the photosensitive resin composition is applied via a photomask. A method for manufacturing a substrate with a resin film, which comprises exposing, removing an unexposed portion by development, and then heating at 140 ° C. or lower to form a predetermined resin film pattern.