JP2021071661A - Photosensitive composition, colored pattern, and method for producing the same - Google Patents

Abstract

To provide a photosensitive composition capable of forming a film which has light reflectivity and is excellent in thermal yellowing resistance and patterning properties.SOLUTION: The photosensitive composition contains a polysiloxane compound, a photoacid generator, a colorant, and a solvent. The content of the colorant is 5 wt.% or more based on the total solid content of the composition. The polysiloxane compound contains a cyclic polysiloxane structure and a cationically polymerizable functional group. The polysiloxane compound may further have an alkali-soluble functional group. The content of the polysiloxane compound is preferably 20-80 wt.% based on the total solid content of the composition. The photosensitive composition is used, for example, for forming a colored pattern.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive composition containing a white filler. Furthermore, the present invention relates to a coloring pattern using a photosensitive composition and a method for producing the same.

A white reflective material is used for the light emitting diode (LED) for the purpose of adjusting the light emitting direction and increasing the brightness. Thermosetting epoxy resin and silicone resin are used for these white reflectors, but in order to reduce the shape and improve productivity with the progress of miniaturization of light emitting diodes, photocurable resin is used. The production of reflectors is more efficient.

On the other hand, in the display panel, a fine pattern made of resin is formed on a substrate for a display element, and is applied to various applications. For example, it is used as a partition wall between display element pixels for the purpose of adjusting the emission color from the light emitting diode element and the emission direction of the color-converted light, and for preventing color mixing of the emission color. Further, such use as a partition wall has become a technique particularly required in recent years with the miniaturization of light emitting portions such as organic EL elements, mini LED elements, and micro LED elements.

Further, in these electronic devices, higher heat resistance is required with the progress of high output and miniaturization of light emitting elements.

As described in Patent Document 1, conventional colored photosensitive resin compositions have been attempted to improve heat-resistant yellowing, but have not yet been sufficient. Further, in the photosensitive resin composition containing the white filler, the patterning property is deteriorated due to the influence of the decrease in the dispersibility and alkali developability of the white filler and the influence of light scattering by the white filler due to the structural change of the binder polymer. May be done. In particular, when forming a white pattern having high reflectance or forming a thick film pattern, the deterioration of patterning property is remarkable, and in Patent Document 2, the pattern width is 150 μm for a film thickness of 15 μm. The aspect ratio (film thickness / pattern width) is 0.1, and in Patent Document 3, the pattern width is 100 μm and the aspect ratio is 0.2 with respect to the film thickness of 20 μm. It was difficult to form a narrow pattern, that is, a pattern having a large aspect ratio.

Patent No. 4891434 Patent No. 6201984 Patent No. 4392464

The present invention has been made in view of the above, and an object of the present invention is to form a reflective film having high light reflectivity and excellent heat-resistant yellowing and patterning property or a white pattern having a large aspect ratio. The purpose is to provide a photosensitive composition.

The present invention has been made based on the finding that a composition using a cyclic polysiloxane compound having a predetermined functional group introduced as a binder has high heat resistance and is excellent in various properties such as dispersibility of a colorant. It is a thing.

The photosensitive composition of the present invention contains a polysiloxane compound (A), a photoacid generator (B), and a white filler (C). The content of the white filler (C) with respect to the total solid content of the composition is 5% by weight or more. The polysiloxane compound (A) contains a cyclic polysiloxane structure and a cationically polymerizable functional group. The content of the polysiloxane compound (A) with respect to the total solid content of the composition is preferably 20 to 95% by weight.

Examples of the cationically polymerizable functional group in the polysiloxane compound (A) include an epoxy group, an oxetanyl group, an alkoxysilyl group and a vinyl ether group. The polysiloxane compound (A) preferably has either an alicyclic epoxy group or an oxetanyl group as a cationically polymerizable functional group. The polysiloxane compound (A) more preferably contains a glycidyl group in addition to an alicyclic epoxy group or an oxetanyl group as a cationically polymerizable functional group.

The polysiloxane compound (A) preferably further has an alkali-soluble functional group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, and an isocyanuric acid derivative structure represented by X1 or X2 below.

The photosensitive composition may further contain the reactive diluent (D). The reactive diluent has two or more cationically polymerizable functional groups in one molecule. Of these, a reactive diluent containing an alicyclic epoxy group or an oxetanyl group as a cationically polymerizable functional group is preferable. The content of the reactive diluent (D) with respect to the total solid content of the composition is preferably 1 to 75% by weight.

The photosensitive composition may further contain a solvent.

The present invention is also a white pattern composed of a cured product of the above-mentioned photosensitive composition and a method for producing the same.

Since the photosensitive composition of the present invention has light reflectivity and is excellent in heat resistance and patterning property, it can be suitably used as a light reflection pattern forming material such as a white reflective material and a partition wall between pixels of a display element.

Embodiments of the present invention will be described in detail below. In the present specification, "A to B" representing a numerical range means "A or more and B or less". Unless otherwise specified, the components and functional groups exemplified in the present specification may be used alone or in combination (coexistence) of two or more.

[Photosensitive composition]
The photosensitive composition of the present invention contains (A) a cyclic polysiloxane compound having a cationically polymerizable functional group, (B) a photoacid generator, and (C) a colorant as solid contents. The solid content is a non-volatile component in the composition, and the total solid content means the total amount excluding the solvent from the constituent components of the composition.

<(A) Polysiloxane compound>
The photosensitive composition contains a cyclic polysiloxane compound having a cationically polymerizable functional group as a resin binder component. Hereinafter, the cyclic polysiloxane compound having a cationically polymerizable functional group may be referred to as "Compound (A)". Compound (A) has a cyclic polysiloxane structure and a cationically polymerizable functional group.

As used herein, the term "cyclic polysiloxane structure" means a cyclic molecular structure skeleton having a siloxane unit (Si—O—Si) as a component of the ring. A compound containing a cyclic polysiloxane structure tends to be superior in film-forming property and heat resistance of the obtained cured product as compared with a compound containing only a linear polysiloxane structure. Compound (A) may contain a cyclic polysiloxane structure in the main chain or in the side chain. When the compound (A) contains a cyclic polysiloxane structure in the main chain, the cured product tends to have excellent heat resistance. The cyclic polysiloxane structure may be a monocyclic structure or a polycyclic structure. The polycyclic structure may be a polyhedral structure. Among the siloxane units constituting the ring, the _{higher the content of T units (XSiO 3/2} ) or Q units (SiO _4/2 ), the higher the hardness of the obtained cured product and the more excellent the heat resistance tends to be. The higher the content of M units (X ₃ SiO _1/2 ) or D units (X ₂ SiO _2/2 ), the more flexible and less stressed the resulting cured product tends to be.

As used herein, the term "cationically polymerizable functional group" means a functional group that polymerizes and crosslinks with an acidic active substance generated from a photoacid generator when irradiated with active energy rays. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. Examples of the cationically polymerizable functional group include an epoxy group, a vinyl ether group, an oxetanyl group, and an alkoxysilyl group. From the viewpoint of stability, compound (A) preferably has an epoxy group as a cationically polymerizable functional group. Among the epoxy groups, an alicyclic epoxy group or a glycidyl group is preferable from the viewpoint of stability. Further, from the viewpoint of photocationic polymerizable, an alicyclic epoxy group or an oxetanyl group is preferable.

Compound (A) may have a plurality of cationically polymerizable functional groups in one molecule. When the compound (A) has a plurality of cationically polymerizable functional groups in one molecule, a cured product having a high crosslink density is obtained, and the heat resistance tends to be improved. The plurality of cationically polymerizable functional groups may be the same, or two or more different functional groups may be used.

Compound (A) may simultaneously contain at least two of an alicyclic epoxy group, a glycidyl group, and an oxetanyl group in one molecule. When one molecule has an alicyclic epoxy group and a glycidyl group, the alicyclic epoxy group is mainly involved in cationic polymerization, and the glycidyl group contributes to the improvement of dispersibility of the colorant. When one molecule has an oxetanyl group and a glycidyl group, the oxetanyl group is mainly involved in cationic polymerization, and the glycidyl group contributes to the improvement of dispersibility of the colorant. When one molecule has an alicyclic epoxy group and an oxetanyl group, the alicyclic epoxy group is mainly involved in the initiation reaction of cationic polymerization, and the oxetanyl group contributes to the growth reaction of cationic polymerization.

Compound (A) may have an alkali-soluble functional group in addition to the cationically polymerizable functional group. As used herein, the alkali-soluble functional group means a functional group that imparts alkali solubility to a compound. Compound (A) shows the possibility of being an alkaline aqueous solution by having an alkali-soluble functional group in the same molecule in addition to the cationically polymerizable functional group. As a result, the photosensitive composition containing the compound (A) can be applied as a colored pattern forming material (colored negative type photosensitive composition) that can be patterned by alkaline development.

Examples of the alkali-soluble functional group include an isocyanuric acid derivative structure represented by X1 or X2 below, a phenolic hydroxyl group, a carboxyl group and the like. From the viewpoint of heat resistance of the obtained cured product, the compound (A) preferably has a structure represented by the above formula X1 or X2 as an alkali-soluble functional group. Since the structure shown in X1 or X2 is an alkali-soluble group having no carboxyl group, it is particularly excellent in heat-resistant yellowing. Further, since the structure shown in X1 or X2 has a highly polar isocyanurate structure, it is characterized in that the white filler is well dispersed.

The method for introducing the cationically polymerizable functional group into the polysiloxane compound is not particularly limited. A method using a hydrosilylation reaction is preferable because a cationically polymerizable functional group can be introduced into a polysiloxane-based compound by a chemically stable silicon-carbon bond (Si—C bond). In other words, compound (A) is preferably a cyclic polysiloxane compound that has been organically modified by a hydrosilylation reaction and has a cationically polymerizable functional group introduced via a silicon-carbon bond. The alkali-soluble functional group is also preferably introduced into the cyclic polysiloxane compound via a silicon-carbon bond by a hydrosilylation reaction.

The cyclic polysiloxane compound into which the cationically polymerizable functional group and the alkali-soluble functional group have been introduced can be obtained, for example, by a hydrosilylation reaction using the following compound as a starting material.
(Α) A compound having a carbon-carbon double bond reactive with a SiH group (hydrosilyl group) and an alkali-soluble functional group in one molecule;
A cyclic polysiloxane compound having at least two SiH groups in one molecule of (β); and a carbon-carbon double bond reactive with a SiH group in one molecule of (γ) and a cationically polymerizable functional group. And a compound having.

(Compound (α))
The compound (α) is not particularly limited as long as it is an organic compound having a carbon-carbon double bond reactive with a SiH group and an alkali-soluble functional group in one molecule. By using the compound (α), an alkali-soluble functional group is introduced into the compound (A).

Examples of the group containing a carbon-carbon double bond reactive with the SiH group (hereinafter, may be simply referred to as “alkenyl group”) include a vinyl group, an allyl group, a metalyl group, an acrylic group, a methacryl group, and 2 -Hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) Examples thereof include a phenyl group, a 2- (allyloxy) ethyl group, a 2,2-bis (allyloxymethyl) butyl group, a 3-allyloxy-2,2-bis (allyloxymethyl) propyl group and a vinyl ether group. From the viewpoint of reactivity with the SiH group, the compound (α) preferably contains a vinyl group or an allyl group as the alkenyl group.

Compound (α) may have two or more alkenyl groups in one molecule. When the compound (α) contains a plurality of alkenyl groups in one molecule, the plurality of compounds (β) can be crosslinked by a hydrosilylation reaction, so that the crosslinked density of the obtained cured product is high and the heat resistance tends to be improved. is there.

From the viewpoint of availability, the compound (α) is diallyl isocyanuric acid, monoallyl isocyanuric acid, vinylphenol, allylphenol, a compound represented by the following general formula (IIa) or (IIb), butenoic acid, pentene acid, heptene. Acids, heptene acids or undecylene acids are preferred. R in the general formulas (IIa) and (IIb) is selected from the group consisting of _{-O-, -CH 2-} , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , and -SO _2-. It is a divalent group to be made.

Among these, from the viewpoint of heat resistance of the cured product, the compound (α) is preferably diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinylphenol or allylphenol. Further, from the viewpoint of electrical properties of the cured product and the like, the compound (α) is particularly preferably diallyl isocyanuric acid or monoallyl isocyanuric acid. By using diallyl isocyanuric acid as the compound (α), the above-mentioned structure X1 is introduced into the compound (A). The structure X2 has a higher acidity (smaller pKa) than the structure X1. Therefore, when monoallyl isocyanuric acid is used, the alkali developability tends to be improved.

When monoallyl isocyanuric acid is used as the compound (α), a compound having two or more alkenyl groups in one molecule (for example, the compound (δ) described later) in order to increase the molecular weight and the cross-linking density of the compound (A). It is preferable to use in combination. As compound (α), diallyl isocyanuric acid and monoallyl isocyanuric acid may be used in combination.

(Compound (β))
Compound (β) is a cyclic polysiloxane compound having at least two SiH groups in one molecule. For example, the compound described in International Publication No. 96/15194, which has at least two SiH groups in one molecule. Can be used. Compound (β) preferably contains 3 or more SiH groups in one molecule. From the viewpoint of heat resistance and light resistance, the group existing on the Si atom is preferably either a hydrogen atom or a methyl group.

The compound (β) is, for example, a cyclic polysiloxane represented by the following general formula (III).

^{R 4} , R ⁵ and R ⁶ in the formula independently represent organic groups having 1 to 20 carbon atoms. m represents an integer of 2 to 10 and n represents an integer of 0 to 10. The m is preferably 3 or more. m + n is preferably 3 to 12.

As R ⁴ , R ⁵ and R ⁶ , an organic group composed of an element selected from the group consisting of C, H and O is preferable. Examples of R ⁴ , R ⁵ and R ⁶ include alkyl groups, hydroxyalkyl groups, alkoxyalkylkyl groups, oxyalkyl groups, aryl groups and the like. Of these, a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group, a cyclic alkyl group such as a cyclohexyl group and a norbornyl group, or a phenyl group is preferable. From the viewpoint of availability of the compound (β), R ⁴ , R ⁵ and R ⁶ are preferably a methyl group, a propyl group, a hexyl group or a phenyl group. R ⁴ and R ⁵ are more preferably chain alkyl groups having 1 to 6 carbon atoms, and particularly preferably a methyl group.

Examples of the cyclic polysiloxane compound represented by the general formula (III) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5-trihydro. Gen-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1,3-dihydrogen-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-hydrogen-1 , 3,3,5,5,7,7-Heptamethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5 -Dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5 , 7,9-Pentahydrogen-1,3,5,7,9-Pentamethylcyclosiloxane and 1,3,5,7,9,11-Hexahydrogen-1,3,5,7,9, Examples include 11-hexamethylcyclosiloxane. Above all, from the viewpoint of availability and reactivity of SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in the general formula (III), m = 4. A compound in which n = 0 and R ⁴ is a methyl group) is preferable.

The compound (β) may be a polycyclic cyclic polysiloxane. The polycycle may have a polyhedral structure. The polysiloxane having a polyhedral skeleton preferably has 6 to 24 Si atoms constituting the polyhedral skeleton, and more preferably 6 to 10 Si atoms. Specific examples of the polysiloxane having a polyhedral skeleton include silsesquioxane (Si atom number = 8) represented by the following general formula (IV).

In the above formula, R ^{10 to} R ¹⁷ are independently hydrogen atom, chain alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl group (cyclohexyl group, etc.), aryl group (phenyl). Groups and trill groups, etc.), groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atoms or cyano groups (chloromethyl group, trifluoropropyl group, cyanoethyl group, etc.), alkenyl It is a monovalent group selected from a group (vinyl group, allyl group, butenyl group, hexenyl group, etc.), a (meth) acryloyl group, an epoxy group, and an organic group containing a mercapto group or an amino group. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The cyclic polysiloxane having a polyhedral skeleton has two or more hydrosilyl groups which are reactive groups of the hydrosilylation reaction. Therefore, at least two of ^{R 10 to} R ^{17 are hydrogen atoms.}

The cyclic polysiloxane may be silylated silicic acid having a polyhedral skeleton. Specific examples of silylated silicic acid having a polyhedral skeleton include a compound represented by the following general formula (V) (Si atom number = 8).

In the above formula, R ^{18 to} R ⁴¹ are the same as the specific examples ^{of R 10 to} R ¹⁷ in the above general formula (IV), and at least two of ^{R 18 to} R ^{41 are hydrogen atoms.}

In silylated silicic acid having a polyhedron skeleton, the Si atom constituting the polyhedron skeleton and the SiH group (reactive group of the hydrosilylation reaction) are bonded via a siloxane bond, so that the cured product has flexibility. Can be granted.

Cyclic polysiloxane is obtained by a known synthetic method. For example, the cyclic polysiloxane represented by the general formula (III) can be synthesized by the method described in International Publication No. 96/15194 or the like. Polysiloxane having a polyhedral skeleton such as silsesquioxane and silylated silicic acid having a polyhedral skeleton are described in, for example, JP-A-2004-359933, JP-A-2004-143449, JP-A-2006-269402 and the like. It can be synthesized by the method described. As the compound (β), a commercially available cyclic polysiloxane compound may be used.

(Compound (γ))
The compound (γ) is not particularly limited as long as it is a compound having an alkenyl group and a cationically polymerizable functional group in one molecule. By using compound (γ), a cationically polymerizable functional group is introduced into compound (A). Therefore, the cationically polymerizable functional group in the compound (γ) is the same as the cationically polymerizable functional group contained in the above-mentioned compound (A), and the preferred embodiment is also the same. The alkenyl group in the compound (γ) is preferably the same as the alkenyl group in the compound (α) described above.

Specific examples of the compound (γ) having an epoxy group as a cationically polymerizable functional group include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate and the like. From the viewpoint of reactivity in photocationic polymerization, a compound having an alicyclic epoxy group is preferable, and vinylcyclohexene oxide is particularly preferable.

The cationically polymerizable functional group of the compound (γ) may be a vinyl ether group, an oxetane group, an alkoxysilyl group or the like. Specific examples of the compound (γ) having an alkoxysilyl group as a cationically polymerizable functional group include alkoxysilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, methyldiethoxyvinylsilane, methyldimethoxyvinylsilane and phenyldimethoxyvinylsilane. .. Examples of the compound (γ) having a vinyl ether group as a cationically polymerizable functional group include propenylethenyl ether and the like. Compounds (γ) having an oxetane group as a cationically polymerizable functional group include 3-allyloxymethyl-3-ethyloxetane, 2-vinyloxetane, 3-allyloxyoxetane and (3-ethyloxetane-3-yl) methyl. Examples include acrylate.

(Other starting materials)
In the synthesis of the compound (A) by the hydrosilylation reaction, other starting materials may be used in addition to the above compounds (α) (β) (γ). For example, as a starting material, compound (δ): a compound having two or more alkenyl groups in one molecule (excluding compound (α) and compound (γ)) may be used. When a compound (δ) containing a plurality of alkenyl groups in one molecule is used as a starting material, the plurality of compounds (β) are crosslinked by the hydrosilylation reaction, so that the molecular weight of the compound (A) is increased and the film-forming property is formed. And the heat resistance of the cured film tends to improve.

The compound (δ) may be either an organic polymerization system compound or an organic monomer system compound. Examples of organic polymerization system compounds include polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, unsaturated hydrocarbon type, polyacrylic acid ester type, polyamide type, and phenol-formaldehyde type (phenol resin type). Alternatively, a polyimide-based compound can be mentioned. Examples of the organic monomer-based compound include aromatic hydrocarbon-based compounds such as phenol-based, bisphenol-based, benzene and naphthalene; aliphatic hydrocarbon-based compounds such as linear and alicyclic-based compounds; and heterocyclic compounds. ..

Specific examples of the compound (δ) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropan diallyl ether, trimethylol propanetriallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1 , 1,2,2-tetraallyloxyetane, diallylidene pentaerythlit, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl imonomethylsocyanurate, 1,2,4-trivinylcyclohexane , 1,4-Butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylpropantrivinyl ether, pentaerythritol tetravinyl ether, bisphenol S diallyl ether, Divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantan, 1,3-bis (vinyloxy) adamantan, 1,3,5- Tris (allyloxy) adamantan, 1,3,5-tris (vinyloxy) adamantan, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadien, diallyl ether, bisphenol A diallyl ether, 2,5- Diallylphenol Allyl ethers and their oligomers, 1,2-polybutadiene (1,2 ratio 10-100%, preferably 1,2 ratio 50-100%), novolak phenol allyl ethers, allylated polyphenylene Examples thereof include oxides and those in which all the glycidyl groups of conventionally known epoxy resins are replaced with allyl groups.

From the viewpoint of heat resistance and light resistance, the compound (δ) is preferably a compound represented by the following general formula (VI).

^{R 1} and R ² in the formula are alkenyl groups and may be the same or different. R ³ represents a monovalent organic group having 1 to 50 carbon atoms.

R ¹ and R ² are preferably the same as the alkenyl group in the above-mentioned compound (α), and among them, a vinyl group and an allyl group are preferable, and an allyl group is particularly preferable. From the viewpoint of increasing the heat resistance of the cured product, ^{the carbon number of R 3} is preferably 1 to 20, and more preferably 1 to 10. Specific examples of R ^{3 are the same as the specific examples of R 10 to} R ¹⁷ in the above-mentioned general formula (IV). R ³ may contain a carbon-carbon double bond that is reactive with the SiH group. Preferred examples of compound (δ) include triallyl isocyanurate and diallyl monomethylisocyanurate.

^{R 3} in the general formula (VI) may be a reactive group such as a glycidyl group. Since a glycidyl group, which is one of the epoxy groups, has cationically polymerizable property ^{, a compound in which R 3} is a glycidyl group in the general formula (VI) is classified into the above-mentioned compound (γ). On the other hand, when a compound containing a functional group having a higher cationically polymerizable than a glycidyl group (for example, a compound containing an alicyclic epoxy group such as vinylcyclohexene oxide) is used as the compound (γ), the alicyclic epoxy is mainly used. Since the group is involved in cationic polymerization, the contribution of the glycidyl group to cationic polymerization is small. ^{Therefore, the compound in which R 3} is a glycidyl group in the general formula (VI) can also be classified into the compound (δ). Specific examples of such a compound (δ) include diallyl monoglycidyl isocyanurate.

As a starting material in the synthesis of compound (A) by the hydrosilylation reaction, compound (ε): a compound having only one functional group involved in the hydrosilylation reaction in one molecule (however, compound (α) and compound (γ) ) May be used. The functional group involved in the hydrosilylation reaction is a SiH group or an alkenyl group. By using a compound containing only one functional group involved in the hydrosilylation reaction, a specific functional group can be introduced at the end of the compound (A).

For example, by using a siloxane compound having one SiH group as the compound (ε), a siloxane structural site can be introduced at the end of the compound (A). Specific examples of the siloxane compound having one SiH group include a cyclic polysiloxane compound having m = 1 in the above-mentioned general formula (III), and one of R ^{10 to} R ^{17 in} the above-mentioned general formula (IV) being hydrogen. Examples thereof include a polyhedron polysiloxane compound which is an atom, a silylated silicic acid compound in which one ^{of R 18 to} R ^{41 in the above general formula (V) is a hydrogen atom, and the like.} The siloxane compound having one SiH group may be a chain siloxane compound.

By using a compound having one group containing one alkenyl group as the compound (ε), a desired functional group can be introduced into the terminal of the compound (A).

In addition to the above, compounds involved in the hydrosilylation reaction, such as chain polysiloxane having two or more SiH groups, may be included in the starting material.

In the above example, by using a compound (α) having an alkenyl group and an alkali-soluble functional group and a compound having an alkenyl group and a cationically polymerizable functional group, a cyclic polysiloxane compound having a plurality of SiH groups (β). ) Introduces an alkali-soluble group and a cationically polymerizable functional group. A compound containing an alkali-soluble functional group and a SiH group may be used instead of the compound (α), and a compound containing a cationically polymerizable functional group and a SiH group may be used instead of the compound (γ). In this case, by using a cyclic polysiloxane compound having an alkenyl group, a cationically polymerizable functional group and / or an alkali-soluble functional group can be introduced into the cyclic polysiloxane compound. As the cyclic polysiloxane compound, a compound having a plurality of alkenyl groups may be used.

Examples of the cyclic siloxane compound containing an alkenyl group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1, 3,5,7-Tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3, 5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexavinyl-1,3 , 5, 7, 9, 11-hexamethylcyclosiloxane and the like. In the cyclic polysiloxane compound having an alkenyl group, the organic group existing on the Si atom is preferably a vinyl group or a methyl group from the viewpoint of heat resistance and light resistance.

(Hydrosilylation reaction)
The order and method of the hydrosilylation reaction are not particularly limited. For example, compound (A) is obtained by a hydrosilylation reaction according to the method described in International Publication No. 2009/075233. From the viewpoint of simplifying the synthesis step, it is preferable to charge all the starting materials in one pot, carry out a hydrosilylation reaction, and finally remove the unreacted compound. On the other hand, from the viewpoint of suppressing the formation of low molecular weight compounds, it is preferable to carry out the introduction of the alkali-soluble functional group and the cationically polymerizable functional group into the cyclic polysiloxane compound in a stepwise manner. For example, a hydrosilylation reaction is carried out using a compound containing a plurality of alkenyl groups (for example, compound (α) and / or compound (δ)) and a compound containing a plurality of SiH groups (for example, compound (β)) in excess of one of them. After removing the unreacted compound, a compound having only one functional group involved in the hydrosilylation reaction (for example, compound (γ) and / or compound (ε)) is added to carry out the hydrosilylation reaction. Is preferable.

The ratio of each compound in the hydrosilylation reaction is not particularly limited, but it is preferable that the total amount of alkenyl groups A and the total amount of SiH groups of the starting material B satisfies 1 ≦ B / A ≦ 30 and 1 ≦ B / A. It is more preferable to satisfy ≦ 10. If the B / A is 1 or more, unreacted alkenyl groups are unlikely to remain, and if the B / A is 30 or less, unreacted SiH groups are unlikely to remain, so that the characteristics of the cured film can be improved.

A hydrosilylation catalyst such as chloroplatinic acid, a platinum-olefin complex, or a platinum-vinylsiloxane complex may be used for the hydrosilylation reaction. A hydrosilylation catalyst and a co-catalyst may be used in combination. ^{The amount of the hydrosilylation catalyst added is not particularly limited, but is preferably 10-8} to ^10-1 times, more preferably ^10-6 to ^10-2, based on the total amount (number of moles) of alkenyl groups contained in the starting material. It is double.

The reaction temperature for hydrosilylation may be appropriately set, preferably 30 to 200 ° C, more preferably 50 to 150 ° C. The oxygen volume concentration in the gas phase portion in the hydrosilylation reaction is preferably 3% or less. From the viewpoint of promoting the hydrosilylation reaction by adding oxygen, the gas phase portion may contain about 0.1 to 3% by volume of oxygen.

A solvent may be used for the hydrosilylation reaction. As the solvent, hydrocarbon solvents such as benzene, toluene, hexane and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; chloroform. , Halogen-based solvents such as methylene chloride and 1,2-dichloroethane and the like. Toluene, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane or chloroform is preferable because it is easy to distill off after the reaction. In the hydrosilylation reaction, a gelation inhibitor may be used if necessary.

(Preferable embodiment of compound (A))
Compound (A) preferably has an alicyclic epoxy group or an oxetanyl group as a cationically polymerizable functional group. Compound (A) more preferably has a glycidyl group in addition to an alicyclic epoxy group or an oxetanyl group as a cationically polymerizable functional group. When the compound (A) has a glycidyl group, the dispersibility of the white filler in the compound (A) is improved, and the uncured coating film is easily dissolved uniformly in the alkaline developer. The alicyclic epoxy group is preferably introduced into the compound (A) using a compound (γ) having a vinyl group and an alicyclic epoxy group in one molecule as a starting material. The oxetanyl group is preferably introduced into the compound (A) using a compound (γ) having a vinyl group and an oxetanyl group in one molecule as a starting material. The glycidyl group is preferably introduced into the compound (A) using an isocyanuric acid derivative represented by the general formula (VI) (one in which R ³ is a glycidyl group) as a starting material.

Compound (A) preferably has an alkali-soluble group. Among the alkali-soluble groups, the above-mentioned structure X1 or structure X2 is preferable. As described above, the structures X1 and X2 can be introduced into the compound (A) using diallyl isocyanuric acid and monoallyl isocyanuric acid as starting materials (compound (α)), respectively.

The cyclic structure of the cyclic polysiloxane is preferably introduced into the compound (A) using a cyclic polysiloxane having two or more SiH groups as a starting material (compound (β)). Above all, it is preferable to use 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane as the compound (β).

<(B) Photoacid generator>
The photosensitive composition contains a photoacid generator (cationic polymerization initiator). A photoacid generator is a compound in which an acidic active substance is produced by irradiation with active energy rays. The acid generated from the photoacid generator reacts with the cationically polymerizable functional group, and the resin composition is photocured.

As the photoacid generator, known photoacid generators such as sulfonate esters, carboxylic acid esters, and onium salts can be applied, and onium salts are particularly preferable.

The onium salt, tetrafluoroborate (BF ₄ ^-), hexafluorophosphate (PF ₆ ^-), hexafluoroantimonate (SbF ₆ ^-), hexafluoroarsenate (AsF ₆ ^-), hexa-chloro antimonate (SbCl ₆ ^-), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluorophenyl methylphenyl) borate, fluoroalkyl fluorophosphate, perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion (CF ₃ SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonic acid ion, sulfonium salts and iodonium salts having an anion such as trinitrobenzene sulfonate anion and trinitrotoluene sulfonate anion. The photoacid generator is preferably an iodonium salt, and an aromatic iodonium salt is particularly preferable.

SbF ₆ Arranging anions in the photoacid generator from those acid strength is strong in the order ^{_{-, B (C 6 F 5}} ) 4 -, PF 6 -, CF 3 SO 3 -, HSO 4 - and becomes. The stronger the acid strength of the anion of the photoacid generator, the higher the residual film ratio tends to be. The pKa of the acid generated from the photoacid generator is preferably less than 3, more preferably less than 1.

The content of the photoacid generator in the photosensitive composition is not particularly limited. From the viewpoint of the curing rate and the balance of physical properties of the cured product, the content of the photoacid generator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the compound (A). preferable.

<(C) White filler>
The photosensitive composition of the present invention contains a white filler. By containing the white filler, a colored cured film can be obtained. White fillers include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, barium sulfate, lead white, zinc sulfide, potassium titanate, zinc titanate, antimony oxide, silicon oxide, aluminum oxide, aluminum hydroxide, silicon nitride, Examples thereof include boron nitride, aluminum nitride, and diamond powder. Titanium oxide, zirconium oxide, or aluminum oxide is preferable when high reflectance is desired in the visible light region and the near infrared region. Zirconium oxide is preferable when high reflectance is desired in the ultraviolet region. Aluminum nitride or aluminum oxide is preferable when it is desired to impart heat dissipation in addition to light reflection.

The lower limit of the average particle size of the white filler is preferably 30 nm, preferably 50 nm, and more preferably 100 nm. When it is desired to efficiently reflect light in the near infrared region, the lower limit of the average particle size is preferably 600 nm or more. On the other hand, the upper limit of the average particle size of the white filler is preferably 5000 nm, more preferably 3000 nm, and even more preferably 2000 nm. When the average particle size of the white filler is in the above range, good dispersibility, light scattering, and the like can be exhibited, and as a result, patterning property and light reflectivity can be improved.

In order to obtain a reflective film, the content ratio of the white filler in the total solid content of the photosensitive composition is preferably 5% by weight or more. In the present invention, by using the above compound (A) as the binder resin component of the photosensitive composition, even when the content of the white filler is increased, it has sufficient dispersibility. Therefore, the photosensitive composition of the present invention is excellent in coating film forming property and patterning property by alkaline development.

The content ratio of the white filler may be adjusted according to the type of the white filler, the reflectance of the reflective film, the patterning property, and the like. The content of the white filler is preferably 7 to 90% by weight, more preferably 10 to 85% by weight, still more preferably 12 to 80% by weight, based on the total solid content of the photosensitive composition. If the content of the white filler is small, the light reflectivity may be insufficient. If the content of the white filler is excessively large, the dispersibility of the colorant may be lowered, and the formability of the coating film and the patterning property by alkaline development may be lowered. From the viewpoint of achieving both dispersibility and light reflectivity of the white filler and enhancing the heat resistance of the cured film, the content of the white filler in the photosensitive composition is 8 to 8 to 100 parts by weight of the compound (A). 500 parts by weight is preferable, 10 to 400 parts by weight is more preferable, and 13 to 300 parts by weight is further preferable.

<(D) Reactive diluent>
The photosensitive composition of the present invention may contain a reactive diluent. By adding a reactive diluent to the composition, it is possible to reduce the curing shrinkage of the obtained cured film and control the mechanical strength of the cured film. Further, by blending the reactive diluent, the reaction points (crosslink points) of the photocationic polymerization are increased, so that the curing speed at the time of exposure can be increased and the exposure time can be shortened. In particular, the photosensitive composition used for forming a colored film or a colored pattern has a large content of the white filler (C), and therefore has a higher crosslink point density than the photosensitive composition for forming a transparent film. It tends to be smaller. Therefore, the effect of improving the photocuring rate by blending the reactive diluent is remarkable.

As the reactive diluent for photocationic polymerization, a compound having two or more cationically polymerizable functional groups in one molecule is used. Examples of the cationically polymerizable functional group of the reactive diluent (D) include those exemplified as the cationically polymerizable functional group of the above-mentioned compound (A). The cationically polymerizable functional group of the reactive diluent (D) may be the same as or different from the cationically polymerizable functional group of the compound (A). Since the reactive diluent (D) has high cationic polymerization reactivity, it is preferable that the reactive diluent (D) has an alicyclic epoxy group or an oxetanyl group as the cationically polymerizable functional group. In a particularly preferred form, compound (A) contains an alicyclic epoxy group or oxetanyl group as a cationically polymerizable functional group, and the reactive diluent (D) contains two or more alicyclic epoxy groups in one molecule. Or it has an oxetanyl group.

Examples of the compound having two or more alicyclic epoxy groups in one molecule include 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate (Dycel's "Ceroxide 2021P") and ε-caprolactone modification. 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Dycel's "Ceroxide 2081"), bis (3,4-epoxycyclohexylmethyl) adipate, epoxy-modified chain siloxane compound of the following formula S1 (Shinetsu) Chemical "X-40-2669"), an epoxy-modified cyclic siloxane compound of the following formula S2 ("KR-470" manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

Examples of the compound having two or more oxetane groups in one molecule include xylylene bisoxetane (“OXT-121” manufactured by Toa Synthetic), 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy]. Examples thereof include methyl} oxetane (“OXT-221” manufactured by Toa Synthetic Co., Ltd.), an oxetanyl-modified chain siloxane compound of the following formula S3, and an oxetanyl-modified chain siloxane compound of the following formula S4.

Above all, when a compound having three or more alicyclic epoxy groups or oxetanyl groups in one molecule is blended as the reactive diluent, the effect of improving the curing rate tends to be remarkable. Further, the reactive diluent having a cyclic polysiloxane skeleton like the compounds of the above formulas S2 and S4 has high heat resistance and low dielectric property of the compound (A) even when the content in the composition is increased. It is preferable because it can maintain.

The content of the reactive diluent in the photosensitive composition is not particularly limited, but from the viewpoint of achieving both an improvement in the curing rate of the photosensitive composition and a physical balance of the cured product, the total solid content of the photosensitive composition is used. On the other hand, 1 to 75% by weight is preferable, 3 to 60% by weight is more preferable, and 5 to 50% by weight is further preferable. The content of the reaction diluent is preferably 10 to 150 parts by weight, more preferably 15 to 100 parts by weight, still more preferably 20 to 70 parts by weight, based on 100 parts by weight of the compound (A).

<(E) Sensitizer>
The photosensitive composition of the present invention may contain a sensitizer. By using a sensitizer, the exposure sensitivity during patterning is improved. As the sensitizer, an anthracene-based sensitizer is preferable. Specific examples of anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene (DBA), 9,10-dipropoxyanthracene, 9, 10-Diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butyl anthracene, 2,6-di-tert-butyl anthracene, 9,10-diphenyl-2,6 -Di-tert-butyl anthracene and the like can be mentioned. Of these, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are preferable from the viewpoint of compatibility with the photosensitive composition.

The content of the sensitizer in the photosensitive composition is not particularly limited, but is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the compound (A) from the viewpoint of curability and physical property balance of the cured product. , 0.1 to 15 parts by weight is more preferable. If the amount of the sensitizer is small, the effect of improving the sensitivity may not be sufficiently obtained. If the amount of the sensitizer is large, the outgas generated from the thin film may increase and the light resistance may decrease.

<Solvent>
A photosensitive composition is obtained by dissolving or dispersing the above components (A) to (C) and, if necessary, the components (D) and (E) in a solvent. The photosensitive composition may be prepared by mixing each component immediately before film formation, or may be stored in a one-component state in which all the components are mixed and prepared in advance.

The solvent may be any solvent as long as it can dissolve the compound (A), and specifically, a hydrocarbon solvent such as benzene, toluene, hexane and heptane; tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether and the like. Ether solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; glycols such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and ethylene glycol diethyl ether. Solvents: Halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be mentioned. From the viewpoint of film formation stability, propylene glycol-1-monomethyl ether-2-acetate and diethylene glycol dimethyl ether are preferable.

The amount of solvent used can be set as appropriate. The preferable amount of the solvent used per 1 g of the solid content of the photosensitive composition is 0.1 to 10 mL. If the amount of the solvent used is small, it may be difficult to obtain the effect of using the solvent such as lowering the viscosity. If the amount of the solvent used is large, the film forming uniformity may deteriorate.

<Other ingredients>
The photosensitive composition of the present invention may contain resin components, additives and the like other than the above (A) to (E).

(Polymer dispersant)
A polymer dispersant may be used to improve the dispersibility of the inorganic filler in the composition. The polymer dispersant is preferably a compound having an acidic functional group or a basic functional group from the viewpoint of affinity for the inorganic filler. Examples of the acidic functional group include a carboxyl group, a sulfo group and a phosphoric acid group, and a carboxyl group is preferable. The acid value of the polymer dispersant is preferably 10 to 100 mgKOH / g. Examples of the basic functional group include an amino group, a piperidyl group, a pyridyl group, an imidazole group, a guanidine group, an amidino group and the like, and an amino group is preferable. Polymer dispersants include urethane, polyimide, alkyd, epoxy, unsaturated polyester, melamine, phenol, acrylic, vinyl chloride, vinyl chloride, vinyl acetate copolymer, polyamide, and polycarbonate. Examples include compounds such as systems. Of these, acrylic and polyester compounds are particularly preferable. The amount of the polymer dispersant used is preferably 5 to 80 parts by weight, particularly preferably 10 to 65 parts by weight, based on 100 parts by weight of the inorganic filler.

(Thermoplastic resin)
It is also possible to add various thermoplastic resins to the photosensitive composition for the purpose of modifying the properties of the photosensitive composition. Examples of the thermoplastic resin include acrylic resin, polycarbonate resin cycloolefin resin, olefin-maleimide resin, polyester resin, polyether sulfone resin, polyarylate resin, polyvinyl acetal resin, polyethylene resin, polypropylene resin, and polystyrene. Examples thereof include resin, polyamide resin, silicone resin, fluororesin, natural rubber and rubber-like resin such as EPDM. The thermoplastic resin may have a crosslinkable group such as an epoxy group, an amino group, a radically polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group and an alkoxysilyl group.

(Filler)
The photosensitive composition may contain a filler, if necessary. Examples of the filler include silver powder, glass fiber, carbon fiber, mica, carbon black, graphite, clay, talc and the like.

(Acid scavenger)
The photosensitive composition may contain an acid scavenger, if necessary. The acid trapping agent captures the acid generated from the acid generator to suppress the diffusion of the acid from the exposed portion to the unexposed portion of the film formed by the photosensitive composition, thereby exposing the film. Increase the difference in solubility of the unexposed area and the unexposed area in the developer.

Examples of the acid trapping agent include nitrogen-containing compounds such as amino group-containing compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

(Additive)
In addition to the above, the photosensitive composition includes an adhesive improver, a coupling agent (silane coupling agent, etc.), a deterioration inhibitor, a radical inhibitor, a mold release agent, a flame retardant, a flame retardant aid, and a surfactant. , Antifoaming agent, Emulsifier, Leveling agent, Repellent inhibitor, Ion trapping agent (Antimon-bismus, etc.), Tixogenic agent, Adhesive agent, Storage stability improver, Ozone deterioration inhibitor, Light stabilizer, Thickening agent Agents, plasticizers, reactive diluents, antioxidants, heat stabilizers, conductivity-imparting agents, antistatic agents, radiation blockers, nucleating agents, phosphorus-based peroxide decomposing agents, lubricants, pigments, metal inerts An agent, a heat conductivity imparting agent, a physical property adjusting agent and the like may be contained within a range that does not impair the object and effect of the present invention.

[Film formation and formation of white reflection pattern]
Since the photosensitive composition contains the compound (A) having a cationically polymerizable functional group and a photoacid generator, a white cured film can be formed by coating, prebaking (dry removal of solvent) and exposure. The cured film has excellent light reflectivity and heat resistance. When the compound (A) has an alkali-soluble functional group, the photosensitive composition can be applied as a negative photosensitive composition. The negative photosensitive composition can be patterned by coating, prebaking, exposure, and alkaline development steps, and then post-baked to form a white pattern.

The method of applying the photosensitive composition onto various substrates is not particularly limited as long as it can be applied uniformly, and general coating methods such as spin coating, slit coating, screening printing, and spray coating can be used. Can be used. Prior to exposure, heating (pre-baking) may be performed for the purpose of solvent drying. The heating temperature can be set as appropriate, but is preferably 60 to 200 ° C, more preferably 80 to 150 ° C. Further, vacuum devolatile may be performed before exposure. Vacuum volatilization may be performed at the same time as heating.

The light source for exposure may be selected according to the absorption wavelength of the photoacid generator and the sensitizer contained in the photosensitive composition. Usually, a light source having a wavelength in the range of 200 to 450 nm (for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, a xenon lamp, a carbon arc lamp, a light emitting diode, etc.) is used.

The amount of exposure is not particularly limited, but is preferably 10 to 50,000 mJ / cm ² , and more preferably 50,000 to 30,000 mJ / cm ² . If the exposure amount is excessively small, curing may be insufficient and the pattern forming property may be lowered, and if the exposure amount is excessively large, the manufacturing cost may increase due to an increase in tact time. Post-exposure baking (PEB) may be performed by applying heat after exposure and before development for the purpose of accelerating the photoreaction. Since the photosensitive composition of the present invention has excellent photosensitivity, a pattern can be formed without performing PEB, and the processability is excellent.

The method for developing the coating film after exposure is not particularly limited. For example, a desired pattern can be formed by bringing an alkaline solution into contact with the coating film by a dipping method, a spray method, or the like to dissolve and remove the unexposed portion. As the alkaline developer, generally used ones can be used without particular limitation. Specific examples of the alkaline developing solution include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. An inorganic alkaline aqueous solution and the like can be mentioned. From the viewpoint of increasing the contrast between the exposed portion and the unexposed portion, the alkali concentration is preferably 25% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less. The developer may contain alcohol, a surfactant and the like for the purpose of adjusting the dissolution rate and the like.

Post-baking conditions after alkaline development can be set as appropriate. The post-bake temperature is preferably 100-400 ° C, more preferably 120-350 ° C.

The thin film formed by the photosensitive composition of the present invention has light reflectivity and is excellent in heat resistance. As the light reflectance, the total light reflectance of the thin film can be used as an index. When the film thickness of the thin film is 2 μm, the total light reflectance at 550 nm is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. As described above, since the photosensitive composition of the present invention is excellent in the dispersibility of the inorganic filler in the resin component, the film-forming property and the patterning property are formed even when a large amount of the inorganic filler is contained so as to have the above-mentioned light shielding property. Excellent in sex. Therefore, it is possible to form a colored pattern having high pattern accuracy and high light reflection. Such a white pattern can be applied to a white reflective resist, a partition wall, or the like of a display element.

In applications such as white reflective resists and partition walls of display elements, the pattern material may be required to have a low dielectric constant from the viewpoint of improving electrical reliability. Since the photosensitive composition of the present invention uses a cyclic siloxane compound as a binder component, it is possible to reduce the dielectric constant. The relative permittivity of the cured product applied to such applications is preferably 4.0 or less, more preferably 3.8 or less, and even more preferably 3.5 or less.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples.

(Synthesis Example 1)
In a 500 mL four-necked flask, 113 g of toluene and 57 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (hereinafter referred to as "TMCTS") are placed and the gas phase part is nitrogen. After the substitution, the internal temperature was set to 105 ° C., and a mixed solution of 18 g of diallyl monomethylisocyanurate, 26 g of diallyl isocyanuric acid, 170 g of dioxane and 0.1 g of a xylene solution of a platinum vinylsiloxane complex (containing 3% by weight as platinum) was added dropwise.

¹ After confirming that the allyl group had disappeared by 1 H-NMR, a mixed solution of 40 g of toluene and 40 g of vinylcyclohexene oxide was added dropwise. ¹ It was confirmed by 1 H-NMR that the vinyl group had disappeared, and the reaction was terminated by cooling. Toluene was distilled off under reduced pressure to obtain a polysiloxane compound 1 (polymer). ^{1 1} H-NMR measurement showed that the polysiloxane compound 1 had an alicyclic epoxy group of 2.4 mmol / g.

(Synthesis Example 2)
In a 500 mL four-necked flask, 113 g of toluene and 57 g of TMCTS were placed to replace the gas phase with nitrogen, and then the internal temperature was set to 105 ° C. A mixed solution of 0.1 g of a xylene solution (containing 3% by weight as platinum) was added dropwise. After confirming the disappearance of the allyl group, a mixed solution of 40 g of toluene and 40 g of vinylcyclohexene oxide was added dropwise, and then the polysiloxane compound 2 (cyclic poly having an epoxy group of 2.3 mmol / g) was obtained in the same manner as in Example 1 above. Siloxane-based polymer) was obtained.

(Synthesis Example 3)
66 g of toluene and 33 g of 1,1,3,3-tetramethyldisiloxane were placed in a 500 mL four-necked flask to replace the gas phase with nitrogen, and then the internal temperature was set to 105 ° C., and tetra (trimethyl), which is a polyhedron-structured polysiloxane. A mixed solution of 25 g of tetra (vinyldimethylsiloxy) octasilsesquioxane, 15 g of diallyl isocyanuric acid, 100 g of dioxane and 0.05 g of a xylene solution (containing 3% by weight as platinum) of a platinum vinylsiloxane complex was added dropwise. After confirming the disappearance of the allyl group, a mixed solution of 23 g of toluene and 23 g of vinylcyclohexene oxide was added dropwise, and then the polysiloxane compound 3 (cyclic poly having a 2.0 mmol / g epoxy group) was obtained in the same manner as in Example 1 above. Siloxane-based polymer) was obtained.

(Synthesis Example 4)
30 g of toluene and 15 g of 1,1,3,3-tetramethyldisiloxane were placed in a 500 mL four-necked flask to replace the gas phase with nitrogen, and then the internal temperature was set to 105 ° C., 3-allyloxymethyl-3-ethyl. A mixed solution of 40 g of oxetane, 160 g of dioxane and 0.05 g of a xylene solution of a platinum vinylsiloxane complex (containing 3% by weight as platinum) was added dropwise. After confirming the disappearance of the allyl group, the reaction was terminated by cooling. Toluene was distilled off under reduced pressure to obtain compound 4.

[Examples 1 to 10, Comparative Examples 1 to 2]
(Preparation of photosensitive composition)
Component (A): Compounds 1 to 3 obtained in the above synthetic examples were used as the alkali-soluble resin having a cationically polymerizable functional group. In the solvent (PGMEA), the above-mentioned component (A), component (B): photoacid generator (“CPI-210S” manufactured by San-Apro), component (C): titanium oxide (average particle size 1. 0 μm, Teika Co., Ltd. “JR-1000”) or zirconium oxide (average particle size 0.14 μm, Kyoritsu Material Co., Ltd. “KZ-0Y-LSF”), component (D): alicyclic as a reactive diluent Formula epoxy compound (“Celoxide 2021P” manufactured by Daicel), alicyclic epoxy-modified cyclic polysiloxane (“KR-470” manufactured by Shin-Etsu Chemical Industry Co., Ltd.), oxetane compound (“OXT-121” manufactured by Toa Synthetic), compound 4, component ( E): Dipropoxyanthracene (DPA; manufactured by Kawasaki Kasei Kogyo Co., Ltd.) as a sensitizer and a solvent (PGMEA) were blended at the ratios (parts by weight) shown in Table 1 to prepare a photosensitive composition.

[Evaluation]
(Film formation)
The compositions of Examples 1 to 6, Comparative Examples 1 to 3 and Reference Examples 1 and 2 are applied on a 50 × 50 mm non-alkali glass substrate by spin coating so that the film thickness after post-baking is 10 to 100 μm. Then, it was prebaked on a hot plate at 100 ° C. for 10 minutes.

(Pattern formation)
After exposing the thin film obtained above through a photomask (line: space = 1: 5 and line: space = 1: 1) using a mask aligner (MA-1300, manufactured by Dainippon Kaken), 23 It was immersed in an alkaline developer (TMAH 1.19% aqueous solution, manufactured by Tama Chemical Industry Co., Ltd.) at ° C. for 2 to 20 minutes for development treatment. Further, post-baking was performed at 150 ° C. for 60 minutes in an oven to form a cured film. For each cured film, the line-and-space portion was observed with a laser microscope (OLS4000 manufactured by Olympus), and the cross-sectional profile was measured. The value obtained by dividing the film thickness by the minimum pattern width at which pattern peeling did not occur was defined as the maximum possible aspect ratio for the pattern. The larger this value is, the finer the pattern can be formed with respect to the film thickness.

(Light reflectivity)
It is applied by spin coating or an applicator so that the film thickness after post-baking is 10 to 100 μm, prebaked at 100 ° C. for 10 minutes on a hot plate, exposed, and then post-baked at 150 ° C. for 60 minutes to form a cured film. did. An integrating sphere unit was attached to an ultraviolet-visible-near-infrared spectroscopic spectrum device (manufactured by Jasco Engineering: V-770), and the light reflectance was measured. The average value of the reflectance in the range of 440 nm to 800 nm was defined as the average reflectance.

(Heat-resistant yellowing)
In general, even if the photosensitive compositions have the same composition, the thicker the film, the more likely it is to turn yellow. Therefore, regarding heat-resistant yellowing, it is applied by spin coating so that the film thickness after post-baking is the same film thickness of 10 μm, prebaked at 100 ° C. for 10 minutes on a hot plate, exposed at 1000 mJ / cm2, and then exposed. A cured film was formed by post-baking at 150 ° C. for 60 minutes, and the light reflectance was measured.

The cured film whose light reflectance was measured was heated in an oven at 150 ° C. for 150 hours, and heat-resistant yellowing was evaluated based on the change in average reflectance before and after heating.
⊚: Average reflectance decrease of less than 2% ○: Average reflectance decrease of less than 4% ×: Average reflectance decrease of 4% or more Photosensitivity of Examples, Comparative Examples and Reference Examples The composition of the composition and the evaluation results are shown in Table 1.

The compositions of Examples 1 to 9 were all excellent in film forming property, and the obtained cured film had excellent heat resistance and light reflection property. In particular, with respect to Examples 1 to 5 and 9 to 10, it was possible to form a fine pattern with an aspect ratio of 1.0 (thickness 10 μm, width 10 μm). In Example 7, it was possible to form a fine pattern with an aspect ratio of 1.33 (thickness 40 μm, width 30 μm). In Example 8, it was possible to form a fine pattern with an aspect ratio of 1.0 (thickness 100 μm, width 100 μm). The composition of Comparative Example 1 in which an acrylic resin was used as a substitute for the component (A) was excellent in film forming property and reflectance, but was insufficient in heat-resistant yellowing. The composition of Comparative Example 1 in which an epoxy resin was used as a substitute for the component (A) was excellent in film forming property and reflectance, but was insufficient in heat-resistant yellowing.

Examples 1 to 6 and 8 to 10 using titanium oxide as the white filler and Example 7 using zirconium oxide are all excellent in film forming property, developability, light reflectivity, and heat-resistant yellowing. It was. From these results, it can be seen that the composition of the present invention can form a white pattern excellent in various properties regardless of the type of colorant.

Examples 2 to 5 and 10 are excellent in film-forming property, developability, and light-shielding property as in Example 1, and are further improved in heat-resistant yellowing as compared with Example 1.

In Example 9 in which Compound 2 was used as the component (A), the amount of the white filler added was the same as in Example 1, but the average reflectance was higher. It is considered that this is because the introduction of the glycidyl group into the polysiloxane compound improved the dispersibility of the white filler.

Claims (17)

Contains polysiloxane compound, photoacid generator, white filler,
The polysiloxane compound contains a cyclic polysiloxane structure and a cationically polymerizable functional group.
A photosensitive composition in which the content of the white filler is 5% by weight or more of the total solid content. The photosensitive composition according to claim 1, wherein the content of the polysiloxane compound is 20 to 95% by weight based on the total solid content. The photosensitive group according to claim 1 or 2, wherein the cationically polymerizable functional group of the polysiloxane compound is one or more functional groups selected from the group consisting of an epoxy group, an oxetanyl group, an alkoxysilyl group and a vinyl ether group. Sex composition. The photosensitive composition according to claim 1 or 2, wherein the cationically polymerizable functional group of the polysiloxane compound is an alicyclic epoxy group or an oxetanyl group. The photosensitive composition according to claim 1 or 2, wherein the polysiloxane compound contains an alicyclic epoxy group and a glycidyl group. The photosensitive composition according to claim 1 or 2, wherein the polysiloxane compound contains an oxetanyl group and a glycidyl group. The photosensitive composition according to claim 1 or 2, wherein the polysiloxane compound contains an alicyclic epoxy group and an oxetanyl group. The photosensitive composition according to any one of claims 1 to 7, wherein the polysiloxane compound further has an alkali-soluble functional group. The photosensitive composition according to claim 8, wherein the alkali-soluble functional group has a structure represented by the following X1 or X2.

The photosensitive composition according to any one of claims 1 to 9, which contains a reactive diluent having two or more cationically polymerizable functional groups in one molecule. The photosensitive composition according to claim 10, wherein the cationically polymerizable functional group of the reaction diluent is an alicyclic epoxy group. The photosensitive composition according to claim 11, wherein the cationically polymerizable functional group of the reaction diluent is an oxetanyl group. The photosensitive composition according to any one of claims 10 to 12, wherein the content of the reaction diluent is 1 to 75% by weight of the total solid content. The white pattern made of the cured product of the photosensitive composition according to any one of claims 1 to 13 has an aspect ratio (film thickness / pattern width) of 0.20 or more when line: space = 1: 1. , A photosensitive composition having a reflectance of 60% or more. The white pattern made of the cured product of the photosensitive composition according to any one of claims 1 to 13 has an aspect ratio (film thickness / pattern width) of 0.50 or more when line: space = 1: 5. , A photosensitive composition having a reflectance of 60% or more. A white pattern comprising a cured product of the photosensitive composition according to any one of claims 1 to 15. A method for producing a white pattern, wherein the photosensitive composition according to any one of claims 1 to 16 is applied onto a substrate, and patterning is carried out by exposure and development.