JP2016014877A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition having excellent pattern forming capability in a photolithography process.SOLUTION: The present invention relates to the negative photosensitive resin composition. The negative photosensitive resin composition contains an alkali-soluble resin (A) containing a first resin and a second resin respectively containing repeating units represented by specific structures, a polymerizable compound (B), a polyfunctional thiol compound (C) having three or more functional groups, a photopolymerization initiator (D), and a solvent (E), and the mixing weight ratio of the first resin to the second resin is 50:50-90:10. Thus, the negative photosensitive resin composition is capable of forming a pattern excellent in reactivity and durability even in a low-temperature curing condition.

Description

  The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition capable of forming a pattern excellent in reactivity and durability even under low temperature curing conditions.

  In the display field, the photosensitive resin composition is used to form various photocuring patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocured pattern. In this process, the yield in the process is improved and the physical properties to be applied are improved. Therefore, a photosensitive resin composition having high sensitivity is required.

  The pattern formation of the photosensitive resin composition is based on photolithography, that is, a change in the polarity of a polymer caused by a photoreaction and a crosslinking reaction. In particular, the property of changing solubility in a solvent such as an alkaline aqueous solution is used after exposure.

  Pattern formation by the photosensitive resin composition is classified into a positive type and a negative type depending on the solubility of the exposed portion with respect to development. In the positive type photoresist, the exposed portion is dissolved by the developer, and in the negative type photoresist, the exposed portion is not dissolved in the developer, and the unexposed portion is dissolved, thereby forming a pattern. It is a method. The positive type and the negative type are different from each other depending on the binder resin, the crosslinking agent, and the like used.

  Recently, the use of touch screens equipped with touch panels has increased explosively, and recently, flexible touch screens have attracted attention. As a result, materials such as various substrates used in touch screens must have flexible characteristics, so that usable materials are also limited to flexible polymer materials, and the manufacturing process is also performed under milder conditions. Is required.

  As a result, the curing conditions of the photosensitive resin composition are not the conventional high-temperature curing, but the need for low-temperature curing is required, but low-temperature curing is a problem of reduced reactivity and reduced durability of the formed pattern. There is.

  In Korean Registered Patent No. 10-1305088, a negative polymer that is excellent in heat resistance and light resistance and can improve sensitivity by including a copolymer polymerized using a cyclohexenyl acrylate monomer. It describes about the photosensitive resin composition. However, the required durability cannot be achieved under low temperature curing conditions.

Korean Registered Patent No. 10-1302508

An object of this invention is to provide the negative photosensitive resin composition which can be hardened | cured at low temperature, was excellent in reactivity, and was excellent in durability, such as chemical resistance of the formed pattern.

  Another object of the present invention is to provide a negative photosensitive resin composition having an excellent pattern forming ability in a photolithography process.

  Moreover, an object of this invention is to provide the photocuring pattern formed with the said photosensitive resin composition.

  1. An alkali-soluble resin (A) comprising a first resin comprising a repeating unit represented by the following chemical formula 1; a second resin comprising a repeating unit represented by the following chemical formula 2; a polymerizable compound (B); The polyfunctional thiol compound (C) higher than the functional group, the photopolymerization disclosure agent (D), and the solvent (E) are included, and the mixing weight ratio of the first resin and the second resin is 50:50. Negative type photosensitive resin composition which is -90: 10.

〔式中、Ｒ_１、Ｒ_２、及びＲ_３は、互いに独立して、水素又はメチル基であり、
Ｒ_４は、メタクリル酸、アクリル酸、２−アクリロイロキシエチルスクシナート、２−アクリロイロキシエチルヘキサヒドロフタレート、２−アクリロイロキシエチルフタレート、及び２−メタクリロイロキシエチルスクシナートからなる群から選択される単量体に由来する構造であり、
Ｒ_５は、下記式（１）〜（９）からなる群から選択される単量体に由来する構造であり、

[Wherein R ₁ , R ₂ and R ₃ are independently of each other hydrogen or a methyl group;
R ₄ consists of methacrylic acid, acrylic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-methacryloyloxyethyl succinate. A structure derived from a monomer selected from the group;
R ₅ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9),

Ｒ_６は、下記式（１０）〜（１２）からなる群から選択される単量体に由来する構造であり、

ａ＝１０〜３０ｍｏｌ％、ｂ＝３０〜６０ｍｏｌ％、ｃ＝２０〜５０ｍｏｌ％。〕

〔式中、Ｒ_７、Ｒ_８、Ｒ_９、及びＲ_１０は、互いに独立して、水素又はメチル基であり、
Ｒ_１１は、メタクリル酸、アクリル酸、２−アクリロイロキシエチルスクシナート、２−アクリロイロキシエチルヘキサヒドロフタレート、２−アクリロイロキシエチルフタレート、及び２−メタクリロイロキシエチルスクシナートからなる群から選択される単量体に由来する構造であり、
Ｒ_１２は、ベンジルメタクリレート、フェノキシエチレングリコールアクリレート、フェノキシジエチレングリコールアクリレート、（２−フェニル）フェノキシエトキシアクリレート、２−ヒドロキシ−（２−フェニル）フェノールプロピルアクリレート、２−ヒドロキシ−（３−フェニル）フェノキシプロピルアクリレート、テトラヒドロフリルアクリレート、スチレン、ビニルトルエン、ビニルナフタレン、Ｎ−ベンジルマレイミド、 メチルメタクリレート、エチルメタクリレート、メトキシエチレングリコールメタクリレート、メトキシジエチレングリコールメタクリレート、メトキシトリエチレングリコールメタクリレート、メトキシテトラエチレングリコールメタクリレート、フェノキシエチレングリコールメタクリレート、フェノキシジエチレングリコールメタクリレート、及びテトラヒドロフリルメタクリレートからなる群から選択される単量体に由来する構造であり、
Ｒ_１３は、前記式（１）〜（９）からなる群から選択される前記単量体に由来する前記構造であり、
Ｒ_１４は、下記式 （１３）〜（１９）からなる群から選択される単量体に由来する構造であり、

ｄ＝１０〜３０ｍｏｌ％、ｅ＝１０〜２０ｍｏｌ％、ｆ＝３０〜６０ｍｏｌ％、ｇ＝１０〜３０ｍｏｌ％。〕

R ₆ is a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12):

a = 10-30 mol%, b = 30-60 mol%, c = 20-50 mol%. ]

[Wherein R ₇ , R ₈ , R ₉ , and R ₁₀ are each independently hydrogen or a methyl group;
R ₁₁ is composed of methacrylic acid, acrylic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-methacryloyloxyethyl succinate. A structure derived from a monomer selected from the group;
R ₁₂ is benzyl methacrylate, phenoxyethyl glycol acrylate, phenoxy diethylene glycol acrylate, (2-phenyl) phenoxy ethoxy acrylate, 2-hydroxy - (2-phenyl) phenol acrylate, 2-hydroxy - (3-phenyl) phenoxypropyl acrylate , Tetrahydrofuryl acrylate, styrene, vinyl toluene, vinyl naphthalene, N-benzylmaleimide, methyl methacrylate, ethyl methacrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, phenoxyethylene glycol methacrylate, E Bruno carboxymethyl diethyleneglycol dimethacrylate, and a structure derived from a monomer selected from the group consisting of tetrahydrofuryl methacrylate,
R ₁₃ is the structure derived from the monomer selected from the group consisting of the formulas (1) to (9),
R ₁₄ is a structure derived from a monomer selected from the group consisting of the following formulas (13) to (19):

d = 10-30 mol%, e = 10-20 mol%, f = 30-60 mol%, g = 10-30 mol%. ]

  2. The negative photosensitive resin composition according to Item 1, wherein the mixing weight ratio of the first resin and the second resin is 70:30 to 80:20.

  3. The negative photosensitive resin composition according to item 1, wherein the first resin has a weight average molecular weight of 6,000 to 12,000.

  4). The negative photosensitive resin composition according to item 1, wherein the second resin has a weight average molecular weight of 20,000 to 30,000.

  5. In the said item 1, the said polyfunctional thiol compound is a negative photosensitive resin composition which is a thiol compound more than tetrafunctional.

  6). In the said item 1, the negative photosensitive resin composition which can be hardened | cured at the low temperature of 70-100 degreeC.

  7). The photocuring pattern formed with the negative photosensitive resin composition of any one item of the said items 1-6.

  8). In the item 7, the photocuring pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer. Curing pattern.

  9. The image display apparatus containing the photocuring pattern of the said item 7.

  The photosensitive resin composition of the present invention exhibits excellent reactivity at low temperature curing, and the pattern produced thereby exhibits high durability such as excellent chemical resistance and heat resistance.

  Moreover, the photosensitive resin composition of this invention shows the outstanding pattern formation capability.

  The present invention provides an alkali-soluble resin (A) containing a first resin containing a repeating unit represented by Chemical Formula 1, a second resin containing a repeating unit represented by Chemical Formula 2, and a polymerizable compound (B). A trifunctional or higher polyfunctional thiol compound (C), a photopolymerization disclosure agent (D), and a solvent (E) are included, and the mixing weight ratio of the first resin and the second resin is 50 : 50-90: 10, and relates to a negative photosensitive resin composition capable of forming a pattern having excellent reactivity and durability even under low-temperature curing conditions.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a polymerizable monomer compound (B), a trifunctional or higher polyfunctional thiol compound (C), a photopolymerization disclosure agent (D), and a solvent ( E).

Alkali-soluble resin (A)
The alkali-soluble resin (A) used in the present invention is a component that imparts solubility to an alkali developer used in a development processing step when forming a pattern, and includes a repeating unit represented by the following chemical formula 1. 1 resin and the 2nd resin containing the repeating unit shown by following Chemical formula 2.

〔式中、Ｒ_１、Ｒ_２、及びＲ_３は、互いに独立して、水素又はメチル基であり、
Ｒ_４は、メタクリル酸、アクリル酸、２−アクリロイロキシエチルスクシナート、２−アクリロイロキシエチルヘキサヒドロフタレート、２−アクリロイロキシエチルフタレート、及び２−メタクリロイロキシエチルスクシナートからなる群から選択される単量体に由来する構造であり、
Ｒ_５は、下記式（１）〜（９）からなる群から選択される単量体に由来する構造であり、

Ｒ_６は、下記式（１０）〜（１２）からなる群から選択される単量体に由来する構造であり、

ａ＝１０〜３０ｍｏｌ％、ｂ＝３０〜６０ｍｏｌ％、ｃ＝２０〜５０ｍｏｌ％。〕

〔式中、Ｒ_７、Ｒ_８、Ｒ_９、及びＲ_１０は、互いに独立して、水素又はメチル基であり、
Ｒ_１１は、メタクリル酸、アクリル酸、２−アクリロイロキシエチルスクシナート、２−アクリロイロキシエチルヘキサヒドロフタレート、２−アクリロイロキシエチルフタレート、及び２−メタクリロイロキシエチルスクシナートからなる群から選択される単量体に由来する構造であり、
Ｒ_１２は、ベンジルメタクリレート、フェノキシエチレングリコールアクリレート、フェノキシジエチレングリコールアクリレート、（２−フェニル）フェノキシエトキシアクリレート、２−ヒドロキシ−（２−フェニル）フェノールプロピルアクリレート、２−ヒドロキシ−（３−フェニル）フェノキシプロピルアクリレート、テトラヒドロフリルアクリレート、スチレン、ビニルトルエン、ビニルナフタレン、Ｎ−ベンジルマレイミド、メチルメタクリレート、エチルメタクリレート、メトキシエチレングリコールメタクリレート、メトキシジエチレングリコールメタクリレート、メトキシトリエチレングリコールメタクリレート、メトキシテトラエチレングリコールメタクリレート、フェノキシエチレングリコールメタクリレート、フェノキシジエチレングリコールメタクリレート、及びテトラヒドロフリルメタクリレートからなる群から選択される単量体に由来する構造であり、
Ｒ_１３は、前記式（１）〜（９）からなる群から選択される単量体に由来する構造であり、
Ｒ_１４は、下記式（１３）〜（１９）からなる群から選択される単量体に由来する構造であり、

ｄ＝１０〜３０ｍｏｌ％、ｅ＝１０〜２０ｍｏｌ％、ｆ＝３０〜６０ｍｏｌ％、ｇ＝１０〜３０ｍｏｌ％。〕。

[Wherein R ₁ , R ₂ and R ₃ are independently of each other hydrogen or a methyl group;
R ₄ consists of methacrylic acid, acrylic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-methacryloyloxyethyl succinate. A structure derived from a monomer selected from the group;
R ₅ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9),

R ₆ is a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12):

a = 10-30 mol%, b = 30-60 mol%, c = 20-50 mol%. ]

[Wherein R ₇ , R ₈ , R ₉ and R ₁₀ are each independently hydrogen or a methyl group;
R ₁₁ is composed of methacrylic acid, acrylic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-methacryloyloxyethyl succinate. A structure derived from a monomer selected from the group;
R ₁₂ is benzyl methacrylate, phenoxyethyl glycol acrylate, phenoxy diethylene glycol acrylate, (2-phenyl) phenoxy ethoxy acrylate, 2-hydroxy - (2-phenyl) phenol acrylate, 2-hydroxy - (3-phenyl) phenoxypropyl acrylate , Tetrahydrofuryl acrylate, styrene, vinyl toluene, vinyl naphthalene, N-benzylmaleimide, methyl methacrylate, ethyl methacrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, phenoxyethylene glycol methacrylate, F A structure derived from a monomer selected from the group consisting of enoxydiethylene glycol methacrylate and tetrahydrofuryl methacrylate,
R ₁₃ is a structure derived from a monomer selected from the group consisting of the formulas (1) to (9),
R ₁₄ is a structure derived from a monomer selected from the group consisting of the following formulas (13) to (19):

d = 10-30 mol%, e = 10-20 mol%, f = 30-60 mol%, g = 10-30 mol%. ].

  In the present invention, each repeating unit represented by Chemical Formulas 1 and 2 should not be construed as limited as shown in Chemical Formulas 1 and 2, and within the mol% range in which the sub-repeating units in parentheses are defined. It can be freely located at any position of the chain. That is, each parenthesis of Chemical Formulas 1 and 2 is shown as one block to express mol%, but each sub-repeating unit is not limited as long as it is within the corresponding resin. Each may be located separately.

〔式中、Ｒ_１、Ｒ_２、及びＲ_３は、互いに独立して、水素又はメチル基であり、ａ＝１０〜３０ｍｏｌ％、ｂ＝３０〜６０ｍｏｌ％、ｃ＝２０〜５０ｍｏｌ％。〕 Preferable examples of the compound of Formula 1 according to the present invention include the compound of Formula 1-1 below.

_Wherein, R 1, _{R 2,} and _{R 3,} independently of one another are hydrogen or methyl, a = 10~30mol%, b = 30~60mol%, c = 20~50mol%. ]

〔式中、Ｒ_７、Ｒ_８、Ｒ_９、及びＲ_１０は、互いに独立して、水素又はメチル基であり、ｄ＝１０〜３０ｍｏｌ％、ｅ＝１０〜２０ｍｏｌ％、ｆ＝３０〜６０ｍｏｌ％、ｇ＝１０〜３０ｍｏｌ％。〕 Moreover, as a preferable example of the compound of Chemical formula 2 by this invention, the compound of the following Chemical formula 2-1 is mentioned.

[Wherein R ₇ , R ₈ , R ₉ and R ₁₀ are independently of each other hydrogen or a methyl group, d = 10 to 30 mol%, e = 10 to 20 mol%, f = 30 to 60 mol%. G = 10-30 mol%. ]

  The first resin according to the present invention has a function of improving the chemical resistance and reactivity of the photosensitive resin composition, and the weight average molecular weight of the first resin is 6,000 to 12,000. It is preferable that The most excellent reactivity and chemical resistance can be exhibited in the molecular weight range.

  The second resin according to the present invention has a function of improving the durability of the photosensitive resin composition such as pattern formability and heat resistance, and the weight average molecular weight of the second resin is 20,000 in this aspect. It is preferably ˜30,000. The most excellent pattern formability, heat resistance, etc. in the molecular weight range can be exhibited.

    The mixing weight ratio of the first resin and the second resin according to the present invention may be 50:50 to 90:10, and preferably 70:30 to 80:20. If the content of the first resin is less than that of the second resin, the low-temperature curability is lowered and a post-development residue is generated. When the content of the first resin exceeds 9 times the weight of the second resin, the pattern formability is lowered.

  The first resin and the second resin according to the present invention further include, independently of each other, repeating units formed of other monomers known in the art in addition to the repeating units of Chemical Formulas 1 and 2. Can be formed only in the repeating unit of Formula 1.

  The monomer that forms a repeating unit that can be further added to Chemical Formulas 1 and 2 is not particularly limited, but examples thereof include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid, and the like. Anhydrides; mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene Fragrance such as p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Tribe Compound: N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N N-substituted maleimide compounds such as -m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide; ) Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, etc. Alkyl (meth) acrylates; cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, alicyclic (meth) acrylates such as 2-dicyclopentanyloxyethyl (meth) acrylate; phenyl (meth) acrylate Aryl (meth) acrylates such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3 Unsaturated oxetane compounds such as-(methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane; methyl glycidyl (meth) Acrylate Unsaturated oxirane compound of; substituted cycloalkane or di cycloalkane ring having 4 to 16 carbon atoms (meth) acrylate; and the like. These can be used individually or in mixture of 2 or more types.

  The alkali-soluble resin (A) preferably has an acid value in the range of 20 to 200 (KOHmg / g). If the acid value is within the above range, excellent developability and stability over time can be obtained.

  Although content of alkali-soluble resin (A) is not specifically limited, For example, it is 10-90 mass parts with respect to 100 mass parts of photosensitive resin compositions on the basis of solid powder, Preferably it is 25-70 mass parts. May be included. When it is contained within the above numerical range, the solubility in the developer is sufficient, so that the developability is good and a photocured pattern having excellent mechanical properties can be formed.

Polymerizable compound (B)
The polymerizable compound (B) used in the photosensitive resin composition of the present invention can increase the crosslink density during the production process and enhance the mechanical properties of the photocuring pattern.

  As the polymerizable compound (B), those used in the art can be used without particular limitation, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers. Although a kind is not specifically limited, The following compound is mentioned as the example.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol. Examples thereof include bis (acryloyloxyethyl) ether of A and 3-methylpentanediol di (meth) acrylate. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) An acrylate etc. are mentioned. Of these, polyfunctional monomers having two or more functions are preferably used.

  Although content of the said polymeric compound (B) is not specifically limited, For example, 10-90 mass parts with respect to 100 mass parts of alkali-soluble resin on the basis of the solid powder in the photosensitive resin composition, Preferably it is 30. It is used in the range of ˜80 parts by mass. When a polymeric compound (B) is contained in the said content range, it can have outstanding durability and can improve the developability of a composition.

Multifunctional thiol compound (C)
The polyfunctional thiol compound according to the present invention is a tri- or higher functional thiol compound, which improves the crosslink density, improves the durability of the photocuring pattern and the adhesion to the substrate, and prevents yellowing at high temperatures. To function.

〔式中、Ｚ_１は、メチレン基又は炭素数２〜１０の直鎖又は分岐鎖であるアルキレン基又はアルキルメチレン基であり、Ｙは単結合、−ＣＯ−、−Ｏ−ＣＯ−又は−ＮＨＣＯ−であり、ｎが３〜１０の整数であり、Ｘが１個又は複数のエーテル結合を有することができる炭素数２〜７０のｎ価の炭化水素基であるか、或いはｎが３であり、Ｘが下記化学式４で示される３価の基である。〕 The trifunctional or higher polyfunctional thiol compound according to the present invention is not particularly limited as long as it is a trifunctional or higher functional thiol compound and can be used in the photosensitive resin composition, and a tetrafunctional or higher functional thiol compound is preferable. . The thiol compound according to the present invention can be represented by the following chemical formula 3, for example.

[In the formula, Z ₁ represents a methylene group or an alkylene group or an alkylmethylene group which is a linear or branched chain having 2 to 10 carbon atoms, and Y represents a single bond, —CO—, —O—CO— or —NHCO. -, N is an integer of 3 to 10, and X is an n-valent hydrocarbon group having 2 to 70 carbon atoms that can have one or more ether bonds, or n is 3. , X is a trivalent group represented by the following chemical formula 4. ]

〔式中、Ｚ_２、Ｚ_３、及びＺ_４は、互いに独立して、メチレン基又は炭素数２〜６のアルキレン基であり、「＊」は結合手を示す。〕

[Wherein, Z ₂ , Z ₃ and Z ₄ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond. ]

  N in Chemical Formula 3 is preferably 4 or more, or an integer of 4 to 10, and more preferably 4, 6 or 8.

  Examples of X when n in Chemical Formula 3 is 3 include a trivalent group represented by the following Chemical Formula 5. Examples of X when n in Chemical Formula 3 is 4, 6, or 8 include, for example, Preferred examples include 4, 6 or 8 valent groups represented by Chemical Formula 6.

〔式中、「＊」は結合手を示す。〕

[In the formula, “*” represents a bond. ]

〔式中、ｍは、０〜２の整数であり、「＊」は結合手を示す。〕

[Wherein, m is an integer of 0 to 2, and “*” represents a bond. ]

  Although content of the polyfunctional thiol compound (C) by this invention is not specifically limited, For example, 0.1-15 with respect to 100 mass parts of alkali-soluble resin on the basis of the solid powder in the photosensitive resin composition. It is used in the range of 1 part by mass, preferably 1-10 parts by mass. When the polyfunctional thiol compound (C) is contained in the above content range, excellent low-temperature curing performance can be achieved.

Photopolymerization disclosure agent (D)
If the photopolymerization disclosure agent (D) by this invention can superpose | polymerize the said polymeric compound (B), the kind in particular will not be restrict | limited, It can use. For example, at least one compound selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, a thioxanthone compound, and an oxime ester compound can be used, and preferably an oxime ester It is preferable to use a system compound.

  Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy). Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4-methylbenzyl)- 2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like can be mentioned.

  Specific examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4- Diethylamino-2-methylphenol Nyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. .

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'- Examples thereof include tetraphenyl-1,2′-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group, preferably 2,2′-bis (2 − Lorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 -Bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole and the like.

  Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and 1,2-octadion-1- (4-phenylthio) phenyl-2- (o-benzoyl). Oxime) or ethanone, 1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) -1- (o-acetyloxime), and the like. As commercially available products, CGI-124 (Ciba Geigy), CGI-224 (Ciba Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeka), NCI-831 ( Adeka).

  In addition, the photopolymerization initiator (D) may further include a photopolymerization initiation auxiliary agent in order to improve the sensitivity of the photosensitive resin composition of the present invention. When the photosensitive resin composition according to the present invention contains a photopolymerization initiation assistant, the sensitivity is further increased and the productivity can be improved.

  Examples of the photopolymerization initiation aid include one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group.

  Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid-2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4′-bis (Diethylamino) benzophenone and the like can be mentioned, and it is preferable to use an aromatic amine compound.

  Specific examples of the carboxylic acid compound are preferably aromatic heteroacetic acids such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthiol. Examples include acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl). -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), penta Examples include erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).

  Although content of the said photopolymerization disclosure agent (D) is not specifically limited, For example, it is 0.1-10 mass parts with respect to 100 mass parts of the whole photosensitive resin composition on the basis of solid powder. It may be contained, and may be contained preferably in an amount of 0.1 to 5 parts by mass. When the numerical value range is satisfied, the exposure time is shortened by increasing the sensitivity of the photosensitive resin composition, so that productivity can be improved and high resolution can be maintained, and the strength of the formed pixel portion and the pixel portion It is preferable at the point from which the smoothness in the surface of becomes favorable.

Solvent (E)
Any solvent (E) can be used without limitation as long as it is usually used in the art.

  Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl. Diethylene glycol dialkyl ethers such as ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl Propylene glycol dialkyl ethers such as ether and propylene glycol ethyl propyl ether; propylene glycol alkyl such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate Ether propionates; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol; Butanediol monoalkyl such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate Alkyl ether acetates; methoxybu Butanediol monoalkyl ether propionates such as tilpropionate, ethoxybutylpropionate, propoxybutylpropionate, butoxybutylpropionate; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl Dipropylene glycol dialkyl ethers such as ethers; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol, hexanol , Cyclohexanol, ethylene glycol, glycerin and other alcohols; methyl acetate, ethyl acetate, propyl acetate, butyl acetate , Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, lactic acid Propyl, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate , Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, propo Butyl butyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-butoxy Butyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl onate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butoxypropion Examples include esters such as methyl acid, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ-butyrolactone, and the like. These can be used alone or in admixture of two or more.

  In consideration of coating properties and drying properties, the solvent is alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate Esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. May be used.

  Content of the said solvent (E) may be contained in the quantity of 40-95 mass parts with respect to 100 mass parts of the whole photosensitive resin composition, Preferably, it is 45-85 mass parts. When the above range is satisfied, the coating property is improved when coating is performed with a coating apparatus such as a spin coater, a slit and spin coater, a slit coater (sometimes referred to as “die coater” or “curtain flow coater”), and an ink jet. Therefore, it is preferable.

Additive (E)
The photosensitive resin composition according to the present invention includes a filler, other polymer compound, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, a chain transfer agent, and the like as necessary. These additives may be further included.

  Specific examples of the filler include glass, silica, alumina and the like.

  Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Is mentioned.

  The said hardening | curing agent is used in order to raise deep part hardening and mechanical strength, and an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound etc. are mentioned as a specific example of a hardening | curing agent.

  Specific examples of the epoxy compound in the curing agent include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, and other aromatic types. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or bromo derivatives of such epoxy resins, epoxy resins and aliphatic, alicyclic or aromatic epoxy compounds other than bromo derivatives, Examples include butadiene (co) polymer epoxy compounds, isoprene (co) polymer epoxy compounds, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

  Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The said hardening | curing agent can use together the hardening auxiliary compound which can carry out the ring-opening polymerization of the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with the said hardening | curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like.

  What is marketed as an epoxy resin hardening | curing agent can be utilized for the said carboxylic acid anhydrides. Examples of the epoxy resin curing agent include trade name ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), Trade name RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.), trade name MH-700 (new Japan Rika ( Etc.). The curing agents exemplified above can be used alone or in admixture of two or more.

  As the leveling agent, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. You may use each individually or in combination of 2 or more types.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other than the above, the product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (Dainippon Ink Chemical Co., Ltd.) Manufactured), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by EFKA CHEMICALS), PB821 (Ajinomoto Co., Inc.) Manufactured) and the like.

  The adhesion promoter is preferably a silane compound, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl. Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Is .

  Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyl Renbis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3, 3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a , A ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like can be mentioned.

  Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

  Specific examples of the anti-aggregation agent include sodium polyacrylate.

  Specific examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

<Photocuring pattern and image display device>
An object of this invention is to provide the photocuring pattern manufactured with the said photosensitive resin composition, and the image display apparatus containing the said photocuring pattern.

  The photocuring pattern produced in the photosensitive resin composition is excellent in low temperature curability and excellent in chemical resistance, heat resistance and the like. Accordingly, in the image display device, it can be used for various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, etc., photoresist, black matrix, column spacer pattern, black column spacer. Although it can utilize for a pattern etc., it is not restrict | limited to this, Especially, it is very preferable as a photoresist pattern.

  Examples of the image display device provided with such a photocuring pattern or using the pattern during the manufacturing process include a liquid crystal display device, an OLED, a flexible display, etc., but are not limited thereto and can be applied. And all image display devices known in the art.

  A photocuring pattern can be manufactured by apply | coating the photosensitive resin composition of the above-mentioned this invention on a base material, and passing through the image development process as needed, and forming a photocuring pattern.

  First, after apply | coating the photosensitive resin composition to a board | substrate, by heating-drying, volatile components, such as a solvent, are removed and a smooth coating film is obtained.

  As the coating method, for example, spin coating, soft coating method, roll coating method, slit and spin coating, or slit coating method can be used. After application, it is heated and dried (prebaked) or dried after drying under reduced pressure to volatilize volatile components such as a solvent. Here, the heating temperature is 70 to 100 ° C., which is a relatively low temperature. The coating thickness after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and accurate alignment between the mask and the substrate is performed. When the ultraviolet ray is irradiated, the portion irradiated with the ultraviolet ray is cured.

  As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like can be used. The irradiation amount of ultraviolet rays can be appropriately selected as necessary, and is not limited in the present invention. If the cured coating film is brought into contact with a developer as necessary, and the unexposed portion is dissolved and developed, a desired pattern shape can be formed.

  As the developing method, any of a liquid addition method, a dipping method, a spray method and the like may be used. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate. Potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc.

  These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

  As the surfactant in the alkaline developer, at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or a cationic surfactant can be used.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acids. Examples include esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.

  Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecyl sodium sulfate. And alkyl aryl sulfonates such as sodium naphthalene sulfonate.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts, and the like. These surfactants can be used alone or in combination of two or more.

  The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight. After development, it is washed with water and post-baked for 10 to 60 minutes at 70 to 100 ° C., which is a relatively low temperature.

  In order to facilitate the understanding of the present invention, preferred examples are shown below, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the scope of the scope and the technical idea, and such changes and modifications are claimed in the appended claims. Of course it belongs to.

Preparation Example 1: Synthesis of alkali-soluble resin (first resin (A-1)) A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was placed in a nitrogen atmosphere, and 300 parts by mass of methyl ethyl diethylene glycol was contained therein. And heated to 70 ° C. with stirring. Subsequently, 300 parts by mass of the following chemical formulas 5 and 6 (molar ratio is 50:50), 150 parts by mass of glycidyl methacrylate, and 50 parts by mass of methacrylic acid were dissolved in 140 parts by mass of methyl ethyl diethylene glycol to prepare a solution. .

  The prepared solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of methylethyldiethylene glycol was used for 4 hours using another dropping funnel. It was dripped in the flask. After dropping of the polymerization initiator solution is completed, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature, so that the solid powder is 36.7% by mass and the acid value is 59 mg-KOH / g (in terms of solid powder). A solution of the polymer (first resin (A-1)) was obtained.

  The weight average molecular weight (Mw) of the obtained resin A-1 was 8,200, and the molecular weight distribution was 1.85.

  At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured using an HLC-8120GPC (manufactured by Tosoh Corp.) apparatus, and the column was TSK-GELG4000HXL and TSK-GELG2000HXL in series. Connected and used. The column temperature was 40 ° C., the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 mL / min, the injection volume was 50 μL, and the detector was RI. The measurement sample concentration is 0.6% by mass (solvent = tetrahydrofuran), and the standard material for calibration is TSK STANDARD POLYSYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation). Using.

  The ratio of the obtained weight average molecular weight and number average molecular weight was defined as molecular weight distribution (Mw / Mn).

Preparation Example 2: Synthesis of alkali-soluble resin (second resin (A-2)) Nitrogen was allowed to flow at 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer. Under a nitrogen atmosphere, 300 parts by mass of methyl ethyl diethylene glycol was added and heated to 70 ° C. with stirring. Next, 30 parts by mass of styrene, 45 parts by mass of methacrylic acid, 135 parts by mass of glycidyl methacrylate, 65 parts by mass of 2- (octahydro-4,7-methano-1H-inden-5-yl) methyl-2-propenoate were added to methyl ethyl diethylene glycol. A solution was prepared by dissolving in 140 parts by mass.

  The prepared solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of methylethyldiethylene glycol was used for 4 hours using another dropping funnel. It was dripped in the flask. After dropping of the solution of the polymerization initiator is completed, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature, and the solid powder is 32.4% by mass and the acid value is 31 mg-KOH / g (solid powder equivalent). A solution of the polymer (second resin (A-2)) was obtained.

  The obtained resin A-2 had a weight average molecular weight (Mw) of 28,000 and a molecular weight distribution of 3.20.

  At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured using an HLC-8120GPC (manufactured by Tosoh Corp.) apparatus, and the column was TSK-GELG4000HXL and TSK-GELG2000HXL in series. Connected and used. The column temperature was 40 ° C., the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 mL / min, the injection volume was 50 μL, and the detector was RI. The measurement sample concentration is 0.6% by mass (solvent = tetrahydrofuran), and the standard material for calibration is TSK STANDARD POLYSYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation). Using.

  The ratio of the obtained weight average molecular weight and number average molecular weight was defined as molecular weight distribution (Mw / Mn).

Preparation Example 3: Synthesis of Alkali-Soluble Resin (A-3) 182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen introducer, and the atmosphere in the flask was adjusted to nitrogen. The air was changed from nitrogen to inflow at 02 L / min, and then the temperature was raised to 100 ° C. Thereafter, 60 parts by mass of methacrylic acid, 40 parts by mass of methacrylic acid methyl ester, 20 parts by mass of 2- (octahydro-4,7-methano-1H-inden-5-yl) methyl-2-propenoate, and propylene glycol monomethyl ether acetate A solution obtained by adding 3.6 g of azobisisobutyronitrile to a mixture containing 136 g was added dropwise to the flask with a dropping funnel over 2 hours, and stirring was further continued at 100 ° C. for 5 hours. Next, 30 parts by mass of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was performed at 110 ° C. for 6 hours, whereby the solid powder acid value was 110 mgKOH / g. A coalescence (third resin (A-3)) was obtained. The polystyrene equivalent weight average molecular weight measured by GPC was 33,000, and the molecular weight distribution (Mw / Mn) was 4.0.

  At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured using an HLC-8120GPC (manufactured by Tosoh Corp.) apparatus, and the column was TSK-GELG4000HXL and TSK-GELG2000HXL in series. Connected and used. The column temperature was 40 ° C., the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 mL / min, the injection volume was 50 μL, and the detector was RI. The measurement sample concentration is 0.6% by mass (solvent = tetrahydrofuran), and the standard material for calibration is TSK STANDARD POLYSYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation). Using.

  The ratio of the obtained weight average molecular weight and number average molecular weight was defined as molecular weight distribution (Mw / Mn).

Examples and Comparative Examples Negative photosensitive resin compositions were prepared with the compositions described in Table 1 below.

Test Method A 2 inch square glass substrate (Eagle 2000, manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. The glass substrate was spin-coated with the photosensitive resin compositions prepared in the above examples and comparative examples, and then pre-baked at 90 ° C. for 125 seconds using a hot plate. After cooling the pre-baked substrate at room temperature, the exposure to 60 mJ / cm ² (365 nm standard) using an exposure machine (UX-1100SM; manufactured by Ushio Co., Ltd.) with an interval of 150 μm from the quartz glass photomask. ). At this time, a photomask in which the next pattern was formed on the same plane was used as the photomask.

  It has a regular square opening (hole pattern) which is a 30 μm square pattern, has a mutual interval of 100 μm, and contains 0.12% of a nonionic surfactant after irradiation with light and 0.04% of potassium hydroxide. The coating film was developed by immersing it in an aqueous developer at 25 ° C. for 60 seconds, washed with water, and post-baked in an oven at 90 ° C. for 1 hour. The physical properties of the pattern thus obtained were evaluated as shown below, and the results are shown in Table 2 below.

  (1) Hole line width: An average value obtained by measuring the X direction and the Y direction of the bottom surface when forming the hole pattern. In the above implementation, pattern formation using a 30 μm square pattern was performed.

  (2) CD-Bias: a value obtained by subtracting the applied mask size from the manufactured actual pattern size. It can be determined that the closer the actual pattern size is to the applied mask size, the better the pattern formation performance.

  In this case, it is judged that the composition having a value close to 0 is more excellent.

  (3) Residue after development: When forming a hole pattern, it is confirmed with a microscope whether or not there is a portion remaining on the surface of the unexposed area after the development stage (preferably not generated).

  (4) Heat-resistant residual film ratio: The post-development cured product after pattern formation is heated at 90 ° C. for 1 hour and finally cured, and further heated at 230 ° C. for 30 minutes, and the degree of film shrinkage due to additional heating is observed. . A material having excellent curing performance under low-temperature curing conditions is recognized as having small film shrinkage due to additional heating, and a material having a high heat-resistant residual film ratio after additional heating can be determined to have further excellent low-temperature curing performance.

(5) Chemical resistance evaluation: The coating film that has been cured at 90 ° C. for 1 hour is immersed in HNO ₃ and HCL aqueous solution and treated for 45 minutes / 6 minutes.

  Then, the adhesiveness was confirmed by the method of peeling after attaching a tape to the surface cut with the cutter based on ASTMD-3359-08 standard test conditions.

  After chemical treatment, the degree to which peeling of the coating film occurs in the cutting / tape test is defined as 0B-5B based on the standard test method, and 5B is judged to have the most excellent performance (5B: 0% peeling) 4B: Peeling less than 5%, 3B: Peeling from 5 to less than 15%, 2B: Peeling from 15 to less than 35%, 1B: Peeling from 35 to less than 65%, 0B: 65% or more).

  (6) Transmittance: The post-development cured product after pattern formation is heated at 90 ° C. for 1 hour and finally cured, and then the transmittance of the coating film portion is measured.

  Referring to Table 2 above, it can be confirmed that the photosensitive resin composition according to the present invention was excellent in pattern formation characteristics, chemical resistance, heat resistance, and the like of a pattern produced under low temperature curing conditions.

  Specifically, the comparative example 1 using only the first resin and the comparative example 4 not using the second resin of the present invention have remarkably low hole pattern implementation characteristics, and the comparative example using only the second resin. No. 2 shows that the development residue is generated and the heat resistant residual film ratio is less than 70%, so that the low temperature curing performance is inferior.

  Moreover, it turns out that the reliability of the comparative example 3 which does not use a thiol compound and the comparative example 5 which uses bifunctional thiol falls remarkably.

Claims (9)

An alkali-soluble resin (A) comprising a first resin comprising a repeating unit represented by the following chemical formula 1; a second resin comprising a repeating unit represented by the following chemical formula 2; a polymerizable compound (B); A polyfunctional thiol compound (C) that is functional or higher, a photopolymerization disclosure agent (D) and a solvent (E);
The negative photosensitive resin composition, wherein the mixing weight ratio of the first resin and the second resin is 50:50 to 90:10.

[Wherein R ₁ , R ₂ and R ₃ are independently of each other hydrogen or a methyl group;
R ₄ consists of methacrylic acid, acrylic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-methacryloyloxyethyl succinate. A structure derived from a monomer selected from the group;
R ₅ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9),

R ₆ is a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12):

a = 10-30 mol%, b = 30-60 mol%, c = 20-50 mol%. ]

[Wherein R ₇ , R ₈ , R ₉ , and R ₁₀ are each independently hydrogen or a methyl group;
R ₁₁ is composed of methacrylic acid, acrylic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, and 2-methacryloyloxyethyl succinate. A structure derived from a monomer selected from the group;
R ₁₂ is benzyl methacrylate, phenoxyethyl glycol acrylate, phenoxy diethylene glycol acrylate, (2-phenyl) phenoxy ethoxy acrylate, 2-hydroxy - (2-phenyl) phenol acrylate, 2-hydroxy - (3-phenyl) phenoxypropyl acrylate , Tetrahydrofuryl acrylate, styrene, vinyl toluene, vinyl naphthalene, N-benzylmaleimide, methyl methacrylate, ethyl methacrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, phenoxyethylene glycol methacrylate, E Bruno carboxymethyl diethyleneglycol dimethacrylate, and a structure derived from a monomer selected from the group consisting of tetrahydrofuryl methacrylate,
R ₁₃ is the structure derived from the monomer selected from the group consisting of the formulas (1) to (9),
R ₁₄ is a structure derived from a monomer selected from the group consisting of the following formulas (13) to (19):

d = 10-30 mol%, e = 10-20 mol%, f = 30-60 mol%, g = 10-30 mol%. ]   The negative photosensitive resin composition according to claim 1, wherein the mixing weight ratio of the first resin and the second resin is 70:30 to 80:20.   The negative photosensitive resin composition according to claim 1 or 2, wherein the first resin has a weight average molecular weight of 6,000 to 12,000.   The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the second resin is 20,000 to 30,000.   The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the polyfunctional thiol compound is a tetrafunctional or higher functional thiol compound.   The negative photosensitive resin composition according to any one of claims 1 to 5, which can be cured at a low temperature of 70 to 100 ° C.   The photocuring pattern formed with the negative photosensitive resin composition as described in any one of Claims 1 thru | or 6.   The photocuring pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer. Photocuring pattern.   The image display apparatus containing the photocuring pattern of Claim 7 or 8.