CN101910945A - Photosensitive resin composition - Google Patents

Abstract

Disclosed is a photosensitive resin composition containing a silicon-containing acrylic resin (A), a siloxane compound (B) (excluding the component (A)), and a photosensitive substance (C).

Description

Photosensitive resin composition

technical field

The present invention relates to a photosensitive resin composition.

Background technique

In recent years, many display elements typified by liquid crystal displays and organic EL displays have been developed and are being put into practical use. In order to manufacture the patterns contained in these display elements, various photosensitive resin compositions have been proposed, for example, the photosensitive resin composition which contains an alkali-soluble resin and a photoinitiator is disclosed (patent document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 11-133600

When a pattern formed using the conventional photosensitive resin composition is exposed to high temperature, there is a problem that transparency falls.

Contents of the invention

The inventors of the present invention have conducted studies on the above-mentioned technical problems, and as a result, have found a photosensitive resin composition capable of forming a pattern excellent in heat-resistant light transmittance.

The present invention is a photosensitive resin composition comprising: a silicon-containing acrylic resin (A), a siloxane compound (B) (wherein (A) is not included), and a photosensitive substance (C).

In addition, the present invention provides a photosensitive resin composition as described above, wherein the silicon-containing acrylic resin (A) contains at least a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom and an unsaturated A copolymer obtained by copolymerizing carboxylic acid and/or unsaturated carboxylic acid anhydride (A2).

Moreover, this invention provides the said photosensitive resin composition whose nonhydrolyzable polymerizable unsaturated compound (A1) which has a silicon atom is a compound represented by formula (I).

[In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents -O-(CH ₂ ) _w -, -C(=O)-O-(CH ₂ ) _w -, or -(CH ₂ ) _w -. Carbon atoms contained in R ² may be replaced by heteroatoms. w represents an integer of 0-8. R ³ to R ⁵ each independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Hydrogen atoms contained in the aliphatic hydrocarbon group, aryl group and aralkyl group may be substituted with halogen atoms. y represents the integer of 1-5, and x and z represent the integer of 0-5 each independently. ]

In addition, the present invention provides a photosensitive resin composition as described above, wherein the silicon-containing acrylic resin (A) further contains a monomer (A3) that can be copolymerized with (A1) and (A2) (wherein , excluding (A1) and (A2).) Copolymers formed by polymerization.

In addition, the present invention provides the photosensitive resin composition as described above, wherein the siloxane compound (B) (excluding (A)) is a structure derived from a monomer represented by formula (II). unit compound.

R ⁸ _n Si(OR ⁹ ) _4-n (II)

[In formula (II), R ⁸ and R ⁹ independently represent an aliphatic hydrocarbon group with 1 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms or an aralkyl group with 7 to 12 carbon atoms , the hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group can be replaced by a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, an alkoxy group with 1 to 4 carbon atoms, an amino group, a mercapto group, an imino group, Epoxy or (meth)acryloyl substituted. n represents an integer of 0-3. When n is an integer of 2 or less, R ⁹ may be the same or different. When n is an integer of 2 or more, R ⁸ may be the same or different. ]

Moreover, this invention provides the said photosensitive resin composition containing a thermosetting accelerator (D).

Moreover, this invention provides the said photosensitive resin composition containing a solvent (E).

Moreover, this invention provides the said photosensitive resin composition containing a photosensitizer (F).

Moreover, this invention provides the pattern formed using the said photosensitive resin composition.

In addition, the present invention provides a display element including the above pattern.

Detailed ways

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention contains a silicon-containing acrylic resin (A).

The silicon-containing acrylic resin (A) refers to a polymer of acrylate or methacrylate containing silicon atoms.

The silicon-containing acrylic resin (A) preferably contains at least a non-hydrolyzable polymerizable unsaturated compound (A1) (hereinafter, sometimes referred to as (A1)) having a silicon atom, and an unsaturated carboxylic acid and/or an unsaturated carboxylic acid. A silicon-containing acrylic resin formed of a copolymer obtained by polymerizing an acid anhydride (A2) (hereinafter, sometimes referred to as (A2)). The term (A1) refers to a compound that is non-hydrolyzable, that is, does not contain a hydrolyzable group (for example, an alkoxy group, an alkoxycarbonyl group, or a carboxyl group) and contains a polymerizable group and an unsaturated bond. The unsaturated carboxylic acid in (A2) means the carboxylic acid which has an unsaturated bond, and the unsaturated carboxylic acid anhydride means the carboxylic anhydride which has an unsaturated bond.

(A1) is preferably a compound represented by formula (I).

[In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents -O-(CH ₂ ) _w -, -C(=O)-O-(CH ₂ ) _w -, or -(CH ₂ ) _w -. Carbon atoms contained in R ² may be replaced by heteroatoms. w represents an integer of 0-8.

R ³ to R ⁵ each independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Hydrogen atoms contained in the aliphatic hydrocarbon groups, aryl groups and aralkyl groups may be substituted with halogen atoms. y represents the integer of 1-5, and x and z represent the integer of 0-5 each independently. ]

Examples of R ² include a single bond; an ester bond; an ether bond; methylene, ethylene, trimethylene, 1-methylethylene, 2-methylethylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, 1-ethylethylene, 2-ethylethylene, and other alkylene groups; oxymethylene, Oxyethylene, propylene glycol, thiomethylene, thioethylene, thiopropylene, aminomethylene, aminoethylene, aminopropylene and other heteroatom-containing alkylene groups etc. Preferably, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are mentioned.

R ³ to R ⁵ can be selected from non-hydrolyzable monovalent groups. As such a non-hydrolyzable group, any group selected from a non-polymerizable group and a polymerizable group may be used. It should be noted that the so-called non-hydrolyzable group refers to a group having a hydrolyzable group (for example, an alkoxy group, an alkoxycarbonyl group, or a carboxyl group, etc.) that can be hydrolyzed and exists stably without being hydrolyzed. group of properties.

Examples of R ³ to R ⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, octyl, dodecyl and the like. The number of carbon atoms is 1-12 aliphatic hydrocarbon groups; aryl groups such as phenyl, biphenyl, naphthyl, etc.; aralkyl groups such as tolyl, xylyl, 3,5-xylyl, etc. Preferable aliphatic hydrocarbon groups include methyl and ethyl groups, and preferable aryl groups include phenyl and pentafluorophenyl, more preferably phenyl. In addition, examples of preferable aralkyl groups include trifluoromethylphenyl and bis(trifluoromethyl)phenyl.

As a compound represented by formula (I), for example, (trimethylsilylmethyl) methacrylate, (phenyldimethylsilyl) methyl methacrylate, 1-(3- Methacryloxypropyl)-1,1,3,3,3-pentamethyldisiloxane, 1-(3-methacryloxypropyl)polydimethylsiloxane, 3-Acryloxypropylmethylbis(trimethylsiloxy)silane, 3-methacryloxypropyltris(trimethylsiloxy)silane, tert-butyldimethylvinylsilane , Allyldimethylsilane, Allyltrimethylsilane, Triphenylvinylsilane, Trimethylsilylmethacrylate, Vinyldiethylmethylsilane, Vinyltri(trimethylsilane) ylsiloxy)silane, vinyltrimethylsilane, vinylmethylbis(trimethylsiloxy)silane, phenyldimethylvinylsilane, phenylmethylvinylsilane, etc., these groups Can be used alone or in combination.

As (A1), for example, FM-0711 (M _w : 1000, formula (I-1-1)), FM-0721 (M _w : 5000, formula (I-1-1)), FM-0725 ( M _w : 10000, formula (I-1-1)), FM-0701 (M _w : 420, formula (I-1-1)), FM-0701T (M _w : 420, formula (I-2-1 )) (all made by Chisso Co., Ltd.), X-22-174DX (M _w : 4600, formula (I-1-1)), X-24-8201 (M _w : 2100), X-22- 2426 (M _w : 12000, formula (I-1-1)), X-22-2404 (M _w : 420, formula (I-2-1)), X-22-2406 (both Shin-Etsu Chemical Industry ( Co., Ltd.) and other commercially available products.

[In formula (I-1-1), R ⁵ , w, and y have the same definitions as above. ]

Examples of (A2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, methylfumaric acid, and itaconic acid; Unsaturated dicarboxylic acids;

Anhydrides of the above-mentioned unsaturated dicarboxylic acids;

Succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], etc. base) acryloyloxyalkyl] esters; unsaturated acrylic esters such as α-(hydroxymethyl)acrylic acid containing hydroxyl and carboxyl groups in the same molecule, etc. Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoint of high copolymerization reactivity and solubility in an aqueous alkali solution. These can be used alone or in combination.

Furthermore, the silicon-containing acrylic resin (A) preferably further contains a monomer (A3) that can be copolymerized with (A1) and (A2) (wherein, (A1) and (A2) are not included. Hereinafter, it may be referred to as " (A3)".) A silicon-containing acrylic resin made of a copolymer formed by polymerization.

(A3) Preferably, a compound having at least one group selected from an epoxy group, an oxetanyl group, an activated methylene group, and an activated methine group, and an unsaturated bond. Examples include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 3 -(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(methyl )acryloyloxymethyloxetane, 2-phenyl-3-(meth)acryloyloxymethyloxetane, 2-trifluoromethyl-3-(meth)propene Acyloxymethyloxetane, 2-pentafluoroethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxy Ethyl oxetane, 3-methyl-3-(meth)acryloxyethyl oxetane, 2-phenyl-3-(meth)acryloxyethyl oxetane Heteretane, 2-trifluoromethyl-3-(meth)acryloxyethyl oxetane or 2-pentafluoroethyl-3-(meth)acryloxyethyl oxetane Heteretane, etc., preferably 3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane , 3-ethyl-3-(meth)acryloyloxymethyloxetane, 2-phenyl-3-(meth)acryloyloxymethyloxetane, 2-tri Fluoromethyl-3-(meth)acryloyloxymethyloxetane, 2-pentafluoroethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl Base-3-(meth)acryloyloxyethyl oxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, 2-phenyl-3- (Meth)acryloyloxyethyloxetane, 2-trifluoromethyl-3-(meth)acryloyloxyethyloxetane or 2-pentafluoroethyl-3- (Meth)acryloyloxyethyloxetane.

The aforementioned compound having an epoxy group and an unsaturated bond is preferably a compound having an epoxy group and an unsaturated bond on the ring of the aliphatic polycyclic compound. Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, and tricycloundecane. Alkanes, bicyclododecanes, tricyclododecanes, etc., preferably compounds having 8 to 12 carbon atoms.

More preferable compounds include at least one compound selected from the compound represented by formula (III) and the compound represented by formula (IV).

[In formula (III) and formula (IV), R represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms substituted by a hydrogen atom or a hydroxyl group.

X represents an alkylene group having 1 to 6 carbon atoms which may contain a single bond or a heteroatom. ]

Examples of R include aliphatic hydrocarbon groups such as a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group; hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, 2-hydroxy-isopropyl, 1-hydroxy- Aliphatic hydrocarbon groups containing hydroxyl groups such as n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, preferably hydrogen atoms, methyl, hydroxymethyl, 1-hydroxyethyl group and 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of X include alkylene groups such as single bonds, methylene groups, ethylene groups, and propylene groups; oxymethylene groups, oxyethylene groups, oxypropylene groups, thiomethylene groups, and thioxo groups; Alkylene groups containing heteroatoms such as ethylene, thiopropylene, aminomethylene, aminoethylene, aminopropylene, etc., preferably single bond, methylene, ethylene, oxymethylene and oxyethylene, more preferably a single bond and oxyethylene.

The compound represented by formula (III) includes, for example, compounds represented by formula (III-1) to formula (III-15), etc., preferably formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9), formula (III-11) ~ formula (III-15), more preferably formula (III-1), formula (III-7), Formula (III-9), formula (III-15).

The compound represented by formula (IV) includes, for example, compounds represented by formula (IV-1) to formula (IV-15), etc., preferably formula (IV-1), formula (IV-3), formula (IV-5), formula (IV-7), formula (IV-9), formula (IV-11) ~ formula (IV-15), more preferably formula (IV-1), formula (IV-7), Formula (IV-9), formula (IV-15).

At least one compound selected from the compound represented by formula (III) and the compound represented by formula (IV) can be used alone. In addition, these can also be mixed in arbitrary ratios. When mixing, the mixing ratio is in molar ratio, preferably (compound represented by formula (III)): (compound represented by formula (IV)) is 5:95～95:5, more preferably 10:90～90 :10, particularly preferably 20:80 to 80:20.

As the compound having at least one group selected from active methylene and active methine and an unsaturated bond, for example, compounds represented by formula (V-1) to formula (V-18) compounds, etc.

Among them, 2-(methacryloyloxy)ethyl acetoacetate represented by formula (V-1) is preferable.

Other copolymerizable monomers (A4) may be added to the silicon-containing acrylic resin (A) (excluding (A1), (A2) and (A3). Hereinafter, it may be referred to as "(A4)".) , As (A4), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylate ) Alkyl (meth)acrylates such as tert-butyl acrylate;

Alkyl acrylates such as methyl acrylate and isopropyl acrylate;

Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2.6 ]decane-8-yl (meth)acrylate (in this technical field, as a customary Name, known as (meth)acrylate dicyclopentenyl ester.), (meth)acrylate dicyclopentenyloxyethyl ester, (meth)acrylate isobornyl ester and other (meth)acrylic rings Alkyl esters;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2.6 ]decane-8-yl acrylate (in this technical field, as a common name, called dicyclopentanyl (meth)acrylate Alkenyl ester.), dicyclopentyloxyethyl acrylate, isobornyl acrylate and other cyclic alkyl acrylates;

Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

Aryl acrylates such as phenyl acrylate, benzyl acrylate, etc.;

Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2 .1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl )bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6 -Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]heptene -2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[ 2.2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-Hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (norbornene diacid anhydride), 5-tert-butoxycarbonylbicyclo[2.2.1 ]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert Butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other ring unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzene Formate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide hexanoate, N-butanedi Imide-3-maleic imide propionate, N-(9-acridyl) maleic imide and other dicarbonyl imide derivatives;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide , methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and other vinyl compounds.

Among them, styrene, N-phenylmaleic imide, N-cyclohexylmaleic imide, and N-benzylmaleic acid are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. imide etc. These can be used alone or in combination.

The silicon-containing acrylic resin (A) is a silicon-containing acrylic resin containing at least a copolymer obtained by polymerizing (A1) and (A2). If necessary, a structural unit represented by (A3) may also be contained, and a structural unit represented by (A4) may also be contained.

When the silicon-containing acrylic resin (A) is composed of only structural units represented by (A1) and (A2), in the silicon-containing acrylic resin (A), the constituent units represented by (A1) and (A2) The ratio is preferably in the following range in terms of mole fraction relative to the total number of moles of the constituent components constituting the above-mentioned copolymer.

Structural units represented by (A1): 50 to 95 mol%

Structural units represented by (A2): 5 to 50 mol%

When the silicon-containing acrylic resin (A) contains structural units represented by (A1) and (A2) in addition to structural units represented by (A3) and (A4), the silicon-containing acrylic resin In (A), the ratio of the constituent components represented by (A1) to (A4) is preferably in the following range in terms of mole fraction relative to the total number of moles of the constituent components constituting the above-mentioned copolymer.

Structural units represented by (A1): 5 to 75 mol%

Structural units represented by (A2): 5 to 50 mol%

Structural units represented by (A3): 0 to 85 mol%

Structural units represented by (A4): 0 to 50 mol%

When the mole fraction of the constituent components is within this range, the compatibility between the silicon-containing acrylic resin (A) and the siloxane compound (B) (excluding (A)) becomes good. It is preferable that film reduction is less likely to occur, and the peeling property of the non-pixel portion at the time of image development is also good, and the resolution becomes good.

The silicon-containing acrylic resin (A) can be, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition, 1st Printing, March 1, 1972) and the cited documents described in this document are made by reference. Specifically, a predetermined amount of the units (A1) and (A2) constituting the copolymer, a polymerization initiator, and a solvent are put into a reaction vessel, and nitrogen is substituted for oxygen, thereby stirring, heating, and Keeping warm to obtain a polymer. In addition, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like.

The polystyrene-equivalent weight average molecular weight of the silicon-containing acrylic resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight-average molecular weight of the silicon-containing acrylic resin (A) is within this range, the applicability is good, film reduction is less likely to occur during development, and the peeling property of the non-pixel portion during development is good, and the resolution becomes good. , and thus preferred. The molecular weight distribution [weight average molecular weight (M _w )/number average molecular weight (Mn)] of the silicon-containing acrylic resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within this range, it is preferable because developability is favorable and resolution is excellent.

The content of the silicon-containing acrylic resin (A), in terms of mass fraction relative to the solid content in the photosensitive resin composition (referring to the components in the composition that are solid at 25° C.), is preferably 5 to 90% by mass, more preferably 10 to 70% by mass. When the content of the silicon-containing acrylic resin (A) is in this range, the heat-resistant light transmittance tends to be improved, which is preferable. In this manual,

The heat-resistant light transmittance refers to the change rate of the light transmittance in the visible light region before and after heating when the coating film containing the photosensitive resin composition is heated.

The photosensitive resin composition of the present invention contains a siloxane compound (B) (but (A) is not included.).

The siloxane compound (B) (but (A) is not included) is preferably a compound containing a structural unit derived from a monomer represented by formula (II).

R ⁸ _n Si(OR ⁹ ) _4-n (II)

[In formula (II), R ⁸ and R ⁹ independently represent an aliphatic hydrocarbon group with 1 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms or an aralkyl group with 7 to 12 carbon atoms , the hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group can be replaced by a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, an alkoxy group with 1 to 4 carbon atoms, an amino group, a mercapto group, an imino group, Epoxy or (meth)acryloyl substituted. n represents an integer of 0-3. When n is an integer of 2 or less, R ⁹ may be the same or different. When n is an integer of 2 or more, R ⁸ may be the same or different. ]

The siloxane compound (B) (wherein (A) is not included) is an oligomer, a polymer, or a mixture thereof containing a structural unit derived from a monomer represented by formula (II).

基、和它们的氘、氟、氯化物。优选作为肪族烃基的甲基、3，3，3-三氟丙基、三氘甲基，优选作为芳基的苯基、五氟苯基、五氘苯基，特别优选作为芳基的苯基。另外，作为优选的芳烷基，可举出三氟甲基苯基、双(三氟甲基)苯基。As R ⁸ and R ⁹ , for example, methyl, ethyl, propyl, butyl, octyl, dodecyl, and their deuterium-substituents as aliphatic hydrocarbon groups; phenyl as aryl groups; , biphenyl, naphthyl, and their respective substituents of deuterium, fluorine, or chlorine; as aralkyl tolyl, xylyl,

groups, and their deuterium, fluorine, chloride. Preference is given to methyl, 3,3,3-trifluoropropyl, trideuteromethyl as aliphatic hydrocarbon groups, preferably phenyl, pentafluorophenyl, pentadeuterophenyl as aryl groups, particularly preferably benzene as aryl groups base. In addition, examples of preferable aralkyl groups include trifluoromethylphenyl and bis(trifluoromethyl)phenyl.

The hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group can be replaced by a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, an alkoxyl group with 1 to 4 carbon atoms, an amino group, a mercapto group, an imino group, an epoxy group, etc. Substituted by group or (meth)acryloyl group.

The monomer represented by formula (II) represents, for example, alkoxysilane and a silane coupling agent. Specifically, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrakis(2-methacryloyloxyethoxy)silane, tetrakis(2-acryloyloxyethyl) oxy)silane, tetrachlorosilane, tetraacetoxysilane, tetraaminosilane, methyltrimethoxysilane, methyltrichlorosilane, methyldichlorosilane, methyldimethoxysilane, methyltriacetylsilane Oxysilane, Methyltriethoxysilane, Methyltributoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, 3,3,3-Trifluoropropyltriethoxysilane , Dimethyldimethoxysilane, Dimethyldichlorosilane, Trimethylchlorosilane, Trimethylmethoxysilane, Triethylsilane, Triethylchlorosilane, Benzyltrimethoxysilane, Benzene phenyltrimethoxysilane, phenylsilane, phenyltriacetoxysilane, phenyltriaminosilane, phenyltrichlorosilane, phenyltriethoxysilane, xylyltrimethoxysilane, trifluoromethyl Phenyltrimethoxysilane, Biphenyltrimethoxysilane, Biphenyltrichlorosilane, Diphenyldimethoxysilane, Diphenyldichlorosilane, Vinyltrimethoxysilane, Vinyltriethoxysilane , vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

The silicone compound (B) (wherein, (A) is not included.) represents, for example, organopolysiloxane resins, and organopolysiloxane resins are roughly classified into methylpolysiloxane resins and methylphenylpolysiloxane resins. alkane resin.

As the methylpolysiloxane resin, generally, a three-dimensional network structure in which structural units of SiO ₂ , CH ₃ SiO _3/2 , (CH ₃ ) ₂ SiO, and (CH ₃ ) ₃ SiO _1/2 are combined of copolymers.

As the methylphenylpolysiloxane resin, generally, combinations of SiO ₂ , CH ₃ SiO _3/2 , C ₆ H ₅ SiO _3/2 , (CH ₃ ) ₂ SiO, (C ₆ H ₅ ) ₃ SiO _3/2 , (CH ₃ ) ₃ SiO _1/2 , (C ₆ H ₅ )(CH ₃ )SiO, (C ₆ H ₅ ) ₂ SiO are three-dimensional network copolymers. Methylpolysiloxane resins are more heat resistant.

As the organopolysiloxane resin, for example, KR-242A, KC-89, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, X-40-9227 can be used , X-40-9247, KR-251, KR-400, KR-401N, KR-510, KR-9218, KR-217, X-41-1053, X-41-1056, X-41-1805, X -41-1810, X-40-2651, X-40-2655A, KR-271, KR-282, KR-300, KR-311, KR-212, KR-213, KR-400, KR-255, ES Commercially available products such as 1001N, ES-1002T, ES-1023, ES-5206, ES-5230, ES-5235, ES-9706 (all are manufactured by Shin-Etsu Chemical Co., Ltd.).

The silanol content of the siloxane compound (B) (here, the silanol content refers to the ratio of the OH group (group derived from silanol) at 3500 cm ^-1 and the silicon-methyl group at 1271 cm ^-1 based on infrared spectroscopic analysis. Abs(3500cm ^-1 )/Abs(1271cm ^-1 ), the absorbance ratio of the absorption peak, is preferably 1% or less.

The content of the siloxane compound (B) is preferably 20 to 90 mass fractions relative to the solid content in the photosensitive resin composition (among the components in the composition, solids at 25° C.). %, more preferably 40 to 80% by mass. When the content of the siloxane compound (B) is within this range, the heat-resistant light transmittance tends to be further improved, which is preferable.

The heat-resistant light transmittance of the photosensitive resin composition of this invention improves with silicon-containing acrylic resin (A) and a siloxane compound (B) (excluding (A)).

The photosensitive resin composition of this invention contains a photosensitive substance (C). A photoacid generator and a photobase generator are mentioned as a photosensitive substance (C).

There are nonionic compounds and ionic compounds in photoacid generators.

As the nonionic compound, for example, a halogen-containing compound, a diazoketone compound, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, a sulfonimide compound, a sulfonebenzotriazole compound, etc. can be used. .

As a halogen-containing compound, the hydrocarbon compound containing a halogenated alkyl group, the heterocyclic compound etc. which contain a halogenated alkyl group are mentioned, for example. Examples of preferred halogen-containing compounds include 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 2-phenyl-4,6-bis(trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine and the like.

Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazoquinone compounds, and diazonaphthoquinone compounds. Preferred diazoketone compounds include, for example, 1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid and 2,3,4,4 '-Tetrahydroxybenzophenone esterification, 1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid with 1,1,1 - three (4-hydroxyphenyl) ethane formed esterification, 1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid with 4, 4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]diphenol, etc.

Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tolyl) Sulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclo Hexylsulfonyl(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonyl(benzoyl)diazomethane wait.

基苯甲酰甲基砜、双(苯基磺酰基)甲烷、4-氯苯基-4-甲基苯基二砜化合物等。Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds and the like. Examples of preferred sulfone compounds include 4-triphenacylsulfone,

phenylphenacylsulfone, bis(phenylsulfonyl)methane, 4-chlorophenyl-4-methylphenyldisulfone compounds, etc.

Examples of the sulfonate compound include alkylsulfonate, haloalkylsulfonate, arylsulfonate, iminosulfonate, and the like. Preferable examples include benzoin tosylate, pyrogallol trimesylate, tribenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrate benzylbenzenesulfonate, etc. Examples of iminosulfonic acid esters include PAI-101 (manufactured by Midori Chemical Co., Ltd.), PAI-106 (manufactured by Midori Chemical Co., Ltd.), and CGI-1311 (manufactured by Ciba Co., Ltd.).

As a carboxylate compound, for example, o-nitrobenzyl carboxylate is mentioned.

Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(bornanesulfonyloxy)succinimide, N-(4-methylbenzene Sulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-( Trifluoromethylsulfonyloxy)phthalimide, N-(camphoranesulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide Dicarboximide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-( Camphanesulfonyloxy)diphenylmaleic imide, 4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy ) diphenylmaleic imide, N-(4-fluorophenylsulfonyloxy)diphenylmaleic imide, N-(4-fluorophenylsulfonyloxy)diphenylmaleic acid Acid imide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.]hept-5-ene-2,3-dicarboxylic acid imide, N-(camphorylsulfonyloxy)bicyclo[2.2 .1] Hept-5-ene-2,3-dicarboxylic acid imide, N-(bornanesulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3- Dicarboxylic imide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide, N-(4 -Methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-methylphenylsulfonyloxy)-7-oxa Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene- 2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy )-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyl oxygen)bicyclo[2.2.1]heptane-5 , 6-oxo-2,3-dicarboxylic acid imide, N-(bornanesulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide , N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide, N-(2-trifluoromethylbenzene Sulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane Alkane-5,6-oxo-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)naphthyl dicarboxylic acid imide, N-(camphorylsulfonyloxy)naphthyl Dicarboxylic acid imide, N-(4-methylbenzene Sulfonyloxy)naphthyl dicarboxylic imide, N-(2-trifluoromethylphenylsulfonyloxy)naphthyl dicarboxylic imide, N-(4-fluorophenylsulfonyloxy) Naphthyl dicarboxylic acid imide, N-(pentafluoroethylsulfonyloxy)naphthyl dicarboxylic acid imide, N-(heptafluoropropylsulfonyloxy)naphthyl dicarboxylic acid imide, N -(Nafluorobutylsulfonyloxy)naphthyl dicarboxylic acid imide, N-(ethylsulfonyloxy)naphthyl dicarboxylic acid imide, N-(propylsulfonyloxy)naphthyl dicarboxylic acid imide Acid imide, N-(butylsulfonyloxy)naphthyl dicarboxylic acid imide, N-(pentylsulfonyloxy)naphthyl dicarboxylic acid imide, N-(hexylsulfonyloxy)naphthalene Dicarboxylic imide, N-(heptylsulfonyloxy)naphthyldicarboxylic imide, N-(octylsulfonyloxy)naphthyldicarboxylic imide, N-(nonylsulfonyl Acyloxy)naphthyl dicarboxylic acid imide, etc.

Examples of sulfone benzotriazole compounds include 1-trifluoromethanesulfonyloxybenzotriazole, 1-nonafluorobutylsulfonyloxybenzotriazole, 1-(4-methylphenyl Sulfonyloxy)-benzotriazole, etc.

As the ionic compound, a compound composed of an onium cation and an anion derived from a Lewis acid can be used. Examples of the onium cation include diphenyliodonium, bis(p-tolyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-octylphenyl)iodonium, bis(p-tolylphenyl)iodonium, Octadecylphenyl)iodonium, bis(p-octyloxyphenyl)iodonium, bis(p-octadecyloxyphenyl)iodonium, phenyl(p-octadecyloxyphenyl) ) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, three (p-tolyl) sulfonium, three (p-isopropylphenyl) sulfonium, three (2,6- Dimethylphenyl)sulfonium, tri(p-tert-butylphenyl)sulfonium, tri(p-cyanophenyl)sulfonium, tri(p-chlorophenyl)sulfonium, dimethyl(methoxy)sulfonium, dimethyl (ethoxy)sulfonium, dimethyl(propoxy)sulfonium, dimethyl(butoxy)sulfonium, dimethyl(octylsulfonium)sulfonium, dimethyl(octadecylsulfonium)sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyl oxygen) sulfonium, dimethyl (cyclohexyl oxygen) sulfonium, dimethyl (fluoromethoxy) base) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8- Nitrooctyloxy)sulfonium, Dimethyl(18-trifluoromethyloctadecyloxy)sulfonium, Dimethyl(2-hydroxyisopropoxy)sulfonium, or Dimethyl(tris(trichloromethane) base) methyl) sulfonium, etc.

Examples of preferred onium cations include bis(p-tolyl)iodonium, (p-tolyl)(p-isopropylphenyl)iodonium, bis(p-tert-butylphenyl)iodonium, triphenylsulfonium Or three (p-tert-butylphenyl) sulfonium, etc.

Examples of the above-mentioned anion derived from a Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate, and the like. Preference is given to hexafluoroantimonate or tetrakis(pentafluorophenyl)borate as anion from Lewis acids. The aforementioned onium cations and anions derived from Lewis acids may be combined arbitrarily.

Examples of cationic polymerization initiators include diphenyliodonium hexafluorophosphate, bis(p-tolyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, Bis(p-octylphenyl)iodonium hexafluorophosphate, bis(p-octadecylphenyl)iodonium hexafluorophosphate, bis(p-octyloxyphenyl)iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl)iodonium hexafluorophosphate, phenyl(p-octadecyloxyphenyl)iodonium hexafluorophosphate, (p-tolyl)(p-isopropylphenyl ) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate, ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris(p-tolyl)sulfonium hexafluorophosphate , Tris(p-isopropylphenyl)sulfonium hexafluorophosphate, tris(2,6-dimethylphenyl)sulfonium hexafluorophosphate, tris(p-tert-butylphenyl)sulfonium hexafluorophosphate, three (p-cyanophenyl)sulfonium hexafluorophosphate, tris(p-chlorophenyl)sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl Dimethyl(methoxy)sulfonium hexafluorophosphate, Dimethyl(ethoxy)sulfonium hexafluorophosphate, Dimethyl(propoxy)sulfonium hexafluorophosphate, Dimethyl(butoxy)sulfonium hexafluorophosphate Fluorophosphate, dimethyl(octyloxy)sulfonium hexafluorophosphate, dimethyl(octadecyloxy)sulfonium hexafluorophosphate, dimethyl(isopropoxy)sulfonium hexafluorophosphate, di Methyl(tert-butoxy)sulfonium hexafluorophosphate, Dimethyl(cyclopentyloxy)sulfonium hexafluorophosphate, Dimethyl(cyclohexyloxy)sulfonium hexafluorophosphate, Dimethyl(fluoromethoxy base) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyano Butoxy)sulfonium hexafluorophosphate, Dimethyl(8-nitrooctyloxy)sulfonium hexafluorophosphate, Dimethyl(18-trifluoromethyloctadecyloxy)sulfonium hexafluorophosphate, Dimethyl(2-hydroxyisopropoxy)sulfonium hexafluorophosphate, dimethyl(tris(trichloromethyl)methyl)sulfonium hexafluorophosphate; diphenyliodonium hexafluoroarsenate, bis (p-tolyl)iodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluoroarsenate, bis(p-octylphenyl)iodonium hexafluoroarsenate, bis(p-deca Octylphenyl)iodonium hexafluoroarsenate, bis(p-octyloxyphenyl)iodonium hexafluoroarsenate, bis(p-octadecyloxyphenyl)iodonium hexafluoroarsenate salt, phenyl(p-octadecyloxyphenyl)iodonium hexafluoroarsenate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroarsenate, methylnaphthyl iodonium Hexafluoroarsenate, ethylnaphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris(p-tolyl)sulfonium hexafluoroarsenate, tris(p-isopropylphenyl) Sulfonium hexafluoroarsenate, tris(2,6-dimethylphenyl)sulfonium hexafluoroarsenate, tris(p-tert-butylphenyl)sulfonium hexafluoroarsenate, tris(p-cyanophenyl) Sulfonium hexafluoroarsenate, tri(p-chlorophenyl)sulfonium hexafluoroarsenate, dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate, dimethyl(formazolium oxy)sulfonium hexafluoroarsenate, dimethyl(ethoxy)sulfonium hexafluoroarsenate, dimethyl(propoxy)sulfonium hexafluoroarsenate, dimethyl(butoxy )sulfonium hexafluoroarsenate, dimethyl(octyloxy)sulfonium hexafluoroarsenate, dimethyl(octadecyloxy)sulfonium hexafluoroarsenate, dimethyl(isopropoxy)sulfonium Hexafluoroarsenate, Dimethyl(tert-butoxy)sulfonium hexafluoroarsenate, Dimethyl(cyclopentyloxy)sulfonium hexafluoroarsenate, Dimethyl(cyclohexyloxy)sulfonium hexafluoroarsenate Dimethyl(fluoromethoxy)sulfonium hexafluoroarsenate, Dimethyl(2-chloroethoxy)sulfonium hexafluoroarsenate, Dimethyl(3-bromopropoxy)sulfonium hexafluoroarsenate Fluoroarsenate, Dimethyl(4-cyanobutoxy)sulfonium hexafluoroarsenate, Dimethyl(8-nitrooctyloxy)sulfonium hexafluoroarsenate, Dimethyl(18-tris Fluoromethyloctadecyloxy)sulfonium hexafluoroarsenate, Dimethyl(2-hydroxyisopropoxy)sulfonium hexafluoroarsenate, Dimethyl(tris(trichloromethyl)methyl)sulfonium Hexafluoroarsenate; diphenyliodonium hexafluoroantimonate, bis(p-tolyl)iodonium hexafluoroantimonate, bis(p-tert-butylphenyl)iodonium hexafluoroantimonate, bis( p-octylphenyl)iodonium hexafluoroantimonate, bis(p-octadecylphenyl)iodonium hexafluoroantimonate, bis(p-octyloxyphenyl)iodonium hexafluoroantimonate, Bis(p-octadecyloxyphenyl)iodonium hexafluoroantimonate, phenyl(p-octadecyloxyphenyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropyl phenyl) iodonium hexafluoroantimonate, methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tri(p-toluene Base) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris (2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butyl Phenyl)sulfonium hexafluoroantimonate, tris(p-cyanophenyl)sulfonium hexafluoroantimonate, tris(p-chlorophenyl)sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate , Diethylnaphthylsulfonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) )sulfonium hexafluoroantimonate, dimethyl(butoxy)sulfonium hexafluoroantimonate, dimethyl(octyloxy)sulfonium hexafluoroantimonate, dimethyl(octadecyloxy)sulfonium hexafluoroantimonate Fluoroantimonate, Dimethyl(isopropoxy)sulfonium hexafluoroantimonate, Dimethyl(tert-butoxy)sulfonium hexafluoroantimonate, Dimethyl(cyclopentyloxy)sulfonium hexafluoroantimonate Dimethyl(cyclohexyloxy)sulfonium hexafluoroantimonate, Dimethyl(fluoromethoxy)sulfonium hexafluoroantimonate, Dimethyl(2-chloroethoxy)sulfonium hexafluoroantimonate salt, dimethyl(3-bromopropoxy)sulfonium hexafluoroantimonate, dimethyl(4-cyanobutoxy)sulfonium hexafluoroantimonate, dimethyl(8-nitrooctyloxy ) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyl octadecyl oxide) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate, Dimethyl(tris(trichloromethyl)methyl)sulfonium hexafluoroantimonate; diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(p-tolyl)iodonium tetrakis(pentafluorophenyl) base) borate, bis(p-tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-octylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis (p-octadecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl[4-(1-methylethyl)benzene Base] iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis(pentafluorophenyl)borate, phenyl(p-octadecyloxyphenyl)iodonium tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-cymene Base) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, three Phenylsulfonium tetrakis(pentafluorophenyl)borate, Tris(p-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, Tris(p-isopropylphenyl)sulfonium tetrakis(pentafluorophenyl)boron salt, tris(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, tri( p-cyanophenyl)sulfonium tetrakis(pentafluorophenyl)borate, tri(p-chlorophenyl)sulfonium tetrakis(pentafluorophenyl)borate, dimethylnaphthylsulfonium tetrakis(pentafluorophenyl) Borate, Diethylnaphthylsulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(methoxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(ethoxy)sulfonium Tetrakis(pentafluorophenyl)borate, Dimethyl(propoxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(butoxy)sulfonium tetrakis(pentafluorophenyl)borate , Dimethyl(octyloxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(octadecyloxy)sulfonium tetrakis(pentafluorophenyl)borate, Dimethyl(isopropoxy base) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyl oxygen) sulfonium tetrakis (pentafluorophenyl) base) borate, dimethyl(cyclohexyloxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(fluoromethoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl (2-Chloroethoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(3-bromopropoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(4-cyano butyloxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(8-nitrooctyloxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(18-trifluoromethane Octadecyloxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(2-hydroxyisopropoxy)sulfonium tetrakis(pentafluorophenyl)borate, dimethyl(tri(tri Chloromethyl)methyl)sulfonium tetrakis(pentafluorophenyl)borate, etc., preferably bis(p-tolyl)iodonium hexafluorophosphate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluorophosphate Fluorophosphate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris(p-tert-butylphenyl)sulfonium hexafluorophosphate, bis(p-tolyl) Ionium hexafluoroarsenate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluoroarsenate, triphenylsulfonium Hexafluoroarsenate, tris(p-tert-butylphenyl)sulfonium hexafluoroarsenate, bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodide Onium hexafluoroantimonate, bis(p-tert-butylphenyl)iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)sulfonium hexafluoroantimonate, Bis(p-tolyl)iodonium tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl ) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) Sulfonium tetrakis(pentafluorophenyl)borate, etc., more preferably bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate, Bis(p-tert-butylphenyl)iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)sulfonium hexafluoroantimonate, bis(p-tolyl)iodonium Onium tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-tert-butylphenyl)iodonium tetrakis (pentafluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, or tris(p-tert-butylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, etc.

As photobase generators, for example, transition metal complexes such as cobalt, o-nitrobenzyl carbamates, α,α-dimethyl-3,5-dimethoxybenzyl carbamates, Oxime compounds, α-aminoacetophenone-based compounds, bis-imidazole compounds, and the like.

As the type of base generated by light irradiation, any of organic or inorganic bases can be suitably used, but from the base generation efficiency of light irradiation, silicon-containing acrylic resin (A) and siloxane compound ( From the viewpoint of the catalyst effect of the base in the polymerization reaction of B) and the solubility of the polymer obtained in the above polymerization reaction in the reaction solution, α-aminoacetophenone-based compounds or bis-imidazole compounds are preferred.

Examples of the above-mentioned transition metal complexes include bromide pentaammonium cobalt perchlorate, bromide pentaammonium cobalt perchlorate, bromide nonpropylammonium cobalt perchlorate, hexaammonia cobalt perchlorate salt, hexamethylammonium cobalt perchlorate, hexapropylammonium cobalt perchlorate, etc.

Examples of the aforementioned o-nitrobenzyl carbamates include [[(2-nitrobenzyl)oxy]carbonyl]methylamine, [[(2-nitrobenzyl)oxy] Carbonyl]propylamine, [[(2-nitrobenzyl)oxy]carbonyl]hexylamine, [[(2-nitrobenzyl)oxy]carbonyl]cyclohexylamine, [[(2-nitrobenzyl) Benzyl)oxy]carbonyl]aniline, [[(2-nitrobenzyl)oxy]carbonyl]piperidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexamethylenediamine , bis[[(2-nitrobenzyl)oxy]carbonyl]phenylenediamine, bis[[(2-nitrobenzyl)oxy]carbonyl]toluenediamine, bis[[(2-nitrobenzyl) benzyl)oxy]carbonyl]diaminodiphenylmethane, bis[[(2-nitrobenzyl)oxy]carbonyl]piperazine, [[(2,6-dinitrobenzyl)oxy ]carbonyl]methylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]propylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]hexylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]aniline, [[(2,6-di Nitrobenzyl)oxy]carbonyl]piperidine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]hexamethylenediamine, bis[[(2,6-dinitro Benzyl)oxy]carbonyl]phenylenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]toluenediamine, bis[[(2,6-dinitrobenzyl) )oxy]carbonyl]diaminodiphenylmethane, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]piperazine and the like.

Examples of the aforementioned α,α-dimethyl-3,5-dimethoxybenzyl carbamates include [[(α,α-dimethyl-3,5-dimethoxy Benzyl)oxy]carbonyl]methylamine, [[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]propylamine, [[(α,α- Dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexylamine, [[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl] Cyclohexylamine, [[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]aniline, [[(α,α-dimethyl-3,5-dimethyl Oxybenzyl)oxy]carbonyl]piperidine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexamethylenediamine, bis[ [(α,α-Dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]phenylenediamine, bis[[(α,α-dimethyl-3,5-dimethyl Oxybenzyl)oxy]carbonyl]toluenediamine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]diaminodiphenylmethane, bis [[(α,α-Dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]piperazine and the like.

Examples of the above-mentioned oxime compound include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime , adipate diacyl acetophenone oxime, adipate diacyl benzophenone oxime, adipate diacyl acetophenone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime, Compound (1,2-octanedione, 1-[4-(phenylthio ) phenyl]-, 2-(O-benzoyl oxime) (IRGACUREOXE-01; Ciba Specialty Chemicals Co., Ltd. system)), compounds represented by formula (V), etc., preferably represented by formula (IV) compound.

Examples of the aforementioned α-aminoacetophenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(2- Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4 -morpholinophenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethyl benzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4- Morpholinophenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,3- Dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino- 1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-( 2-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4 -morpholinophenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl Base)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino Phenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl Base)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholino (Phenylolinophenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2- (2-Methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methoxybenzyl) - oligomers of 2-dimethylamino-1-(4-morpholinophenyl)-butanone, etc.

Examples of the aforementioned bisimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3 -dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -Tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open 62-174204, etc.), 4,4', 5,5'-position phenyl is substituted by an alkoxycarbonyl imidazole compound (for example, refer to JP-A-7-10913, etc.), etc., preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bis Imidazole, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

The content of the photosensitive material (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, in terms of mass fraction relative to the total amount of the silicon-containing acrylic resin (A) and the siloxane compound (B) .

When the total amount of the photosensitive material (C) is in the above-mentioned range, the photosensitive resin composition has high sensitivity, and the strength of the pixel portion formed using the above-mentioned photosensitive resin composition and the smoothness of the surface of the above-mentioned pixel are changed. A good trend is obtained, so it is preferred.

Moreover, a photosensitizer (F) can be used in the range which does not impair the effect of this invention, For example, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned.

More specifically, the following compounds can be used, each alone or in combination of two or more.

Examples of the above-mentioned benzophenone-based compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Examples of the above-mentioned thioxanthone-based compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Xanthone, 1-chloro-4-propoxythioxanthone, etc.

Examples of the aforementioned anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethoxyanthracene, Base-9,10-diethoxyanthracene and so on.

In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphanequinone, methyl phenylglyoxylate, titanocene compound, etc. can be exemplified. .

In addition, as the photosensitizer (F), a compound having a group capable of causing chain transfer described in Japanese Patent Application Publication No. 2002-544205 can be used.

Examples of the compound having a group capable of causing chain transfer include compounds of the following formulas (5) to (10).

The above-mentioned compound having a group capable of causing chain transfer can be contained in the photosensitive resin composition as a constituent component of the above-mentioned copolymer.

In addition, the content of the photosensitizer (F) is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass relative to the total amount of the silicon-containing acrylic resin (A) and the silicone compound (B). 40% by mass.

Moreover, the photopolymerization start adjuvant (G) can be used together with a photosensitive material (C), and a photopolymerization start adjuvant can be used in various combinations.

As a photopolymerization start adjuvant (G), the compound represented by an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, a formula (VII), etc. are mentioned, for example.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate , 4-Dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N,N-dimethyl-p-toluidine, Aromatic amine compounds such as 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) and 4,4'-bis(diethylamino)benzophenone.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxybenzene Thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxy Aromatic heteroacetic acids such as glycolic acid.

Examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolic acid ester, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane Propane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4- Bis(3-mercaptobutyryloxy)butane.

[In the formula (VII), the ring X represents an aromatic ring having 6 to 12 carbon atoms substituted by a halogen atom. Y represents an oxygen atom or a sulfur atom. R ¹⁰ represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms. R ¹¹ represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms substituted by a halogen atom or an aryl group substituted by a halogen atom. ]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned, for example. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring, a naphthalene ring, and the like.

Examples of aromatic rings having 6 to 12 carbon atoms substituted by halogen atoms include benzene rings, methylbenzene rings, dimethylbenzene rings, ethylbenzene rings, propylbenzene rings, butyl Benzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, etc.

Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-n-propyl, 2-methyl- n-propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl , 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, etc.

Examples of aliphatic hydrocarbon groups having 1 to 12 carbon atoms substituted by halogen atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-n-propyl, 2 -Methyl-n-propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl -n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro-n-butyl , 3-chloro-n-butyl, etc.

Examples of aryl groups substituted with halogen atoms include phenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorobromophenyl, biphenyl, chlorobiphenyl, dichlorobiphenyl , bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl, etc.

As the compound represented by formula (VII), for example, 2-benzoylmethylene-3-methyl-naphthalene[2,1-d]thiazoline,

2-Benzoylmethylene-3-methyl-naphtho[1,2-d]thiazoline,

2-Benzoylmethylene-3-methyl-naphtho[2,3-d]thiazoline,

2-(2-naphthoylmethylene)-3-methylbenzothiazoline,

2-(1-naphthoylmethylene)-3-methylbenzothiazoline,

2-(2-naphthoylmethylene)-3-methyl-5-phenylbenzothiazoline,

2-(1-naphthoylmethylene)-3-methyl-5-phenylbenzothiazoline,

2-(2-naphthoylmethylene)-3-methyl-5-fluorobenzothiazoline,

2-(1-naphthoylmethylene)-3-methyl-5-fluorobenzothiazoline,

2-(2-naphthoylmethylene)-3-methyl-5-chlorobenzothiazoline,

2-(1-naphthoylmethylene)-3-methyl-5-chlorobenzothiazoline,

2-(2-naphthoylmethylene)-3-methyl-5-bromobenzothiazoline,

2-(1-naphthoylmethylene)-3-methyl-5-bromobenzothiazoline,

2-(4-Bibenzoylmethylene)-3-methylbenzothiazoline,

2-(4-bibenzoylmethylene)-3-methyl-5-phenylbenzothiazoline,

2-(2-naphthoylmethylene)-3-methyl-naphtho[2,1-d]thiazoline,

2-(2-naphthoylmethylene)-3-methyl-naphtho[1,2-d]thiazoline,

2-(4-bibenzoylmethylene)-3-methyl-naphthalene[2,1-d]thiazoline,

2-(4-bibenzoylmethylene)-3-methyl-naphthalene[1,2-d]thiazoline,

2-(p-Fluorobenzoylmethylene)-3-methyl-naphthalene[2,1-d]thiazoline,

2-(p-fluorobenzoylmethylene)-3-methyl-naphthalene[1,2-d]thiazoline,

2-benzoylmethylene-3-methyl-naphthalene[2,1-d]oxazoline,

2-benzoylmethylene-3-methyl-naphthalene[1,2-d]oxazoline,

2-benzoylmethylene-3-methyl-naphthalene[2,3-d]oxazoline,

2-(2-naphthoylmethylene)-3-methylbenzoxazoline,

2-(1-naphthoylmethylene)-3-methylbenzoxazoline,

2-(2-naphthoylmethylene)-3-methyl-5-phenylbenzoxazoline,

2-(1-naphthoylmethylene)-3-methyl-5-phenylbenzoxazoline,

2-(2-naphthoylmethylene)-3-methyl-5-fluorobenzoxazoline,

2-(1-naphthoylmethylene)-3-methyl-5-fluorobenzoxazoline,

2-(2-naphthoylmethylene)-3-methyl-5-chlorobenzoxazoline,

2-(1-naphthoylmethylene)-3-methyl-5-chlorobenzoxazoline,

2-(2-naphthoylmethylene)-3-methyl-5-bromobenzoxazoline,

2-(1-naphthoylmethylene)-3-methyl-5-bromobenzoxazoline,

2-(4-Bibenzoylmethylene)-3-methylbenzoxazoline,

2-(4-bibenzoylmethylene)-3-methyl-5-phenylbenzoxazoline,

2-(2-naphthoylmethylene)-3-methyl-naphtho[2,1-d]oxazoline,

2-(2-naphthoylmethylene)-3-methyl-naphtho[1,2-d]oxazoline,

2-(4-bibenzoylmethylene)-3-methyl-naphthalene[2,1-d]oxazoline,

2-(4-bibenzoylmethylene)-3-methyl-naphthalene[1,2-d]oxazoline,

2-(p-fluorobenzoylmethylene)-3-methyl-naphthalene[2,1-d]oxazoline,

2-(p-fluorobenzoylmethylene)-3-methyl-naphthalene[1,2-d]oxazoline,

wait.

Among them, 2-(2-naphthoylmethylene)-3-methylbenzothiazoline represented by formula (VII-1), 2-benzoylmethylene represented by formula (VII-2) are preferred Base-3-methyl-naphthalene[1,2-d]thiazoline and 2-(4-bibenzoylmethylene)-3-methyl-naphthalene[1, 2-d] Thiazoline.

As a photopolymerization start adjuvant (G), the compound represented by an amine compound, polyfunctional thiol, and formula (VII) is more preferable.

The content of the photopolymerization initiation aid (G) is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, based on the mass fraction relative to the total amount of the silicon-containing acrylic resin (A) and the siloxane compound (B). 40% by mass.

When the amount of the photopolymerization initiation adjuvant (G) is within the above-mentioned range, the sensitivity of the obtained photosensitive resin composition is further improved, and the productivity of the patterned substrate formed using the above-mentioned photosensitive resin composition tends to be improved, so it is preferable .

The photosensitive resin composition of this invention may contain a thermosetting accelerator (D). The above-mentioned thermal curing accelerator (D) is not particularly limited as long as it can accelerate the dehydration condensation reaction of alkoxysilane in the presence of heat. Among them, organic titanium-containing compounds and organic zirconium compounds are preferable.

For compounds containing organic titanium,

Tetraisopropoxytitanium (TPT; manufactured by Nippon Soda Co., Ltd.), tetra-n-butoxytitanium (TBT; manufactured by Nippon Soda Co., Ltd.), tetrakis(2-ethylhexyloxy)titanium ( TOT; manufactured by Nippon Soda Co., Ltd.), titanium isopropoxy suberate (TOG; manufactured by Nippon Soda Co., Ltd.), diisopropoxybis(acetylacetonate)titanium (T-50; Nippon Soda Co., Ltd.), propanedioxytitanium bis(ethyl acetylacetonate) (T-60; Nippon Soda Co., Ltd.), tri-n-butoxytitanium monostearate (TBSTA; Nippon Soda Co., Ltd.), titanium stearate (S-151; Nippon Soda Co., Ltd.), diisopropoxytitanium diisostearate (s-152; Nippon Soda Co., Ltd. manufactured), (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium (S-181; manufactured by Nippon Soda Co., Ltd.), etc.

In addition, D-20 (manufactured by Shin-Etsu Chemical Co., Ltd.), D-25 (manufactured by Shin-Etsu Chemical Co., Ltd.), D-30 (manufactured by Shin-Etsu Chemical Co., Ltd.), B-1 (manufactured by Nippon Soda (Co., Ltd.), B-2 (Nippon Soda Co., Ltd.), B-3 (Nippon Soda Co., Ltd.), B-4 (Nippon Soda Co., Ltd.), B-5 (Japan Soda Co., Ltd. Soda Co., Ltd.), B-6 (Nippon Soda Co., Ltd.), B-7 (Nippon Soda Co., Ltd.), B-8 (Nippon Soda Co., Ltd.), B-9 (Nippon Soda Co., Ltd. product), B-10 (Nippon Soda Co., Ltd. product) and other commercially available items.

For organozirconium compounds,

Examples include tetra-1-butoxyzirconium-containing substances (TBZR; manufactured by Nippon Soda Co., Ltd.), substances containing reaction products of tetrabutoxyzirconium (IV) and acetylacetone (ZR-181; Nippon Soda Co., Ltd. Co., Ltd.), a product containing a reaction product of zirconium tetrabutoxide and acetylacetone (ZAA; manufactured by Nippon Soda Co., Ltd.), and the like. In addition, commercial items such as ZR-151 (manufactured by Nippon Soda Co., Ltd.) can be used.

The photosensitive resin composition of this invention may not contain a solvent, and may contain a solvent (E). The solvent (E) may be various organic solvents used in the field of photosensitive resin compositions. Specific examples thereof 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 dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether kind;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Alkyl glycol alkyl ether acetates;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, and propylene glycol ethyl propyl ether;

Propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate;

butanediol monoalkyl ethers such as methoxybutanol, ethoxybutanol, propoxybutanol and butoxybutanol;

butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, and butoxybutyl acetate;

Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, and butoxybutyl propionate kind;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin;

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxy Propyl propionate, Butyl 3-hydroxypropionate, Methyl 2-Hydroxy-3-methylbutanoate, Methyl methoxyacetate, Ethyl methoxyacetate, Propyl methoxyacetate, Methoxy butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propoxy Propyl acetate, propoxybutyl acetate, butoxymethyl acetate, butoxyethyl acetate, butoxypropyl acetate, butoxybutyl acetate, 2-methoxymethylpropionate, 2 -Ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -Propyl ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2 - Butyl butoxypropionate, 3-methoxymethyl propionate, 3-methoxy ethyl propionate, 3-methoxy propyl propionate, 3-methoxy butyl propionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3 -Ethyl propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3 - Esters such as propyl butoxypropionate and butyl 3-butoxypropionate;

Cyclic ethers such as tetrahydrofuran and pyran;

Cyclic esters such as γ-butyrolactone, etc.

Among the above-mentioned solvents, organic solvents having a boiling point of 100°C to 200°C among the above-mentioned solvents are preferred from the viewpoint of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, butanes, etc. Esters such as alkanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, especially propylene glycol monomethyl Ethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate and 3-methoxypropionate acid methyl ester.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent (E) in the photosensitive resin composition of the present invention is preferably 60 to 90% by mass, more preferably 70 to 85% by mass, in terms of mass fraction relative to the photosensitive resin composition. When the content of the solvent (E) is within the above-mentioned range, use a spin coater, a slit spin coater, a slit coater (sometimes called a die coater, a curtain coater.), inkjet coating, etc. Coatability becomes good when coating with a cloth device, so it is preferable.

In the photosensitive resin composition of the present invention, additives such as fillers, other polymer compounds, leveling agents, antioxidants, ultraviolet absorbers, coagulants, and chain transfer agents can be used in combination as needed.

As a filler, glass, silicon oxide, aluminum oxide, etc. can be illustrated, for example.

As other polymer compounds, curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyvinyl alcohols, etc., can be used. Thermoplastic resins such as esters and polyurethanes, etc.

As the leveling agent, commercially available surfactants can be used, for example, silicone-based, fluorine-based, ester-based, cationic, anionic, non-ionic, amphoteric and other surfactants can be used, and they can be used separately Use or mix two or more. Examples of the aforementioned surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyethers, Esters, tertiary amine-modified polyurethanes, polyethyleneimines, etc., in addition to the trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Toichi Chemical Prodakutsu Co., Ltd.), MegaFac (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluorado (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard, Surflon (manufactured by Asahi Glass Co., Ltd. ), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As an antioxidant, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxyl-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1- (2-Hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy- 5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine, 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'-methylenebis(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, octadecyl-3,3'-thiodipropionate Dipropionate, pentaerythritol tetrakis(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"-(three Toluene-2,4,6-methylphenyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl -4-Methylphenol etc.

Examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.

Moreover, as an aggregating agent, sodium polyacrylate etc. are mentioned, for example.

Examples of the chain transfer agent include dodecylmercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

The photosensitive resin composition can be patterned, for example, by applying it on a substrate as described below, and performing photocuring and development. First, the composition is coated on a substrate (usually glass) or a pre-formed layer formed of the solid content of the photosensitive resin composition, and prebaked from the coated photosensitive resin composition layer. Volatile components such as solvents are removed to obtain a smooth coating film. At this time, the thickness of the coating film is approximately 1 to 6 μm. The thus obtained coating film is irradiated with ultraviolet rays through a mask used for forming the intended pattern. At this time, it is preferable to uniformly irradiate the entire exposure portion with parallel light rays, and to correct the correct positions of the mask and the substrate using a device such as a mask aligner or a stepper. Furthermore, after that, the cured coating film is brought into contact with an aqueous alkali solution to dissolve the non-exposed portion and develop to obtain a target pattern shape. As the image development method, any of a liquid flow method (液四りmethod), a dipping method, and a spraying method can be used. Furthermore, the substrate can be tilted at any angle during image development.

As a coating method, for example, a spin coating method, a cast coating method, a roll coating method, a slit spin coating method, a slit coating method, or the like can be used. After coating, heat drying (prebaking) or drying under reduced pressure is performed to volatilize volatile components such as solvents to form a photosensitive resin composition layer. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The photosensitive resin composition layer contains almost no volatile components. Moreover, the thickness of the said photosensitive resin composition layer is about 1.5-8 micrometers.

In addition, after exposure, heat treatment is preferably performed in order to accelerate curing of the exposed portion. The heating conditions can be changed according to the blending composition of the photosensitive resin composition, the types of additives, etc., but are usually 30 to 200°C, preferably 50 to 150°C.

A developer used for development after pattern exposure is usually an aqueous solution containing a basic compound and a surfactant.

The basic compound may be any of inorganic and organic basic compounds. Examples of inorganic basic compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, silicic acid Potassium, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia water, etc.

In addition, examples of organic basic compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylammonium Amine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. These inorganic and organic basic compounds can be used alone or in combination of two or more. The concentration of the basic compound in the alkali developing solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

In addition, the surfactant in the alkaline developing solution may be any of nonionic surfactant, anionic surfactant, or cationic surfactant.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, ethylene oxide/propylene oxide block Copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine wait.

As anionic surfactants, for example, higher alcohol sulfates such as sodium lauryl sulfate and oleyl sodium sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, ten Alkylarylsulfonates such as sodium dialkylbenzenesulfonate and sodium dodecylnaphthalenesulfonate, and the like.

Examples of cationic surfactants include stearylamine hydrochloride, amine salts such as 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 alkali developing solution is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by mass.

After image development, washing with water is performed, and further post-baking is implemented on 100-300 degreeC conditions for 10-60 minutes as needed.

Using the photosensitive resin composition of the present invention, a pattern can be formed on a substrate or a color filter substrate through the above steps. This pattern is useful as a photo spacer used in liquid crystal and organic EL display devices. In addition, when patterned exposure is performed on a dry coating film, holes can be formed using an optical mask for hole formation, and it is useful as an interlayer insulating film. Furthermore, when exposing a dried coating film, it is possible to expose and heat-cure the whole surface without using an optical mask, or to form a transparent film only by heat-curing, and this transparent film is useful as an overcoat (over coat). In addition, It can also be used on touch panels.

The linear resin composition of the present invention can provide a cured resin excellent in heat-resistant light transmittance. In addition, when the linear photosensitive resin composition of the present invention is used, it is possible to easily form a cured resin pattern of a desired shape, an optical spacer, an insulating film, a protrusion for controlling liquid crystal alignment, an overcoat layer, and a film thickness for matching a colored pattern. Coatings, which can be used in the formation of films used in display devices, can be used for light-guiding passage materials and optical switch materials, etc.

According to the present invention, a pattern excellent in heat-resistant light transmittance can be formed.

Example

Hereinafter, the present invention will be described in more detail based on examples. In the example, content and usage-amount % and parts are shown, and unless otherwise specified, all refer to a mass basis.

Synthesis Example 1

Introduce nitrogen gas at a rate of 0.02 L/min into a 1 L flask equipped with a reflux cooler, dropping funnel and stirrer to form a nitrogen atmosphere, add 300 parts of propylene glycol monomethyl ether acetate, and heat to 90°C while stirring . Next, 30 parts of methacrylic acid, 135 parts of 3-methacryloxypropyl tris(trimethylsiloxy)silane [formula (1-3)], 2-(methacryloyl acetoacetate) 180 parts of oxy)ethyl ester [formula (V-1)] and 160 parts of propylene glycol monomethyl ether acetate were dissolved to make a solution, and the solution was dropped into an insulated flask at a temperature of 90°C using a dropping funnel . On the other hand, 15 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 180 parts of propylene glycol monomethyl ether acetate to obtain a solution, and the solution was used The other dropping funnel was used to drip into the flask over 4 hours. After the dropwise addition of the solution of the polymerization initiator was completed, it was kept at 90° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Aa) having a solid content of 35.0% and an acid value of 65 mg-KOH/g (solid content conversion) solution. The weight average molecular weight M _w of the obtained resin Aa was 9.9×10 ³ .

Synthesis example 2

In a 1L flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen gas was introduced at a rate of 0.02L/min to form a nitrogen atmosphere, and then 200 parts of 3-methoxy-1-butanol and 3-methoxy 105 parts of butyl acetate were heated to 70°C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (II-1) and the compound represented by the formula (III-1) The compound is mixed according to the molar ratio of 50:50.) 240 parts and 140 parts of 3-methoxybutyl acetate are dissolved to make a solution, and the solution is added dropwise to a flask kept at 70°C using a dropping funnel . On the other hand, 30 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate to prepare a solution, and the solution Use another dropping funnel to drop into the flask over a period of 4 hours. After the dropwise addition of the solution of the polymerization initiator was completed, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ab) with a solid content of 32.6% and an acid value of 110 mg-KOH/g (solid content conversion). solution. The weight average molecular weight M _w of the obtained resin Ab was 1.3×10 ⁴ .

Synthesis example 3

The used 3-methacryloyloxypropyl tris(trimethylsiloxy)silane [formula (1-3)], 2-(methacryloyloxy)ethyl acetoacetate [formula ( Resin Ac was obtained in the same manner as in Example 1 except that V-1)] was changed to 180 parts and 140 parts. The weight average molecular weight M _w of the obtained resin Ac was 1.1×10 ⁴ .

Synthesis Example 4

3-methacryloyloxypropyl tris(trimethylsiloxy)silane [formula (1-3)], 2-(methacryloyloxy)ethyl acetoacetate [formula (V-1 )] was changed to 220 parts and 100 parts, respectively, and resin Ad was obtained in the same manner as in Example 1. The weight average molecular weight M _w of the obtained resin Ad was 1.1×10 ⁴ .

Synthesis Example 5

In a 1L flask equipped with a reflux cooler, dropping funnel and stirrer, feed nitrogen with a flow rate of 0.02L/min to form a nitrogen atmosphere, add 200 parts of propylene glycol monomethyl ether acetate, and heat to 90°C. Next, 38 parts of methacrylic acid, 150 parts of 3-methacryloxypropyl tris(trimethylsiloxy)silane [formula (1-3)], 2-(methacryloyl acetoacetate) 210 parts of oxy)ethyl ester [formula (V-1)] and 155 parts of propylene glycol monomethyl ether acetate were dissolved to prepare a solution, and the solution was dropped into a flask kept at 90° C. using a dropping funnel. On the other hand, a solution was prepared by dissolving 17 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 180 parts of propylene glycol monomethyl ether acetate, and the solution was prepared using another The dropping funnel was added dropwise to the flask in 4 hours. After the dropwise addition of the solution of the polymerization initiator was completed, it was kept at 90° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ae) having a solid content of 40.0% and an acid value of 61 mg-KOH/g (solid content conversion) . The weight average molecular weight M _w of the obtained resin Ae was 1.4×10 ⁴ .

Synthesis Example 6

In a 1L flask equipped with a reflux cooler, a dropping funnel and a stirrer, feed nitrogen at a rate of 0.02L/min to form a nitrogen atmosphere, add 200 parts of propylene glycol monomethyl ether acetate, and heat to 90 while stirring. ℃. Next, 43 parts of methacrylic acid, 170 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane [formula (1-3)], 2-(methacryloxy) 240 parts of ethyl acetoacetate [formula (V-1)] and 150 parts of propylene glycol monomethyl ether acetate were dissolved to prepare a solution, and the solution was dropped into a flask kept at 90° C. using a dropping funnel. On the other hand, 17 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 180 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was used Another dropping funnel took 4 hours to drop into the flask. After the addition of the solution of the polymerization initiator was completed, it was kept at 90°C for 4 hours, and then cooled to room temperature to obtain a solid content of 46.0%, an acid value of 60mg-KOH/ The solution of the copolymer (resin Af) of g (solid content conversion). The weight average molecular weight M _w of the obtained resin Af was 1.5×10 ⁴ .

The measurement of the weight average molecular weight ( _Mw ) and the number average molecular weight (Mn) of the above-mentioned binder polymer was carried out under the following conditions using the GPC method.

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40°C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI

Example 1

143 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (50 parts in terms of solid content), 20 parts of KR-213 (manufactured by Shin-Etsu Chemical Co., Ltd.) (B), 20 parts of KC-89S (Shin-Etsu Chemical Co., Ltd. Industrial Co., Ltd.) 30 parts (B), 4-methylphenyl[4-(1-methylethyl)phenyl]iodonium tetrakis(pentafluorophenyl)borate (PI-2074; Rhodia Manufactured by the company) (C) 5 parts, 2,4-Diethylthioxanthone (F) 1.5 parts, D-20 (Shin-Etsu Chemical Co., Ltd.) 4 parts (D), propylene glycol monomethyl ether acetic acid 130 parts of esters were mixed, the photosensitive resin composition 1 was obtained, and it evaluated by the following method. The results are shown in Table 6.

<pattern formation>

A 2-inch square glass substrate (Eagle 2000, manufactured by Corning Incorporated) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The photosensitive resin composition 1 was apply|coated by the spin coating method on this glass substrate, and it prebaked at 100 degreeC for 3 minutes in the purification heating furnace. After cooling, light irradiation was performed at an exposure amount of 100 mJ/cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK: manufactured by Topcon Co., Ltd.).

In addition, as an optical mask, what formed the following pattern on the same plane was used. In addition, when performing light irradiation, the space|interval between the board|substrate to which the photosensitive resin composition was apply|coated, and the optical mask made from quartz glass was set to 100 micrometers.

One side has a 7 μm LINE (rectangular)-shaped light-transmitting portion (pattern), and the interval of the LINE (rectangular) shape is 7 μm.

One side has a 30 μm LINE (rectangular)-shaped light-transmitting portion (pattern), and the interval of the LINE (rectangular) shape is 30 μm.

After light irradiation, the film containing the photosensitive resin composition was immersed in an aqueous developer solution containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 25°C for 80 seconds for development, washed with water, and then baked. oven at 220°C for 30 minutes post-bake. After standing to cool, the film thickness of the obtained film was measured with a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 3.1 μm.

<Solubility>

After obtaining the photosensitive resin composition described in Example 1, the solution was visually observed. The photosensitive resin composition 1 is a transparent and uniform solution. Hereinafter, when it was a transparent and uniform solution, it was set to o, and when the solution was inhomogeneous or cloudy, it was set to x.

<Coating state>

A cured resin film was formed on a transparent glass substrate (#1737; manufactured by Corning Incorporated) in the same manner except that light was not irradiated, and the state of the coating film was visually observed. The photosensitive resin composition 1 is a transparent and uniform coating film. Hereinafter, when the coating film is transparent, it is set to o, and when it is cloudy, it is set to x.

<Line width, section shape>

The line width and shape (section) were observed and measured using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.).

On the patterns corresponding to the respective patterns of 7 μm and 30 μm on the optical mask, the measured line widths were 8.0 μm at the 7 μm portion and 30.3 μm at the 30 μm portion. For the cross-sectional shape, the angle with respect to the pattern of the substrate is less than 90 degrees, and it is forward tapered. In addition, when the angle with respect to the pattern of a board|substrate is 90 degrees or more, it judges that it is an inverted taper. When it is forward tapered, it is less likely to cause disconnection of ITO wiring at the time of formation of a liquid crystal display device, so it is preferable. Set the forward taper to o.

<Heat resistant light transmittance>

At the time of light irradiation, except not using a photomask, it carried out similarly, and produced the coating film. The produced coating film was left to stand in a clean furnace under the conditions described in the table, and the light transmittance before and after heating was measured. The light transmittance (%) at a wavelength of 400 nm was measured using a microspectrophotometer (OSP-SP200, manufactured by Olympus Co., Ltd.).

Based on the formula (I), the heat-resistant light transmittance was obtained and used as an index of heat resistance. The obtained values were 100% at 240°C, 97% at 260°C, 95% at 280°C, and 96% at 300°C.

The heat-resistant light transmittance mentioned above is preferably 90% or more.

Example 2

143 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (50 parts in terms of solid content), 50 parts of KR-213 (manufactured by Shin-Etsu Chemical Co., Ltd.) (B), 2, 2′, 4 -Tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole (CHEMCURE TCDM, manufactured by CHEMBRIDGE INTERNATIONALCORP.) 10 Part (C), 4 parts of D-20 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 228 parts of propylene glycol monomethyl ether acetate were mixed to obtain photosensitive resin composition 1, which was prepared by the following method Make an evaluation. The results are shown in Table 7.

<pattern formation>

A pattern was formed in the same manner as in Example 1 except that an optical mask in which the following patterns were formed on the same plane was used as the optical mask.

・One side has a 10 μm LINE (rectangular)-shaped light-transmitting portion (pattern), and the interval of the LINE (rectangular) shape is 10 μm.

・One side has a 15 μm LINE (rectangular)-shaped light-transmitting portion (pattern), and the interval of the LINE (rectangular) shape is 15 μm.

<Solubility>

Evaluation was carried out by the same method as in Example 1.

<Coating state>

Evaluation was carried out by the same method as in Example 1.

<line width, section shape>

Evaluation was carried out by the same method as in Example 1.

<Heat resistant light transmittance>

Evaluation was carried out by the same method as in Example 1.

[Table 1]

Example 3

In the form of composition shown in Table 1, the photobase generator represented by formula (IV) (1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O- Benzoyl oxime) (IRGACUREOXE-01; manufactured by Ciba Seika Co., Ltd.)) was mixed, and in <pattern formation>, light was irradiated with an exposure amount of 500mJ/ ^cm2 (365nm basis), and in addition, the Photosensitive resin composition 1 was carried out similarly to obtain photosensitive resin composition 2, and it evaluated similarly to Example 2. The results are shown in Table 7.

Comparative example 1

153 parts of resin solution (A) containing resin Ab obtained in Synthesis Example 2 (50 parts in terms of solid content), 50 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co., Ltd.) 4 parts, 2,4 - 0.5 parts of diethylthioxanthone (DETX), 3 parts of pentaerythritol tetrathiopropionate (PEMP; manufactured by SAKAI Chemical Industry Co., Ltd.), 88 parts of 3-ethoxyethylpropionate (D), 5 parts of 3-methoxybutanol (D) and 65 parts of 3-methoxybutyl acetate (D) were mixed, and the photosensitive resin composition 2 was obtained. This was evaluated in the same manner as in Example 1. The results are shown in Table 6.

Comparative example 2

According to the composition shown in Table 1, the photosensitive resin composition 3 was obtained similarly to the photosensitive resin composition 1, and it evaluated similarly to Example 2. The results are shown in Table 7.

Embodiment 4-30

It mixed according to the following composition, and obtained the photosensitive resin composition. It was evaluated in the same manner as in Example 1. The results are shown in Tables 8-10.

[Table 2]

※Resin is only the amount of solid content.

※Photosensitizer (F): 2,4-diethylthioxanthone (KAYACURE DETX-s; manufactured by Nippon Kayaku Co., Ltd.)

※Solvent (E): Propylene glycol monomethyl ether acetate

[table 3]

※Resin is only the amount of solid content.

※Photopolymerization initiator (C)SP-172: Triarylsulfonium hexafluoroantimonate

※Photosensitizer (F): 2,4-diethylthioxanthone (KAYACURE DETX-s; manufactured by Nippon Kayaku Co., Ltd.)

※Solvent (E): Propylene glycol monomethyl ether acetate

[Table 4]

[table 5]

Photopolymerization Initiator (C) Example 18 D-20; manufactured by Shin-Etsu Chemical Co., Ltd. Example 19 D-25; manufactured by Shin-Etsu Chemical Co., Ltd. Example 20 TOT; manufactured by Nippon Soda Co., Ltd. Example 21 B-1; Nippon Soda Co., Ltd. Example 22 B-2; Nippon Soda Co., Ltd. Example 23 B-4; Nippon Soda Co., Ltd. Example 24 B-7; Nippon Soda Co., Ltd.

Example 25 B-10; Nippon Soda Co., Ltd. Example 26 D-30; manufactured by Shin-Etsu Chemical Co., Ltd. Example 27 ZR-151; Nippon Soda Co., Ltd. Example 28 ZR-181; Nippon Soda Co., Ltd. Example 29 TBZR; manufactured by Nippon Soda Co., Ltd. Example 30 ZAA; manufactured by Nippon Soda Co., Ltd.

[Table 6]

-; cannot form a pattern.

[Table 7]

[Table 8]

[Table 9]

[Table 10]

From the result of the Example shown to Tables 6-10, it turns out that the coating film containing the photosensitive resin composition of this invention is excellent in the heat-resistant light transmittance. It can be seen that the heat-resistant light transmittance is very poor in the comparative example.

Industrial Utilization Possibility

According to the linear resin composition of the present invention, a pattern excellent in heat-resistant light transmittance can be formed.

Claims (10)

1. A photosensitive resin composition comprising: a silicon-containing acrylic resin A, a siloxane compound B excluding A, and a photosensitive substance C. 2. The photosensitive resin composition according to claim 1, wherein the silicon-containing acrylic resin A contains at least a non-hydrolyzable polymerizable unsaturated compound A1 having a silicon atom and an unsaturated carboxylic acid and/or unsaturated A copolymer formed by polymerization of saturated carboxylic acid anhydride A2. 3. The photosensitive resin composition according to claim 2, wherein the non-hydrolyzable polymerizable unsaturated compound A1 having a silicon atom is a compound represented by formula (I),

In formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents -O-(CH ₂ ) _w -, -C(=O)-O-(CH ₂ ) _w - or -(CH ₂ ) _w -, the carbon atoms contained in ^R2 can be replaced by heteroatoms, W represents an integer of 0 to 8, R ³ to R ⁵ independently represent an aliphatic hydrocarbon group with 1 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 12 carbon atoms, and the aliphatic hydrocarbon group, Hydrogen atoms contained in aryl and aralkyl groups may be replaced by halogen atoms, y represents the integer of 1-5, and x and z represent the integer of 0-5 each independently. 4. The photosensitive resin composition according to claim 2 or 3, wherein the silicon-containing acrylic resin A also contains a copolymer that can be polymerized with monomer A3 that can be copolymerized with A1 and A2, wherein A3 is not Including A1 and A2. 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the siloxane compound B excluding A is a compound containing a structural unit derived from a monomer represented by formula (II) , R ⁸ _n Si(OR ⁹ ) _4-n (II) In formula (II), R ⁸ and R ⁹ independently represent an aliphatic hydrocarbon group with 1 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms or an aralkyl group with 7 to 12 carbon atoms, The hydrogen atoms of the aliphatic hydrocarbon groups, aryl groups and aralkyl groups can be replaced by deuterium atoms, fluorine atoms, chlorine atoms, cyano groups, hydroxyl groups, alkoxy groups with 1 to 4 carbon atoms, amino groups, mercapto groups, imino groups, Replaced by epoxy group or (meth)acryloyl group, n represents an integer from 0 to 3, Wherein, when n is an integer of 2 or less, R ⁹ may be the same or different, and when n is an integer of 2 or more, R ⁸ may be the same or different. The photosensitive resin composition in any one of Claims 1-5 containing thermosetting accelerator D. The photosensitive resin composition in any one of Claims 1-6 containing solvent E. The photosensitive resin composition in any one of Claims 1-7 containing a photosensitizer (F). The pattern formed using the photosensitive resin composition in any one of Claims 1-8. 10. A display element comprising the pattern according to claim 9.