JP6022870B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a cured product or a transparent insulating film obtained by curing the photosensitive resin composition.

In recent years, high heat-resistant transparency is required for insulating materials used in order to increase the light utilization efficiency of display devices such as liquid crystal displays and organic EL displays.
When a photosensitive resin is used for this insulating material, it is applied to a substrate, soft baked, irradiated with actinic light (exposure) through a desired patterning mask, developed, and subjected to thermosetting treatment. Often applied. In this development process, the pattern formation method using an alkali developer has advantages in that the burden on the environment is low and the cost can be reduced as compared with the case of developing using an organic solvent. Resin is strongly desired.
For example, Patent Document 1 discloses a photosensitive resin composition capable of alkali development. On the other hand, polysiloxane is known as a material having high heat-resistant transparency, and Patent Documents 2 and 3 disclose photosensitive siloxane-based materials capable of alkali development.

JP 2008-216563 A JP 2009-19093 A International Publication No. 2012/019734 Pamphlet

  However, although the technique disclosed in Patent Document 1 has alkali developability and high hardness, the heat-resistant transparency when used in a thick film is considered insufficient. Moreover, when using the technique disclosed by patent document 2 and 3 with a thick film, the improvement of suppression of a development residue is desired when developing with an alkaline developing solution. Therefore, in a transparent film used as a thick film as a display device or an optical material, there is still room for study on alkali developability.

  Therefore, in a field requiring high transparency, such as a display device or an optical system material, a transparent film used as a thick film satisfies alkali developability, heat-resistant transparency in the atmosphere, and crack resistance. The present condition is that the photosensitive film-forming material has not been found yet.

  Therefore, an object of the present invention is to provide a pattern by alkali development in a field requiring high transparency such as a display device or an optical system material, and when the transparent film is used as a thick film. It is to provide a novel photosensitive resin composition that satisfies the physical properties of high heat-resistant transparency and high crack resistance.

  In order to solve the above problems, the present inventor has intensively studied and has completed the present invention. That is, the present invention is as follows.

[1] Alkali-soluble silicone resin (A) having a carboxyl group or dicarboxylic anhydride group in one molecule;
Surfactant (B);
Dissolution promoter (C);
A compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule; and a photopolymerization initiator (E);
A photosensitive resin composition comprising:

[2] The alkali-soluble silicone resin (A): 100 parts by mass;
The surfactant (B): 1 part by mass to 80 parts by mass;
The dissolution accelerator (C): 1 part by mass to 80 parts by mass;
Compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule: 1 part by mass to 300 parts by mass; and the photopolymerization initiator (E): 0.01 part by mass ~ 50 parts by mass;
The photosensitive resin composition according to [1], comprising:

  [3] The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble silicone resin (A) further has a photopolymerizable double bond group in one molecule.

[4] The alkali-soluble silicone resin (A) is:
The following general formula (I):
R ¹ R ² _a Si (R ³ ) _3-a (I)
{Wherein R ¹ is a monovalent organic group having 4 to 20 carbon atoms including a carboxyl group or a dicarboxylic anhydride group, R ² is a methyl group, R ³ is a methoxy group, ethoxy group And at least one monovalent organic group selected from the group consisting of a group, a propoxy group and an isopropoxy group, a hydroxyl group, or chlorine (Cl), and a is an integer of 0 or 1. }
A silane compound (A-1) represented by:
The following general formula (II):
R ⁴ _b R ⁵ _c Si (R ³ ) _4-bc (II)
{Wherein R ³ is at least one monovalent organic group selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group, a hydroxyl group, or Cl, and R ⁴ and R ⁵ are A group having 2 to 20 carbon atoms, a photopolymerizable double bond group or a polymerizable cyclic ether bond group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, a mercapto 4 or 4 carbon atoms including an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carboxyl group or dicarboxylic anhydride group which may be substituted with a group or an amino group R ⁴ and R ⁵ may be the same or different, and may be bonded to each other via a covalent bond, b is an integer selected from 0 to 2, c Is 0 or 1 And b + c does not exceed 2. }
A silane compound (A-2) represented by the following general formula (III):
R ⁶ ₂ Si (OH) ₂ (III)
{In the formula, R ⁶ represents an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, or a carbon atom number of 1 to 1 which may be substituted with a mercapto group or an amino group. 20 alkyl groups or cycloalkyl groups having 5 to 20 carbon atoms, which may be the same as or different from each other, and may be bonded to each other via a covalent bond. }
A silanediol compound (A-3) represented by:
The photosensitive resin composition according to any one of [1] to [3], which is obtained by reacting in the presence of a catalyst.

  [5] The photosensitive resin composition according to any one of [1] to [4], wherein the surfactant (B) is a nonionic surfactant.

  [6] The photosensitive resin composition according to any one of [1] to [5], wherein the surfactant (B) is a silicone-based surfactant.

｛上記式（ＩＶ−１）又は（ＩＶ−２）中、Ｒ⁷〜Ｒ¹⁶は、独立して、炭素原子数が１〜６のアルキル基を表し、Ｒ¹⁷は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｄ及びｅは、独立して１以上の整数を表し、ＥＯは、エチレンオキシ基を表し、ＰＯは、プロピレンオキシ基を表し、ｆ及びｇは、０以上の整数を表すが、ｆ＋ｇは、１以上の整数を表し、ｍは、１〜６の整数を表し、ＥＯ及びＰＯは、［（ＥＯ）_ｆ−（ＰＯ）_ｇ］内においてその順序は問わず、ランダムであってもブロックであってもよい。｝
で表されるポリエーテル変性オルガノシロキサンである、［１］〜［６］のいずれか１項に記載の感光性樹脂組成物。 [7] The surfactant (B) is represented by the following general formula (IV-1) or (IV-2):

{In the above formula (IV-1) or (IV-2), R ^{7 to} R ¹⁶ independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁷ represents a hydrogen atom or the number of carbon atoms. 1 to 6 alkyl groups, d and e independently represent an integer of 1 or more, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and f and g are 0 or more. Represents an integer, f + g represents an integer of 1 or more, m represents an integer of 1 to 6, and EO and PO are in any order within [(EO) _f − (PO) _g ], It may be random or block. }
The photosensitive resin composition of any one of [1]-[6] which is the polyether modified organosiloxane represented by these.

  [8] The photosensitive resin composition according to any one of [1] to [7], wherein the dissolution accelerator (C) is a carboxylic acid compound.

｛上記式（Ｖ−１）、（Ｖ−２）又は（Ｖ−３）中、Ｒ¹⁸及びＲ¹⁹は、それぞれ独立に、炭素原子数２〜４のアルキレン基であり、Ｒ²⁰及びＲ²¹は、それぞれ独立に、水素原子又はメチル基であり、ｈ及びｉは、整数であるが、それぞれ同じであっても異なっていてもよく、ｈ＋ｉ＝０〜２４であり、そして上記式（Ｖ−３）におけるフルオレン骨格は、炭素原子数１〜２８の置換基を有していてもよい。｝
から成る群から選択される少なくとも１つである、［１］〜［８］のいずれか１項に記載の感光性樹脂組成物。 [9] The compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule,
Di (meth) acrylate having a bisphenol A skeleton having an alkylene oxide addition mole number of 0 to 30 represented by the following general formula (V-1);
Diglycidyl ether di (meth) acrylate having a bisphenol A skeleton represented by the following general formula (V-2), and full orange (meth) acrylate represented by the following general formula (V-3):

{In the above formula (V-1), (V-2) or (V-3), R ¹⁸ and R ¹⁹ are each independently an alkylene group having 2 to 4 carbon atoms, and R ²⁰ and R ²¹ Each independently represents a hydrogen atom or a methyl group, and h and i are integers, which may be the same or different, h + i = 0 to 24, and the above formula (V− The fluorene skeleton in 3) may have a substituent having 1 to 28 carbon atoms. }
The photosensitive resin composition according to any one of [1] to [8], which is at least one selected from the group consisting of:

  [10] 0.1% by mass to 20% by mass of the surfactant (B) and 0.1% by mass to 20% by mass of the dissolution based on the mass of the total solid content in the photosensitive resin composition. The photosensitive resin composition of any one of [1]-[9] containing an accelerator (C).

  [11] The photosensitive resin composition according to any one of [1] to [10], further including a solvent (J).

  [12] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [11].

  [13] A transparent insulating film obtained by curing the photosensitive resin composition according to any one of [1] to [11].

[14] The following steps:
A step of applying the photosensitive resin composition according to any one of [1] to [11] onto a substrate to obtain a coating film;
A step of irradiating the coating film with an actinic ray to photocur the exposed portion;
Removing the uncured portion of the coating film using a developer; and heating the substrate and the photocured portion of the coating film;
A method for forming a cured relief pattern, comprising:

  [15] A cured relief pattern formed by the method according to [14].

  The photosensitive resin composition of the present invention is capable of forming a pattern by alkali development in a field requiring high transparency such as a display device or an optical system material, and when using a thick transparent film, in the atmosphere. It is possible to provide a novel photosensitive resin composition that satisfies the physical properties of high heat-resistant transparency and high crack resistance. Furthermore, the cured product and transparent insulating film of the present invention enable the production of a display device having a cured relief pattern that simultaneously achieves excellent transparency and high heat resistance.

Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as embodiments) will be described in detail. In addition, this invention is not limited to the following embodiment, It can deform | transform and implement within the range of the summary.
In an embodiment of the present invention, the photosensitive resin composition has the following components:
(A) an alkali-soluble silicone resin having a carboxyl group or a dicarboxylic anhydride group in one molecule;
(B) a surfactant;
(C) a dissolution accelerator;
(D) a compound having at least two photopolymerizable double bonds and two aromatic rings in one molecule;
(E) a photopolymerization initiator;
If desired, UV absorber (F);
If desired, a silane coupling agent (G);
If desired, antioxidant (H);
Optionally, the nitroxy compound (I);
If desired, it is preferable to include a solvent (J); and, if desired, other additives such as a polymerization inhibitor and a plasticizer. The components (A) to (I) and other additives will be described below.

<Alkali-soluble silicone resin (A)>
The alkali-soluble silicone resin (A) has a carboxyl group or a dicarboxylic anhydride group in one molecule. The alkali-soluble silicone resin (A) has a carboxyl group or a dicarboxylic anhydride group in the silicone resin, thereby improving the alkali solubility of the silicone resin, suppressing residues after development, and good pattern formability. Can be granted.

  The silicone resin is obtained, for example, by polymerizing an organosilane compound having 1 to 4 reactive groups such as an alkoxysilyl group and a chlorosilyl group described in “Silicone Handbook” (1990) published by Nikkan Kogyo Shimbun. It has a two-dimensional or three-dimensional network structure, has a Si—O—Si bond, and has a weight average molecular weight (Mw) of 500 or more in terms of polystyrene measured by gel permeation chromatography (GPC). By increasing the molecular weight of the silicone resin, the content of Si—O—Si bonds increases, and the heat-resistant transparency can be improved.

  Specifically, as the silicone resin, BY16-880, BY16-750, SF8418 (manufactured by Toray Dow Corning), X-22-162C, X-22-3701E, X-22-3710 (manufactured by Shin-Etsu Silicone) ), TSF4770 (manufactured by Momentive Performance Materials), Silaplane FM-6611, FM-6621, FM-6625 (manufactured by Chisso), and the like.

  The content of the carboxyl group or dicarboxylic anhydride group of the alkali-soluble silicone resin (A) is not particularly limited as long as it has these groups, but from the viewpoint of reduction of residues after development and crack resistance of the cured film. The acid value is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more. From the viewpoint of pattern adhesion, the acid value is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / gmol or less, and still more preferably 180 mgKOH / g or less.

Moreover, when it contains 2 or more types of alkali-soluble silicone resins (A), it is preferable that at least 1 type is content of the carboxyl group or dicarboxylic anhydride group within the said acid value range.
In the present specification, the acid value means the number of milligrams of potassium hydroxide necessary to neutralize the carboxyl group in 1 g of a sample.
An example of a method for measuring the acid value is as follows:
A 3 g sample is accurately weighed and dissolved in 20 ml of ethanol. Stir the resulting solution at room temperature, add another 5 g of purified water and stir for an additional hour at room temperature. Thereafter, several drops of a phenolphthalein methanol solution are added as an indicator, neutralized with a 1/2 N aqueous potassium hydroxide solution, and the acid value is calculated from the amount of the aqueous potassium hydroxide solution used.

  The alkali-soluble silicone resin (A) has a carboxyl group or a dicarboxylic anhydride group in one molecule, and further contains a photopolymerizable double bond group or a polymerizable cyclic ether bond group, and has 2 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl having 5 to 20 carbon atoms It preferably has a group. There is no particular limitation as long as these groups are present, but by having a photopolymerizable double bond group in the alkali-soluble silicone resin, the adhesion of the pattern, the hardness of the film, and the crack resistance are increased, which is favorable. In order to obtain film properties, the alkali-soluble silicone resin (A) preferably contains a photopolymerizable double bond group.

  The molar concentration of the photopolymerizable double bond group of the alkali-soluble silicone resin (A) is preferably 0.01 mmol / g or more, more preferably 0, from the viewpoints of pattern adhesion, film hardness, and crack resistance. .1 mmol / g or more, more preferably 0.5 mmol / g or more. From the viewpoint of reducing the residue during development, the molar concentration is preferably 10.0 mmol / g or less, more preferably 7.5 mmol / g or less, and still more preferably 5.0 mmol / g or less.

  The weight average molecular weight (Mw) of the alkali-soluble silicone resin (A) is not particularly limited, but is 500 or more in terms of polystyrene measured by gel permeation chromatography (GPC) from the viewpoint of the heat resistance of the silicone resin. , Preferably 800 or more. From the viewpoints of solubility during development and pattern formability, this Mw is preferably 100,000 or less, more preferably 80,000 or less.

  In the embodiment of the present invention, the content of the alkali-soluble silicone resin (A) is not particularly limited and can be arbitrarily selected depending on the desired film thickness or application, but from the viewpoint of heat-resistant transparency, it is transparent. On the basis of the mass of all components other than the solvent in the alkali-soluble silicone resin composition, 1% by mass or more is preferable, more preferably 10% by mass or more, and further preferably 15% by mass or more. 99 mass% or less is preferable from a crack property viewpoint, More preferably, it is 90 mass% or less, More preferably, 80 mass% or less is preferable.

The alkali-soluble silicone resin (A) of the present invention is:
(A-1) Resin design and that it is obtained by reaction with the silane compound represented by the following general formula (I) and (A-2) the silane compound represented by the following general formula (II). It is preferable from the viewpoint of ease of manufacturing.
R ¹ R ² _a Si (R ³ ) _3-a (I)
{Wherein R ¹ is a monovalent organic group having 4 to 20 carbon atoms including a carboxyl group or a dicarboxylic anhydride group, R ² is a methyl group, R ³ is a methoxy group, ethoxy group And at least one monovalent organic group selected from the group consisting of a group, a propoxy group, and an isopropoxy group, a hydroxyl group, or chlorine (Cl), and a is an integer of 0 or 1. }
R ⁴ _b R ⁵ _c Si (R ³ ) _4-bc (II)
{In the formula, R ⁴ and R ⁵ are a group having 2 to 20 carbon atoms including a photopolymerizable double bond group or a polymerizable cyclic ether bond group, an aryl group having 6 to 20 carbon atoms, a carbon atom A C2-C20 alkyl group, a C5-C20 cycloalkyl group, a carboxyl group or a dicarboxylic group, which may be substituted with an alkylaryl group having 2 to 20 carbon atoms, a mercapto group or an amino group a group number of carbon atoms is 4 to 20 containing an acid anhydride group, R ⁴ and R ⁵ may be the same or different, may also be tied together further through a covalent bond, R ³ is , A methoxy group, an ethoxy group, a propoxy group and an isopropoxy group, at least one monovalent organic group selected from the group consisting of a hydroxyl group or Cl, and b is an integer selected from 0 to 2, c Is 0 or 1 It is an integer and b + c does not exceed 2. }

｛式中、Ｒｘは、炭素原子数が１〜６の直鎖状又は分岐鎖状の２価の有機基であり、Ｒｙ及びＲｚは、メチル基、エチル基、プロピル基、イソプロピル基及び水素から成る群より選ばれる少なくとも１種であり、ＲｙとＲｚの一方又は両方は水素であり、Ｒａは、炭素原子数が２〜１６の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｓは、炭素原子数が１〜２０の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｔは、炭素原子数が１〜１８の直鎖状、分岐鎖状又は環状の２価の有機基であり、そしてＲｕ及びＲｖは、炭素原子数が１〜２０の直鎖状、分岐鎖状若しくは環状の１価の有機基、又は下記一般式（２）で表される１価の有機基である。｝

｛式中、Ｒｗは、炭素原子数が１〜１６の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｂは、炭素原子数が１〜２０の直鎖状、分岐鎖状若しくは環状の１価の有機基又は光重合性二重結合基を有する１価の有機基であり、そしてＲｃは、下記一般式（３）で表される基又は水素である。｝

｛式中、Ｒａは、炭素原子数が２〜１６の直鎖状、分岐鎖状又は環状の２価の有機基である。｝ The alkali-soluble silicone resin (A) is not particularly limited as long as it has a carboxyl group or a dicarboxylic anhydride group in one molecule, but R ^{1 of the} silane compound represented by the general formula (I) is as follows. It is preferably a monovalent organic group containing 4 to 20 carbon atoms, including the carboxyl group or dicarboxylic anhydride group represented by the general formula (1).

{In the formula, Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms, and Ry and Rz are methyl, ethyl, propyl, isopropyl, and hydrogen. And at least one of Ry and Rz is hydrogen, and Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms. Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms, and Rt is a linear, branched or linear group having 1 to 18 carbon atoms. A cyclic divalent organic group, and Ru and Rv are each a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or represented by the following general formula (2): A monovalent organic group. }

{In the formula, Rw is a linear, branched or cyclic divalent organic group having 1 to 16 carbon atoms, and Rb is a linear or branched chain having 1 to 20 carbon atoms. A cyclic or monovalent organic group or a monovalent organic group having a photopolymerizable double bond group, and Rc is a group represented by the following general formula (3) or hydrogen. }

{In the formula, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms. }

In the above general formula (I), preferred organic groups as R ¹ include, for example, a succinic anhydride group (R ¹ -1), a cyclohexanedicarboxylic anhydride group (R ¹ -2), and 4-methyl-cyclohexanedicarboxylic acid. acid anhydride group (R ¹ -3), 5- methyl - cyclohexane dicarboxylic anhydride group (R ¹ -4), bicycloheptane dicarboxylic acid anhydride group (R ¹ -5), 7- oxa - bicycloheptane dicarboxylic acid anhydride groups (R ¹ -6), phthalic acid anhydride group (R ¹ -7), succinic acid, or a half ester group (R ¹ -8), cyclohexane dicarboxylic acid, or its half ester groups (R ¹ -9), 4-methyl - cyclohexanedicarboxylic acid, or half ester group (R ¹ -10 thereof), 5-methyl - cyclohexane dicarboxylic acid, or its Hafue Ether group (R ¹ -11), bicycloheptane dicarboxylic acid, or its half ester groups (R ¹ -12), 7- oxa - bicycloheptane dicarboxylic acid or half ester group (R ¹ -13) thereof, phthalic acid, or its half ester groups (R ¹ -14), group (R ¹ -15) having an amide bond by reaction with the amino groups and a dicarboxylic acid anhydride, the group (R ¹ -16) having an isocyanuric skeleton Can be mentioned. These groups may be used alone or in combination of two or more.

  Rx in the general formula (1) is a linear or branched divalent organic group having 1 to 6 carbon atoms. Among these, from the viewpoint of ease of synthesis, Rx is preferably a hydrocarbon group. Examples include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, and tert-pentylene group. It is done. These groups may contain a double bond and / or a triple bond, and may be used alone or in combination of two or more. Of these, a propylene group is most preferred.

Group having an amide bond in the general formula (1) (R ¹ -15) is obtained by reaction of an amino group with a dicarboxylic acid anhydride, a group containing a carboxyl group. Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms. Examples of the dicarboxylic acid anhydride include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid anhydride, 7-oxabicyclo Heptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinic anhydride, (3-tri And polybasic acid anhydrides such as ethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

The group (R ¹ -16) having an isocyanuric skeleton in the general formula (1) is converted from a isocyanuric skeleton having a glycidyl group to a hydroxyl group generated through a ring-opening reaction of glycidyl by a reaction with a carboxyl group or a hydroxyl group. It is a group containing a carboxyl group obtained by reacting an acid anhydride.

In the above general formula (I), the most preferable group as R ¹ is a propyl succinic anhydride group (R ¹ -1), a propyl succinic acid group, or a half methyl ester group thereof, or a half ethyl ester group thereof (R ¹ -8).
In the general formula (I), the most preferable group as R ³ is a methoxy group or an ethoxy group.

  Of the alkoxysilane compounds containing a carboxyl group or dicarboxylic anhydride group represented by the above general formula (I), the most preferred compound is (3-trimethoxysilylpropyl) succinic anhydride, (3-triethoxysilyl) Propyl) succinic anhydride, (3-trimethoxysilylpropyl) succinic acid, (3-triethoxysilylpropyl) succinic acid, (3-trimethoxysilylpropyl) succinic acid half methyl ester, (3-triethoxysilyl) Propyl) succinic acid half methyl ester, (3-trimethoxysilylpropyl) succinic acid half ethyl ester, and (3-triethoxysilylpropyl) succinic acid half ethyl ester.

In the general formula (II), R ⁴ and R ⁵ are as defined above.
Among specific examples of the silane compound represented by the general formula (II), the compound having a photopolymerizable double bond group includes 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxy. Propyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenyl Phenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenylphenyl) trimethoxysilane, p- (2-propenylphenyl) triethoxysilane, and the like.

  Among specific examples of the silane compound represented by the general formula (II), as the compound having a polymerizable cyclic ether bond group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triethoxysilane, 2 -(3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane and the like can be mentioned.

  Other than the above, specific examples of the compound represented by the general formula (II) include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxylane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Diethyldimethoxysilane, diethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, diphenyldi Toxisilane, diphenyldiethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2 -Aminoe Ru-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltrichlorosilane, Examples thereof include phenyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, and tri-i-propylchlorosilane. These may be used alone or in combination of two or more.

  The alkali-soluble silicone resin (A) is obtained by, for example, hydrolyzing the silane compound represented by the general formula (I) and the silane compound represented by the general formula (II) by adding water and a catalyst, and then hydrolyzing the silane compound. It can be obtained by condensing the product in the presence or absence of a solvent.

  In the hydrolysis reaction, an acidic catalyst and water are added to the silane compound in a solvent over 1 to 180 minutes. The temperature in the process of obtaining the hydrolyzate is preferably 10 ° C or higher from the viewpoint of hydrolysis reactivity, more preferably 20 ° C or higher, while 150 ° C or lower is preferable from the viewpoint of protecting functional groups. Preferably, it is 120 ° C. or less. The reaction time in the process of obtaining the water monster is preferably 0.1 hour or more from the viewpoint of hydrolysis reactivity, more preferably 0.5 hour or more, while 10 minutes from the viewpoint of protection of the functional group. The time is preferably not more than 5 hours, more preferably not more than 5 hours.

  The hydrolysis reaction is preferably performed in the presence of an acidic catalyst. As the acidic catalyst, an acidic aqueous solution containing hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or phosphoric acid is preferable. The preferable content of these acidic catalysts is preferably 0.01 parts by mass or more from the viewpoint of the reactivity of hydrolysis with respect to 100 parts by mass of the total silane compounds used during the hydrolysis reaction, and from the viewpoint of protection of the functional group. 10 parts by mass or less is preferable.

  After obtaining the silanol compound by the hydrolysis reaction of the silane compound, it is preferable to carry out the condensation reaction by heating the reaction solution as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. Moreover, in order to raise the polymerization degree of alkali-soluble silicone resin (A), you may add reheating and / or pressure reduction, and / or a basic catalyst.

  The solvent used for the hydrolysis reaction of the silane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent.

  Specific examples of the solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, isopentyl alcohol, diacetone alcohol and other alcohols, ethylene glycol, propylene glycol and the like. Glycols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and other ethers, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, Such as methyl isobutyl ketone and cyclopentanone Tons, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetates such as methyl lactate, ethyl lactate, butyl lactate, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, etc. be able to.

When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the reaction. Moreover, after hydrolysis according to the purpose, an appropriate amount of the produced alcohol may be distilled off under heating and / or reduced pressure, and then a suitable solvent may be added.
The amount of the solvent used for hydrolysis is preferably 80 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of all silane compounds.
The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of silane atoms.

  In the production method of the alkali-soluble silicone resin (A) used in the present invention, when silanol is handled in addition to the above reaction, water is generated due to dehydration condensation between silanols, so that it is not necessary to add water. When handling chlorosilane, it can be reacted without the addition of water and catalyst.

  The alkali-soluble silicone resin (A) should have a small amount of residual silanol from the viewpoint of reducing shrinkage due to condensation between silanols during baking, and reducing degassing derived from water generated by condensation, and the residual silanol is almost eliminated. It is more preferable.

More preferably, the alkali-soluble silicone resin (A) is
(A-1) an alkoxysilane containing a carboxyl group and / or an acid anhydride group represented by the general formula (I) (A-2) an alkoxysilane represented by the general formula (II), and (A- 3) It is obtained by a method in which a silanediol compound represented by the following general formula (III) is reacted in the presence of a catalyst or preferably condensed without actively adding water.
R ⁶ ₂ Si (OH) ₂ (III)
{In the formula, R ⁶ represents an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or 5 to 5 carbon atoms. 20 cycloalkyl groups, which may be the same or different from each other, and may be linked to each other via a covalent bond. }

In the silanediol compound represented by the general formula (III), R ⁶ is as defined above. Examples of R ⁶ include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, a methyl group, an ethyl group, a cyclopentyl group, and a cyclohexyl group.

  Specific examples of the silane diol compound represented by the general formula (III) include diphenyl silane diol, di-p-toluyl silane diol, dixyl silane diol, ditrimethyl phenyl silane diol, di-p-styryl silane diol, Examples include dinaphthyl silane diol, dicyclopentyl silane diol, and cyclohexyl methyl silane diol. From the viewpoint of copolymerization and heat resistance, diphenyl silane diol, dicyclopentyl silane diol, and cyclohexyl methyl silane diol are particularly preferable.

  The alkali-soluble silicone resin (A) used in the present invention has a small amount of residual silanol or almost no residual silanol, for example, an alkoxysilane compound represented by the general formula (I) and a general formula (II). It can be obtained by a method in which an alkoxysilane compound represented by formula (III) and a silanediol compound represented by formula (III) are condensed in the presence of a catalyst without actively adding water.

The reaction temperature for the condensation without positively adding water is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of condensation reactivity, while 150% is preferred from the viewpoint of protecting functional groups. C. or lower is preferable, and 120 C or lower is more preferable.
The reaction time for the condensation without actively adding water is preferably 0.5 hours or more, more preferably 1 hour or more from the viewpoint of condensation reactivity, while 15 hours from the viewpoint of protection of the functional group. The following is preferable, and 10 hours or less is more preferable.

In the reaction of condensation without positively adding water, a catalyst is used and water is not positively added. As the catalyst, a basic catalyst or an acidic catalyst can be used.
As the basic catalyst, a trivalent or tetravalent metal alkoxide can be used. Specifically, trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, tri-iso-propoxy aluminum, tri-n-butoxy aluminum, tri-iso-butoxy aluminum, tri-sec-butoxy aluminum, tri- tert-butoxyaluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-iso-propoxyboron, tri-n-butoxyboron, tri-iso-butoxyboron, tri-sec-butoxyboron, tri- tert-butoxyboron, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, teto -Sec-butoxysilane, tetra-tert-butoxysilane, tetramethoxygermanium, tetraethoxygermanium, tetra-n-propoxygermanium, tetra-iso-propoxygermanium, tetra-n-butoxygermanium, tetra-iso-butoxygermanium, tetra -Sec-butoxygermanium, tetra-tert-butoxygermanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-iso-propoxytitanium, tetra-n-butoxytitanium, tetra-iso-butoxytitanium, tetra -Sec-butoxytitanium, tetra-tert-butoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium , Tetra -iso- propoxy zirconium, tetra -n- butoxy zirconium, tetra -iso- butoxy zirconium, tetra -sec- butoxy zirconium, tetra--tert- butoxy zirconium and the like.

Alkali metal hydroxides or alkaline earth metal hydroxides such as barium hydroxide, sodium hydroxide, potassium hydroxide, strontium hydroxide, calcium hydroxide, and magnesium hydroxide are used as basic catalysts. May be. NH ₄ F, that is, ammonium fluoride may be used as a basic catalyst. Among these, barium hydroxide, sodium hydroxide, strontium hydroxide, tetra-tert-butoxy titanium, and tetra-iso-propoxy titanium are preferable. In order to achieve a rapid and uniform polymerization reaction, the basic catalyst is preferably liquid in the reaction temperature range.

  The preferable content of these basic catalysts is preferably 0.01 parts by mass or more from the viewpoint of condensation reactivity with respect to 100 parts by mass of the total silane compound, and is preferably 10 parts by mass or less from the viewpoint of protection of the functional group.

  As the acidic catalyst, an organic acidic catalyst containing no water can be used. Specifically, acetic acid, trifluoroacetic acid, acrylic acid, methacrylic acid, citric acid, malic acid, succinic acid, phthalic acid, (3-trimethoxysilylpropyl) succinic acid, or a half ester thereof, (3-triethoxy Silylpropyl) succinic acid or its half ester.

  A preferable content of these acidic catalysts is preferably 0.01 parts by mass or more from the viewpoint of condensation reactivity with respect to 100 parts by mass of all silane compounds, and is preferably 10 parts by mass or less from the viewpoint of protection of the functional group.

<Surfactant (B)>
In the embodiment of the present invention, the surfactant (B) can be used in combination with the dissolution accelerator (C), thereby improving the developability of the photosensitive resin composition. Although not wishing to be bound by theory, it is considered that an oligomerized resin that does not sufficiently cure exists at the interface between the UV cured portion and the unexposed portion of the photosensitive resin composition. Since the oligomerized resin has a low molecular weight, it has solubility in a developer and is easily eluted during development, but unlike an unexposed portion, it is difficult to develop. As a result, the oligomerized resin may cause the resin to remain on the substrate after development as a development residue. In addition, a compound containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule, such as component (D), has poor developability. It is considered that the development residue is likely to be reduced. While improving the developability of the oligomerized resin with a dissolution accelerator and facilitating dispersion in the developer, the surfactant forms micelles in the dispersed oligomer, thereby forming a photosensitive resin composition. It is expected that high developability can be obtained even if a compound having poor developability such as component (D) is used.

｛上記式（ＩＶ−１）又は（ＩＶ−２）中、Ｒ⁷〜Ｒ¹⁶は、独立して、炭素原子数が１〜６のアルキル基を表し、Ｒ¹⁷は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｄ及びｅは、独立して１以上の整数を表し、ＥＯは、エチレンオキシ基を表し、ＰＯは、プロピレンオキシ基を表し、ｆ及びｇは、０以上の整数を表すが、ｆ＋ｇは、１以上の整数を表し、ｍは、１〜６の整数を表し、ＥＯ及びＰＯは、［（ＥＯ）_ｆ−（ＰＯ）_ｇ］内においてその順序は問わず、ランダムであってもブロックであってもよい。｝
（５）フッ素系界面活性剤
パーフルオロアルキルカルボン酸、パーフルオロアルキルスルホン酸、パーフルオロアルキル基含有オリゴマー（大日本インキ化学工業製、商標名メガファック、品番Ｒ−０８）、下記一般式（ＩＶ−３）で表される化合物。

（上記式（ＩＶ−３）中、Ｒ_jは、トリフルオロメチル基又はペンタフルオロエチル基であり、そしてｋは、１〜２５の整数である。）
上記化合物（１）〜（５）は、単独で、又は２種以上の混合物として使用されることができる。 As the surfactant (B), it is preferable to add a nonionic surfactant rather than an ionic surfactant from the viewpoint of preventing corrosion of the wiring metal. Preferred nonionic surfactants include the following compounds (1) to (5):
(1) Ether type polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxypropylene alkyl ether,
(2) Ester ether type polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester,
(3) Ester type Polyethylene glycol fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester,
(4) Silicone surfactant A polyether-modified organosiloxane represented by the following general formula (IV-1) or (IV-2):

{In the above formula (IV-1) or (IV-2), R ^{7 to} R ¹⁶ independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁷ represents a hydrogen atom or the number of carbon atoms. 1 to 6 alkyl groups, d and e independently represent an integer of 1 or more, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and f and g are 0 or more. Represents an integer, f + g represents an integer of 1 or more, m represents an integer of 1 to 6, and EO and PO are in any order within [(EO) _f − (PO) _g ], It may be random or block. }
(5) Fluorosurfactant Perfluoroalkyl carboxylic acid, perfluoroalkyl sulfonic acid, perfluoroalkyl group-containing oligomer (manufactured by Dainippon Ink and Chemicals, trade name: Megafuck, product number R-08), the following general formula (IV) -3) The compound represented.

(In the above formula (IV-3), R _j is a trifluoromethyl group or a pentafluoroethyl group, and k is an integer of 1 to 25.)
The said compounds (1)-(5) can be used individually or as a 2 or more types of mixture.

  Among the nonionic surfactants, (4) silicone surfactants are preferable from the viewpoint of compatibility. Among them, preferred is a polyether-modified organosiloxane represented by the above general formula (IV-1) or (IV-2), and more preferred is poly (ethyleneoxy) siloxane.

  (4) Silicone surfactants as described above are generally available on the market. Examples of commercially available products include DBE-224, DBE-712, DBE-821 (manufactured by Gelest), KF-640, KF. -642, KF-643 (made by Shin-Etsu Silicone), etc.

  The addition amount of the surfactant (B) when adding the surfactant (B) to the photosensitive resin composition is 1 part by mass to 80 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin (A). Preferably there is. This addition amount is preferably 1 part by mass or more from the viewpoint of improving alkali developability. Further, from the viewpoint of suppressing pattern lifting and peeling, and further suppressing cracking and yellowing in heat treatment, the amount added is preferably 80 parts by mass or less, more preferably 40 parts by mass or less, and most preferably 20 parts by mass or less.

<Solubility Accelerator (C)>
In the embodiment of the present invention, the dissolution accelerator (C) can be used in combination with the surfactant (B) to improve the developability of the photosensitive resin composition. Examples of the dissolution accelerator (C) include carboxylic acid compounds. The carboxylic acid compound is preferably added to the photosensitive resin composition and remains in the film after soft baking, so that the effect of the dissolution accelerator (C) can be exhibited. In this connection, carboxylic acid compounds having 6 or more carbon atoms are preferred. On the other hand, a carboxylic acid compound having 18 or less carbon atoms is preferable from the viewpoint of being uniformly dissolved in the composition.

  Specifically, as the carboxylic acid compound, sorbic acid, lauric acid, myristic acid, oleic acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 2-methyl-n-valeric acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, decanoic acid, DL -Leucic acid, N-acetyl-DL-methionine, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 9-decenoic acid, 2-dodecenoic acid, 10-undecenoic acid, 3-cyclohexene -1-carboxylic acid, 1-cyclohexene-3-carboxylic acid, cyclohexanecarboxylic acid, cyclopentylacetic acid, cyclohexylacetic acid, cyclohexylpropionic acid, 4-cyclohexanebutyric acid, 5-nor Borene-2-carboxylic acid, m-anisic acid, m-toluic acid, m-tolylacetic acid, o-anisic acid, o-toluic acid, o-tolylacetic acid, p-anisic acid, p-toluic acid, p-tolyl Examples include acetic acid and benzoic acid. As the carboxylic acid compound, isononanoic acid is preferable.

  The amount of the dissolution accelerator (C) added to the photosensitive resin composition is preferably 1 part by mass to 80 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin (A). From the viewpoint of improving alkali developability, the amount added is preferably 1 part by mass or more. Further, from the viewpoint of suppressing pattern lifting and peeling, and further suppressing cracking and yellowing in heat treatment, the addition amount is preferably 80 parts by mass or less, more preferably 40 parts by mass or less, and most preferably 20 parts by mass or less.

  Further, in the embodiment of the present invention, from the viewpoint of imparting optimum developability, cracking and yellowing resistance to the photosensitive resin composition, the photosensitive resin composition is a mass of the total solid content in the photosensitive resin composition. Is preferably 0.1% by mass to 20% by mass of the surfactant (B) and 0.1% by mass to 20% by mass of the dissolution accelerator (C), preferably 0.5% by mass to 10% by mass. It preferably contains 1% by mass of surfactant (B) and 1% by mass of 1% by mass to 5% by mass of surfactant (B) and 0.5% by mass to 10% by mass of dissolution accelerator (C). Most preferably, it contains ~ 5% by weight of a dissolution promoter (C).

｛上記式（Ｖ−１）、（Ｖ−２）又は（Ｖ−３）中、Ｒ¹⁸及びＲ¹⁹は、それぞれ独立に、炭素原子数２〜４のアルキレン基であり、Ｒ²⁰及びＲ²¹は、それぞれ独立に、水素原子又はメチル基であり、ｈ及びｉは整数であり、ｈ＋ｉ＝０〜２４であり、それぞれ同じであっても異なっていてもよく、そして上記式（Ｖ−３）におけるフルオレン骨格は、炭素原子数１〜２８の置換基を有していてもよい。｝ <Compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule>
The compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule is added to the photosensitive resin composition for the purpose of improving crack resistance and heat yellowing of the cured film. It is important that it is added.
Examples of the compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule include the following compounds 1 to 3. These may be used alone or in combination of two or more.
1. Di (meth) acrylate having a bisphenol A skeleton having 0-30 alkylene oxide addition moles Here, the di (meth) acrylate having a bisphenol A skeleton having 0-30 alkylene oxide addition moles is represented by the following general formula ( The compound represented by V-1).
2. Diglycidyl ether di (meth) acrylate having bisphenol A skeleton Here, diglycidyl ether di (meth) acrylate having a bisphenol A skeleton refers to a compound represented by the following general formula (V-2).
3. Full orange (meth) acrylate Here, full orange (meth) acrylate refers to a compound represented by the following general formula (V-3).

{In the above formula (V-1), (V-2) or (V-3), R ¹⁸ and R ¹⁹ are each independently an alkylene group having 2 to 4 carbon atoms, and R ²⁰ and R ²¹ Each independently represents a hydrogen atom or a methyl group, h and i are integers, h + i = 0 to 24, and may be the same or different, and the above formula (V-3) The fluorene skeleton in may have a substituent having 1 to 28 carbon atoms. }

  The addition amount to the photosensitive resin composition of the compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule is 100 parts by mass of the alkali-soluble silicone resin (A). 1 mass part-300 mass parts are preferable, and 5 mass parts-200 mass parts are more preferable. This addition amount is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, from the viewpoint of sufficiently crosslinking and exhibiting adhesion to the substrate, on the other hand, from the viewpoint of reducing residue after development and suppressing thermal yellowing Therefore, 200 parts by mass or less is preferable, and 150 parts by mass or less is more preferable.

<Photopolymerization initiator (E)>
It is important that the photopolymerization initiator (E) is added to the photosensitive resin composition in order to impart photosensitivity and pattern forming property to the resin composition.

Examples of the photopolymerization initiator (E) include the following photopolymerization initiators (1) to (10):
(1) Benzophenone derivatives: for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone (2) acetophenone derivatives: for example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE651 manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (IRGACURE184 manufactured by BASF), 2-methyl -1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907 manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -Benzyl] -pheny } -2-Methylpropan-1-one (IRGACURE127 manufactured by BASF), methyl phenylglyoxylate (3) thioxanthone derivative: for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone (4) benzyl derivative: for example , Benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal (5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF, DAROCURE 1173)
(6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (IRGACURE OXE01 manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzo) Le) -9H- carbazol-3-yl] -, 1- (O- acetyloxime) (BASF Corp. IRGACURE OXE02)
(7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane (8) α-aminoalkylphenone system Compound: For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by BASF), 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) butan-1-one (IRGACURE 379 manufactured by BASF)
(9) Phosphine oxide compounds: For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819 manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, LUCIRIN TPO)
(10) Titanocene compound: for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (manufactured by BASF) IRGACURE784)
The photopolymerization initiators (1) to (10) may be used alone or in combination of two or more.

  Among the above-described photopolymerization initiators, (5) benzoin derivatives or (9) phosphine oxide compounds are more preferable, particularly from the viewpoint of improving photosensitivity and transparency. The addition amount of the photopolymerization initiator (E) to the photosensitive resin composition is 0.01% with respect to 100 parts by mass of the alkali-soluble silicone resin (A) from the viewpoint of obtaining sufficient sensitivity of the photosensitive resin composition. From the viewpoint of sufficiently curing the bottom portion of the photosensitive resin layer, 50 parts by mass or less is preferable, and 15 parts by mass or less is more preferable. Preferably, 10 mass parts or less are more preferable.

<Ultraviolet absorber (F)>
In the embodiment of the present invention, it is preferable to add an ultraviolet absorber (F) in order to improve the light resistance of the photosensitive resin composition and reduce the residue during development.

  Examples of such ultraviolet absorber (F) include benzotriazole compounds and benzophenone compounds. For example, the reaction product (BASF) of 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester TINUVIN405), 2- (2Hbenzotriazol-2-yl) phenol, 2- (2Hbenzotriazol-2-yl) -4,6-t-pentylphenol, 2- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2Hbenzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2'-hydroxy-5'-) Methacryloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzophenone, and the like.

  In the case of adding the ultraviolet absorber (F), the amount added is preferably 0.01% by mass or more from the viewpoint of preventing curing of the unexposed portion, based on the mass of all components other than the solvent in the photosensitive resin composition. More preferably, it is 0.1% by mass or more. On the other hand, it is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of pattern formation by radical generation during exposure.

<Silane coupling agent (G)>
In an embodiment of the present invention, a silane coupling agent (G) is added to a transparent alkali-soluble silicone resin composition in order to improve the adhesion between the cured film after exposure and development of the transparent alkali-soluble silicone resin composition and the substrate. It is preferable to add to the product.

  Examples of the silane coupling agent (G) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p -(2-propenylphenyl) trimethoxysilane, p- (2-propenylphenyl) triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 3-g Sidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxy Lan, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2 Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercapto Propylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltri Examples include methoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, and 3-triethoxysilylpropyl succinic anhydride.

  In the case of adding the silane coupling agent (G), the addition amount is 0.1% by mass or more from the viewpoint of developing adhesion with the substrate on the basis of the mass of all components other than the solvent in the photosensitive resin composition. Is more preferable, and more preferably 0.5% by mass or more. On the other hand, from the viewpoint of curing reactivity of the photosensitive composition, 20% by mass or less is preferable, and more preferably 15% by mass or less.

<Antioxidant (H)>
In the embodiment of the present invention, it is preferable to add an antioxidant (H) to the photosensitive resin composition in order to improve the thermal stability of the photosensitive resin composition in the presence of oxygen. Examples of the antioxidant (H) include hindered phenol type, phosphorus type, lactone type, vitamin E type, sulfur type and the like.

  Specifically, the antioxidant (H) is not limited, but triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] ( IRGANOX 245) manufactured by BASF, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (IRGANOX 259 manufactured by BASF), 2,4-bis- (n -Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX565 manufactured by BASF), pentaerythrityl tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate) (IRGANOX 1010 manufactured by BASF), 2,2-thio-die Renbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX 1035 manufactured by BASF), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX1076 manufactured by BASF), N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (IRGANOX1098 manufactured by BASF), 3,5-di-t- Butyl-4-hydroxybenzylphosphonate-diethyl ester (IRGAMOD295 manufactured by BASF), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl ) Benzene (IRGANOX 1330, manufactured by BASF), Tris- (3,5-di-t-) Til-4-hydroxybenzyl) -isocyanurate (IRGANOX3114 manufactured by BASF), octylated diphenylamine (IRGANOX5057 manufactured by BASF), 2,4-bis [(octylthio) methyl) -o-cresol (IRGANOX1520L manufactured by BASF), Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX 1135 manufactured by BASF), 2,4-bis (dodecylthiomethyl) -6-methylphenol (IRGANOX 1726 manufactured by BASF), 2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) chroman-6-ol (IRGANOX E201 manufactured by BASF), 5,7-di-t-butyl-3- ( 3,4-dimethylphenyl) Nzofuran-2 (3H) -one (IRGANOX HP-136), tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS168 manufactured by BASF), tris [2-[[2,4,8,10 -Tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (BASF, IRGAFOS12), bis (2, 4-di-t-butyl-6-methylphenyl) ethyl phosphite (IRGAFOS38 manufactured by BASF), 3,3-thiobispropionic acid didodecyl ester (IRGANOX PS800 manufactured by BASF), 3,3-thiobispropionic acid And dioctadecyl ester (IRGANOX PS802, manufactured by BASF).

  Specifically, the antioxidant (H) is not limited, but 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl. Oxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (SUMILIZER GA-80 manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis (6-t- (Butyl-4-methylphenol) (SUMIZER MDP-S manufactured by Sumitomo Chemical Co., Ltd.), 4, 4′-butylidenebis (6-t-butyl-3-methylphenol) (SUMILIZER BBM-S manufactured by Sumitomo Chemical Co., Ltd.), 4, 4 '-Thiobis (6-t-butyl-3-methylphenol) (SUMIZER WX-R manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl-tetrakis (3-lauryl) Thiopropionate) (SUMILIZER TP-D made by Sumitomo Chemical Co., Ltd.), 2-mercaptobenzimidazole (SUMILIZER MB made by Sumitomo Chemical Co., Ltd.), biphenyl-4,4′-diyl-bis [bis (2,4-di-t -Butyl-5-methylphenoxy) phosphine] (GSY-P101 manufactured by Osaki Kogyo Co., Ltd.), cyclohexane and peroxide N-butyl-2,2,6,6, -tetramethyl-4-piperidineamine-2,4,6 -A reactive organism with trichloro 1,3,5-triazine and a reactive organism with 2-aminoethanol (TINUVIN 152 manufactured by BASF) and the like.

  These antioxidants (H) can be used alone or as a mixture of two or more. The content of the antioxidant (H) in the photosensitive resin composition is from the viewpoint of expressing the thermal stability effect in the presence of oxygen with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 0.001 part by mass or more is preferable, more preferably 0.01 part by mass or more, and further preferably 0.1 part by mass or more. On the other hand, from the viewpoint of pattern formation due to radical generation during exposure, 15 parts by mass The following is preferable, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.

（式中、Ｒ²⁰、Ｒ²¹、Ｒ²²及びＲ²³は、各々独立に、炭素数１〜１０の１価の有機基を表わし、そしてＲ²⁰とＲ²¹、又はＲ²²とＲ²³は、互いに結合して環構造を形成していてもよい。） <Nitroxy Compound (I)>
In an embodiment of the present invention, a nitroxy compound (I) containing a structure represented by the following general formula (VI) is added to a photosensitive resin composition in order to improve heat-resistant yellowing and heat cracking properties of the photosensitive resin composition. It is preferable to add to.

(Wherein R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents a monovalent organic group having 1 to 10 carbon atoms, and R ²⁰ and R ²¹ , or R ²² and R ²³ are They may be bonded to each other to form a ring structure.)

In the general formula (VI), R ²⁰ , R ²¹ , R ²² and R ²³ may each independently be an alkyl group or an alkyl group substituted with a hetero atom. As the alkyl group, a methyl group, an ethyl group, a propyl group and the like are preferable, and as the hetero atom, a halogen, oxygen, sulfur, nitrogen and the like are preferable.

  Preferred nitroxy compounds (I) include 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-amino -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-cyano-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radical, 4-methacrylic acid-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acrylic acid-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl Lia radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- (2- Chloroacetamido) -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylbenzoate free radical, 4-isothiocyanato-2, 2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- (2-iodoacetamido) -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-methoxy-2,2,6 , 6-Tetramethylpiperidine 1-oxyl free radical. (I) A nitroxy compound may be used independently and may be used in combination of 2 or more types.

  (I) The nitroxy compound may be contained in a small amount in the photosensitive resin composition, but from the viewpoint of crack resistance, the content of (I) the nitroxy compound is the total solid content in the photosensitive resin composition. 0.005 parts by mass or more is preferable with respect to 100 parts by mass, more preferably 0.009 parts by mass or more. On the other hand, from the viewpoint of transparency, 2 parts by mass or less is preferable, and more preferably 1 part by mass or less. Is preferred.

<Solvent (J)>
In the embodiment of the present invention, it is preferable to add a solvent (J) to the photosensitive resin composition to adjust its viscosity.

Suitable solvents (J) include the following solvents (1) to (6):
(1) Aliphatic alcohol: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol , Isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctyl alcohol, 2-octanol, 3-octanol, 1-nonanol, isononyl alcohol, 3, 5, 5 -Trimethyl hex 1-decanol, isodecyl alcohol, 3,7-dimethyl-1-octanol, 1-hendecanol, 1-dodecanol, isododecyl alcohol, allyl alcohol, propargyl alcohol, hexynol (2) aromatic alcohol: benzyl alcohol, ( 2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) benzene-1,2-diol, (4-hydroxy-3-methoxyphenyl) methanol, ( 3,4-dimethoxyphenyl) methanol, (4-isopropylphenyl) methanol, 2-phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-tolyl alcohol, 2- (4-hydroxy 3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropan-2-ol, cinnamyl alcohol, 3 -(4-hydroxy-3-methoxyphenyl) prop-2-en-1-ol, 3- (4-hydroxy-3,5-methoxyphenyl) prop-2-en-1-ol, diphenylmethanol, trityl alcohol 1,2-diphenylethane-1,2-diol, 1,1,2,2, -tetraphenylethane-1,2-diol, benzene-1,2-dimethanol, benzene-1,3-dimethanol , Benzene-1,4-dimethanol (3) alicyclic alcohol: cyclohexanol, methylcyclohexanol, furfuryl alcohol , Tetrahydrofurfuryl alcohol, tetrahydro-2-furanmethanol (4) glycol and derivatives thereof: for example, ethylene glycol, ethylene glycol monoalkyl (1-8 carbon atoms) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, Dioxane, diethylene glycol monoalkyl (1 to 6 carbon atoms) ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (1 to 3 carbon atoms) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl Ether, tetraethylene glycol monophenyl ether, propylene glycol, propylene glycol Alkyl (1 to 4 carbon atoms) ether, propylene glycol monophenyl ether, dipropylene glycol monoalkyl (1 to 3 carbon atoms) ether, ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate ( 5) Ketone compounds: acetone, methyl ethyl ketone, 3-butyn-2-one, methyl-n-propyl ketone, methyl isopropyl ketone, 3-pentyn-2-one, methyl isopropenyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone Mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, 2 Octanone, 3-octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutylketone, trimethylnonanone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, Propiophenone, isophorone (6) and others: N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine, γ-butyrolactone, α -Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone

  These solvents can be used alone or in combination of two or more. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable from the viewpoint of compatibility.

  Although a solvent (J) can be suitably added to a transparent alkali-soluble silicone resin composition according to a coating film thickness and a viscosity, it is 50- on the mass reference | standard of all components other than the solvent in the photosensitive resin composition. It is preferable to use in the range of 1,000% by mass.

<Polymerization inhibitor>
In order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition may contain a polymerization inhibitor (for example, a radical polymerization inhibitor). Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis ( 4-hide Carboxymethyl-3,5-di-tert- butyl) can be used phenyl methane.

  When the polymerization inhibitor is added to the photosensitive resin composition, the content of the polymerization inhibitor is such that the polymerization inhibiting effect of the photopolymerizable double bond is 100 parts by mass with respect to the total solid content in the photosensitive resin composition. From the viewpoint of expression, 0.001 part by mass or more is preferable, more preferably 0.01 part by mass or more, while from the viewpoint of pattern formation due to radical generation during exposure, 5 part by mass or less is preferable. Preferably it is 1 mass part or less.

<Plasticizer>
Furthermore, you may make the photosensitive resin composition contain additives, such as a plasticizer, as needed. Examples of such additives include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. The content of the plasticizer when adding the plasticizer to the photosensitive resin composition is 0.1 mass from the viewpoint of increasing the flexibility of the film with respect to 100 mass parts of the total solid content in the photosensitive resin composition. Part or more is preferred, more preferably 0.5 parts by weight, and even more preferably 0.7 parts by weight. On the other hand, from the viewpoint of the glass transition temperature, 10 parts by weight or less is preferred, more preferably 8 parts by weight or less. More preferably, it is 5 parts by mass or less.

<Hardened product of photosensitive resin composition>
In the cured product obtained by curing the photosensitive resin composition used in the present invention, the transmittance of light at a wavelength of 400 nm after baking at 220 ° C. for 30 minutes in the atmosphere of the cured product having a thickness of 50 μm, It is preferably 90% or more. Moreover, it is also preferable to obtain a transparent insulating film by curing the photosensitive resin composition used in the present invention.

  Next, the suitable example of the method of forming a hardening relief pattern using the said photosensitive resin composition is shown below.

The method of forming a cured relief pattern includes a first step of applying a photosensitive resin composition on a substrate to obtain a coating film, a second step of irradiating the coating film with actinic rays, and uncured with a developer. It comprises a third step of removing the part, and a fourth step of heating and curing the substrate and the photocured part.
First, the said photosensitive resin composition is apply | coated on desired base materials, such as a silicon wafer, a ceramic substrate, an aluminum substrate, a glass substrate. As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used. After the coated substrate is soft baked at 80 ° C. to 200 ° C. for 1 to 15 minutes, it is irradiated with actinic rays through a desired photomask using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. .

  X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used as the actinic rays, but in the embodiment of the present invention, those having a wavelength of 200 nm to 500 nm are preferably used. From the viewpoint of pattern resolution and handleability, the light source wavelength is particularly preferably UV-i rays (365 nm), and a stepper is particularly preferable as the exposure projection apparatus.

  Thereafter, for the purpose of improving photosensitivity and the like, a combination of any temperature and time is used as necessary (preferably, the temperature is 40 ° C. to 200 ° C., and the time is 10 seconds to 360 seconds). Post-exposure baking (PEB) or pre-development baking may be performed.

  Next, development is carried out, and it can be carried out by selecting from methods such as dipping method, paddle method, shower method and rotary spray method. As the developer, an organic solvent or an alkaline developer is preferable. The good solvent of the composition of the present invention can be used alone, or a good solvent and a poor solvent can be appropriately mixed.

  Examples of suitable alkali developers include ammonium hydroxides such as alkali metal or alkaline earth metal carbonate aqueous solutions, alkali metal hydroxide aqueous solutions, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like. And amines such as diethylamine, triethylamine, diethanolamine, and triethanolamine. In particular, carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amines such as diethylamine and diethanolamine are contained in an amount of 0.05% by mass to 10% by mass. It is good to develop at the temperature of 20 to 35 degreeC using the weak alkaline aqueous solution to do.

  Examples of suitable organic solvent developers include, for example, glycol, ethylene glycol, propylene glycol and the like, and glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl. Examples include ether and propylene glycol monoethyl ether. Other organic solvent developers include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl- Examples thereof include gamma butyrolactone, cyclopentanone, and cyclohexanone.

  After the development is completed, the film is washed with a rinse solution, and the developer solution is removed to obtain a coating film with a relief pattern. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether and the like can be used alone, or appropriately mixed, or these can be used in a stepwise combination.

  The relief pattern thus obtained is converted into a cured relief pattern at a curing temperature of 150 ° C. to 250 ° C., which is much lower than the conventional polyimide precursor composition. This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven in which a temperature program can be set, and the like. Air may be used as the atmospheric gas for heat curing the relief pattern, and an inert gas such as nitrogen or argon may be used as necessary.

  The above-mentioned cured relief pattern is applied between a micro structure such as a surface protective film, an interlayer insulating film, an α-ray shielding film, and a micro lens array of a semiconductor device formed on a substrate such as a silicon wafer and the package material. Various semiconductor devices including an optical element such as a CMOS image sensor are used as any one selected from the group consisting of the supports (partition walls) and other processes are performed by applying known semiconductor device manufacturing methods. Can be manufactured. Moreover, an electronic component or a semiconductor device having a coating film made of a resin obtained by curing the photosensitive resin composition can be obtained.

  Hereinafter, the method of the present invention will be described in detail according to examples. However, the present invention is not limited to the following examples.

(Method of evaluation)
1. Evaluation of developability The photosensitive resin composition was applied to a glass substrate washed with an alkali so that the film thickness after baking was 50 μm, and baked on a hot plate at 95 ° C. for 4 minutes.

The substrate having the above coating film was exposed using an i-line stepper (NSR2005 i8A manufactured by Nikon) through a reticle with a test pattern. Exposure was carried out in air, and irradiated at intervals of 50 mJ / cm ² in the range of exposure amount of from 100 mJ / cm ² to 650 mJ / cm ^2. The exposure was performed in the atmosphere and the focus was set to zero.

  Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 60 seconds × 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned above was baked in an oven at 220 ° C. for 30 minutes in the atmosphere to be cured.

The portion of the obtained pattern with an exposure amount of 400 mJ / cm ² that was shielded from light with a square of 100 μm × 100 μm was observed with an optical microscope and evaluated according to the following criteria.
◎: The development residue is not seen at all when 10 openings are confirmed with an optical microscope. ○: When 10 openings are confirmed with an optical microscope, development residues are generated at 1 to 3 locations. Things △: When 10 openings were confirmed with an optical microscope, development residue occurred at 4 to 10 places ×: When 10 openings were confirmed with an optical microscope, development residue occurred at all And the remaining development occupies 30% or more of the area of the opening.

2. Evaluation of Crack Resistance and Transmittance The photosensitive resin composition was applied to a glass substrate washed with alkali so that the film thickness after baking was 50 μm, and baked on a hot plate at 95 ° C. for 4 minutes.

The substrate having the above-described coating film was exposed at an exposure amount of 400 mJ / cm ² using an i-line stepper through a reticle with a test pattern. The exposure was performed in the atmosphere and the focus was set to zero.

Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 60 seconds × 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned above was baked in an oven at 220 ° C. for 30 minutes in the atmosphere to be cured. Then, it observed with the visual observation and the optical microscope, and evaluated the crack on the following reference | standard.
◎: No cracks confirmed in 5 substrates ○: 1-5 cracks occurred in 5 substrates △: 6-15 cracks occurred in 5 substrates ×: 5 substrates There are more than 16 cracks inside

  A spectrophotometer UV-1600PC (manufactured by Shimadzu Corporation) was used for the above substrate, a glass substrate without a coating film was placed in the reference portion, the light transmittance of 800 nm to 300 nm was measured, and the light transmittance of 400 nm was confirmed. .

(Synthesis of polysiloxane A-1)
In a 1 L eggplant-shaped flask, 0.60 mol (173.14 g) of (3-trimethoxypropyl) succinic anhydride (trade name: X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.), Ba (OH) _2. 4.00 mmol (0.83 g) of H ₂ O powder (manufactured by SIGMA-ALDRICH) and 0.58 mol (20.30 g) of methanol were charged and stirred using a magnetic stirrer. A Dimroth was attached, and using an oil bath, the temperature was raised from room temperature to 75 ° C. and refluxed for 2.5 hours to open succinic anhydride.

  In a 2 L separable flask, DPD (diphenylsilanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxysilane) 1.40 mol (347.69 g) 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), prepared above ( The total amount of 3-trimethoxypropyl) succinic anhydride ring-opened product was charged and stirred using a stirring blade and a three-one motor. A Dimroth was attached and the temperature was raised from room temperature to 95 ° C. using an oil bath. After 1 hour, with the heating continued, the Dimroth was removed and connected to a three-way cock, cold trap, vacuum controller, and vacuum pump to remove methanol. Heating was continued for 10 hours while evacuating, and then the pressure was returned to normal pressure and cooled to room temperature, whereby transparent polysiloxane (A-1, viscosity at 40 ° C. was 83 poise) was obtained.

(Preparation of photosensitive resin composition)
The resin compositions of Examples 1 to 20 and Comparative Examples 1 to 15 were prepared as follows. In a wide-mouthed sample container, a plurality of components described in Table 1 or 2 below were blended in the ratios described in Table 1 or 2 below, and stirred and mixed with a web rotor. The mixture was pressure filtered through a PP filter having a pore size of 2.5 microns to obtain a resin composition.

  The results of the above evaluations for the resin compositions of Examples 1 to 20 and Comparative Examples 1 to 15 are shown in Table 1 or 2 below.

(Explanation of abbreviations in Table 1 or 2)
1. Surfactant (B)
B-1: DBE-821 (manufactured by Gelest)
B-2: DBE-712 (manufactured by Gelest)
2. Dissolution promoter (C)
C-1: isononanoic acid C-2: benzoic acid 3.1 Compound containing at least two photopolymerizable double bonds and at least two aromatic rings in the molecule (D)
D-1: Ethoxylated bisphenol A dimethacrylate “BPE-500” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-2: Ethoxylated bisphenol A diacrylate “A-BPE-10” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-3: Ethoxylated bisphenol A dimethacrylate “BPE-900” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-4: Bisphenol A type epoxy acrylate “EA-1020” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
4.1 Compound (X) containing two photopolymerizable double bonds in one molecule but not containing an aromatic ring
X-1: Polyethylene glycol # 600 diacrylate “A-600” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
X-2: Polyethylene glycol # 600 dimethacrylate “14G” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
5. Photopolymerization initiator (E)
E-1: Irugacure 819 (BASF)
6). UV absorber (F)
F-1: TINUVIN 405 (manufactured by BASF)
7. Silane coupling agent (G)
G-1: 3-methacryloxypropyltrimethoxysilane G-2: 3-acryloxypropyltrimethoxysilane8. Antioxidant (H)
H-1: TINUVIN 152 (hindered amine stabilizer having radical scavenging action, manufactured by BASF)

  The present invention relates to an insulating material used for a display device, formation of a surface protective film, an interlayer insulating film, an α-ray shielding film, and the like in a semiconductor device, and manufacture of an image sensor, a micromachine, or a semiconductor device mounted with a microactuator. In addition, it can be suitably used.

Claims (13)

An alkali-soluble silicone resin (A) having a carboxyl group or a dicarboxylic anhydride group in one molecule;
Surfactant (B);
Dissolution promoter (C);
A compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule; and a photopolymerization initiator (E);
Only including,
The alkali-soluble silicone resin (A)
The following general formula (I):
R ¹ R ² _a Si (R ³ ) _3-a (I)
{Wherein R ¹ is a monovalent organic group having 4 to 20 carbon atoms including a carboxyl group or a dicarboxylic anhydride group, R ² is a methyl group, R ³ is a methoxy group, ethoxy group And at least one monovalent organic group selected from the group consisting of a group, a propoxy group and an isopropoxy group, a hydroxyl group, or chlorine (Cl), and a is an integer of 0 or 1. }
A silane compound (A-1) represented by:
The following general formula (II):
R ⁴ _b R ⁵ _c Si (R ³ ) _4-bc (II)
{Wherein R ³ is at least one monovalent organic group selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group, a hydroxyl group, or Cl, and R ⁴ and R ⁵ are A group having 2 to 20 carbon atoms, a photopolymerizable double bond group or a polymerizable cyclic ether bond group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, a mercapto 4 or 4 carbon atoms including an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carboxyl group or dicarboxylic anhydride group which may be substituted with a group or an amino group R ⁴ and R ⁵ may be the same or different, and may be bonded to each other via a covalent bond, b is an integer selected from 0 to 2, c Is 0 or 1 And b + c does not exceed 2. }
A silane compound (A-2) represented by:
The following general formula (III):
R ⁶ ₂ Si (OH) ₂ (III)
{In the formula, R ⁶ represents an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, or a carbon atom number of 1 to 1 which may be substituted with a mercapto group or an amino group. 20 alkyl groups or cycloalkyl groups having 5 to 20 carbon atoms, which may be the same as or different from each other, and may be bonded to each other via a covalent bond. }
A silanediol compound (A-3) represented by:
A photosensitive resin composition obtained by reacting in the presence of a catalyst . The alkali-soluble silicone resin (A): 100 parts by mass;
The surfactant (B): 1 part by mass to 80 parts by mass;
The dissolution accelerator (C): 1 part by mass to 80 parts by mass;
Compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule: 1 part by mass to 300 parts by mass; and the photopolymerization initiator (E): 0.01 part by mass ~ 50 parts by mass;
The photosensitive resin composition of Claim 1 containing this.   The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble silicone resin (A) further has a photopolymerizable double bond group in one molecule. The photosensitive resin composition according to any one of claims 1 to 3 , wherein the surfactant (B) is a nonionic surfactant. The photosensitive resin composition according to any one of claims 1 to 4 , wherein the surfactant (B) is a silicone-based surfactant. The surfactant (B) is represented by the following general formula (IV-1) or (IV-2):

{In the above formula (IV-1) or (IV-2), R ^{7 to} R ¹⁶ independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁷ represents a hydrogen atom or the number of carbon atoms. 1 to 6 alkyl groups, d and e independently represent an integer of 1 or more, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and f and g are 0 or more. Represents an integer, f + g represents an integer of 1 or more, m represents an integer of 1 to 6, and EO and PO are in any order within [(EO) _f − (PO) _g ], It may be random or block. }
The photosensitive resin composition of any one of Claims 1-5 which is a polyether modified organosiloxane represented by these. The dissolution promoter (C) is a carboxylic acid compound, the photosensitive resin composition according to any one of claims 1-6. Compound (D) containing at least two photopolymerizable double bonds and at least two aromatic rings in one molecule,
Di (meth) acrylate having a bisphenol A skeleton having an alkylene oxide addition mole number of 0 to 30 represented by the following general formula (V-1);
Diglycidyl ether di (meth) acrylate having a bisphenol A skeleton represented by the following general formula (V-2), and full orange (meth) acrylate represented by the following general formula (V-3):

{In the above formula (V-1), (V-2) or (V-3), R ¹⁸ and R ¹⁹ are each independently an alkylene group having 2 to 4 carbon atoms, and R ²⁰ and R ²¹ Each independently represents a hydrogen atom or a methyl group, and h and i are integers, which may be the same or different, h + i = 0 to 24, and the above formula (V− The fluorene skeleton in 3) may have a substituent having 1 to 28 carbon atoms. }
Is at least one selected from the group consisting of photosensitive resin composition according to any one of claims 1-7. Based on the mass of the total solid content in the photosensitive resin composition, 0.1% by mass to 20% by mass of the surfactant (B) and 0.1% by mass to 20% by mass of the dissolution accelerator ( The photosensitive resin composition of any one of Claims 1-8 containing C). Including solvent (J) In addition, the photosensitive resin composition according to any one of claims 1-9. Cured product obtained by curing the photosensitive resin composition according to any one of claims 1-10. A transparent insulating film obtained by curing the photosensitive resin composition according to any one of claims 1-10. The following steps:
The process of apply | coating the photosensitive resin composition of any one of Claims 1-10 on a base material, and obtaining a coating film;
A step of irradiating the coating film with an actinic ray to photocur the exposed portion;
Removing the uncured portion of the coating film using a developer; and heating the substrate and the photocured portion of the coating film;
A method for forming a cured relief pattern, comprising: