JP2010031162A - Siloxane resin composition and hardened film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a siloxane resin composition which provides a hardened film having a high hardness and being excellent in abrasion resistance by UV hardening and thermal hardening as well as having high crack resistance. <P>SOLUTION: A siloxane resin composition comprises: (A) a polysiloxane having a phenyl group; (B) a photo-radical polymerization initiator; and (C) at least one radical polymeric monomer selected from the group consisting of tripentaerithritol poly(meth)acrylate, tertrapentaerythritol poly(meth)acrylate, and pentapentaerythritol poly(meth)acrylate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a siloxane resin composition and a cured film using the same.

  Currently, hard coat materials are used for various purposes, and are used to improve the surface hardness of, for example, containers for automobile parts, cosmetics, sheets, films, optical disks, thin displays, and the like. Properties required for the hard coat include heat resistance, weather resistance, adhesiveness, etc. in addition to hardness and scratch resistance. A representative example of the hard coat material is a radical polymerization type UV curable hard coat (see, for example, Non-Patent Document 1), and the constitution thereof is a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives. It is. The oligomer and the monomer are radically polymerized by UV irradiation to crosslink and obtain a high hardness film. This hard coat has the advantage that the time required for curing is short and productivity is improved, and a negative photosensitive material with a general radical polymerization mechanism can be used, and the production cost is low. However, since there are many organic components, the hardness and scratch resistance are low compared to other hard coats, and there is a problem that cracks are caused due to volume shrinkage due to UV curing.

Touch panels are one of the main uses of hard coat. The current mainstream resistive film type touch panel cannot be processed at high temperature because the sensor is mounted on the film. For this reason, the above-mentioned UV curable hard coat that does not require thermal curing or can obtain a cured film by low-temperature curing has been favorably used (for example, see Patent Document 1). On the other hand, in the case of a capacitive touch panel that has been attracting attention in recent years, the protective film is required to have a higher hardness than the resistance film type because it is vulnerable to scratches on the surface. As a capacitive touch panel, for example, a touch panel having a protective film formed of high-hardness inorganic SiO ₂ , SiNx, transparent resin, or the like using glass that can be processed at high temperature is disclosed (for example, Patent Document 2). However, the inorganic hard coat is formed by forming SiO ₂ or SiNx by CVD (Chemical Vapor Deposition) or by performing high-temperature treatment near 300 ° C. for a long time after coating SOG (Spin On Glass). There was a problem that would increase. Therefore, a UV curable hard coat having a high hardness is required.

On the other hand, the UV curable coating composition includes (A) a metal oxide colloidal sol, (B) an alkoxysilane hydrolyzed condensate containing a specific organic functional group at least partially and having a controlled molecular weight distribution, (C) A composition containing a photopolymerization initiator is disclosed (for example, see Patent Document 3).
Noboru Ohara, “Material Design / Coating Technology and Improvement of Hardness in Hard Coat Films Focusing on Plastic Substrates”, Technical Information Association, April 28, 2005, p. 301 JP 2001-330707 A JP 2007-279819 A JP 2007-277332 A

  An object of the present invention is to provide a siloxane resin composition that provides a cured film having high hardness and excellent scratch resistance and high crack resistance by UV curing and heat curing.

  The present invention relates to (A) a polysiloxane having a phenyl group, (B) a photoradical polymerization initiator and (C) tripentaerythritol poly (meth) acrylate, tetrapentaerythritol poly (meth) acrylate and pentapentaerythritol poly (meta). ) A siloxane resin composition comprising at least one radically polymerizable monomer selected from the group consisting of acrylates.

  According to the siloxane resin composition of the present invention, a cured film having high hardness and excellent scratch resistance and crack resistance can be obtained.

  The present invention will be specifically described below.

  The siloxane resin composition of the present invention comprises (A) a polysiloxane having a phenyl group, (B) a photoradical polymerization initiator and (C) tripentaerythritol poly (meth) acrylate, tetrapentaerythritol poly (meth) acrylate and penta It contains at least one radical polymerizable monomer selected from the group consisting of pentaerythritol poly (meth) acrylate.

  The siloxane resin composition of the present invention contains (A) a polysiloxane having a phenyl group. Generation | occurrence | production of the crack of a cured film can be suppressed by containing a phenyl group. Further, since alkali solubility is improved, developability (pattern processability) is improved in applications requiring pattern processing, and it is possible to form a good pattern having no residue after development.

  The polysiloxane having a phenyl group (A) used in the siloxane resin composition of the invention is obtained by hydrolyzing an organosilane compound containing an organosilane compound having a phenyl group and condensing the hydrolyzate. Specific examples of the organosilane compound having a phenyl group include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri (methoxyethoxy) silane, phenyltriacetoxysilane, phenylsilanetriol, diphenyldimethoxysilane, diphenyldiethoxysilane, and diphenyl. Examples include di (methoxyethoxy) silane, diphenyldiacetoxysilane, methylphenyldimethoxysilane, diphenylsilanediol, triphenylmethoxysilane, triphenylethoxysilane, and triphenylsilanol. Two or more of these may be used in combination, or may be used in combination with other organosilane compounds.

(A) As for the content rate of the phenyl group in the polysiloxane which has a phenyl group, 0.1 mol or more is preferable with respect to 1 mol of Si atoms, and the crack resistance of a cured film can be improved more. More preferably, it is 0.2 mol or more, More preferably, it is 0.3 mol or more. Moreover, 0.8 mol or less is preferable, More preferably, it is 0.6 mol or less. If it is the said range, the cured film which can make hardness and crack resistance compatible at a higher level will be obtained. The phenyl group content is determined, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of polysiloxane and determining the ratio of the peak area of Si bonded to the phenyl group and the peak area of Si bonded to no phenyl group. Can do. Moreover, when Si and a phenyl group are not directly bonded, the phenyl group content of the whole polysiloxane is calculated from the integration ratio of the peak derived from the phenyl group and other peaks excluding silanol from ¹ H-nuclear magnetic resonance spectrum. Then, the content of the phenyl group indirectly bonded is calculated together with the result of the ²⁹ Si-nuclear magnetic resonance spectrum described above.

  The polysiloxane having a phenyl group (A) used in the siloxane resin composition of the present invention preferably has a radical polymerizable group. By having a radical polymerizable group, a crosslinking reaction with a radical polymerizable monomer described later occurs, the crosslinking density of the resulting cured film is improved, and the hardness of the cured film can be further improved. Moreover, since it can harden | cure with little light irradiation amount, the effect which a sensitivity improves in the use which requires pattern processing is acquired. Specific examples of the radical polymerizable group include unsaturated groups such as vinyl group, α-methylvinyl group, acryloyl group, methacryloyl group, and styryl group. Of these, an acryloyl group or a methacryloyl group is preferred because the curing reaction in the film proceeds smoothly and the sensitivity can be further improved.

  The polysiloxane having a radical polymerizable group is obtained by hydrolyzing an organosilane compound containing an organosilane compound having a radical polymerizable group and condensing the hydrolyzate. Since the polysiloxane of component (A) in the present invention has a phenyl group, an organosilane compound having a phenyl group, an organosilane compound having a radical polymerizable group, and, if necessary, other organosilane compounds are hydrolyzed. It is preferable to condense the hydrolyzate. Specific examples of the organosilane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and γ-glycidoxypropylvinyldimethoxysilane. Γ-glycidoxypropylvinyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styryltriacetoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane , Γ-methacryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-actyl Acryloyloxy propyl methyl dimethoxy silane, such as γ- acryloyl propyl methyl diethoxy silane. Two or more of these may be used in combination. Of these, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-methacryloylpropyltriethoxysilane in terms of hardness of the cured film and sensitivity during pattern processing. Is particularly preferably used.

  (A) The content of the radical polymerizable group in the polysiloxane having a phenyl group is preferably 0.01 mol or more, more preferably 0.1 mol or more with respect to 1 mol of the Si atom. Moreover, 0.6 mol or less is preferable and 0.4 mol or less is more preferable. If it is the said range, the cured film which can make hardness and crack resistance compatible at a higher level will be obtained.

  (A) The polysiloxane having a phenyl group used in the siloxane resin composition of the present invention hydrolyzes an organosilane compound containing an organosilane compound represented by the following general formula (1), and condenses the hydrolyzate. Since the hardness of a cured film improves more since the crosslinking density of siloxane improves, it is preferable that it is obtained. For example, an organosilane compound having a phenyl group and an organosilane compound represented by the following general formula (1) may be hydrolyzed, and the organosilane compound represented by the following general formula (1) has a phenyl group. In some cases, it may be hydrolyzed only.

In general formula (1), R ^{1 to} R ⁴ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a substituted product thereof. Represents. n represents an integer of 2 to 8, but may have a distribution. The plurality of R ² and R ⁴ may be the same or different.

  Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

  (A) The content ratio of the organosilane residue represented by the general formula (1) in the polysiloxane having a phenyl group is preferably 1 mol% or more in terms of the Si atom mole ratio relative to the number of moles of Si atoms in the whole polysiloxane. Preferably it is 5 mol% or more. Moreover, 40 mol% or less is preferable. If it is the said range, the cured film which can make hardness and crack resistance compatible at a higher level will be obtained.

  Specific examples of the organosilane represented by the general formula (1) include methyl silicate 51 (manufactured by Fuso Chemical Co., Ltd.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Co., Ltd.), methyl Examples thereof include silicate 51, methyl silicate 53A, ethyl silicate 40, and ethyl silicate 48 (manufactured by Colcoat Co., Ltd.).

  (A) The polysiloxane having a phenyl group used in the siloxane resin composition of the present invention hydrolyzes an organosilane compound containing an organosilane compound having a phenyl group in the presence of metal compound particles described later, and the hydrolyzate. If it is obtained by condensing, the hardness, scratch resistance and crack resistance of the cured film are further improved. By polymerizing polysiloxane in the presence of metal compound particles, chemical bonds (covalent bonds) with metal compound particles occur in at least part of the polysiloxane, and the metal compound particles are uniformly dispersed and the coating solution is stored. This is considered to improve stability and homogeneity of the cured film. Moreover, the refractive index of the cured film obtained can be adjusted with the kind of metal compound particle. In addition, as a metal compound particle, what is illustrated as a below-mentioned (E) metal compound particle can be used.

  The polysiloxane having a phenyl group (A) used in the siloxane resin composition of the present invention preferably has fluorine. By containing fluorine, the scratch resistance of the cured film is further improved. The polysiloxane having fluorine is obtained by hydrolyzing an organosilane compound containing an organosilane compound having fluorine and condensing the hydrolyzate. Since the polysiloxane of the component (A) in the present invention has a phenyl group, an organosilane compound having a phenyl group, an organosilane compound having fluorine, and another organosilane compound as necessary are hydrolyzed, and It is preferable to condense the decomposition product. Specific examples of the organosilane having fluorine include trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltrimethoxysilane. Ethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, Heptadecafluorodecyltrimethoxysilane, Heptadecafluorodecyltriethoxysilane, Bis (trifluoromethyl) dimeth Sisilane, bis (trifluoropropyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane And heptadecafluorodecylmethyldimethoxysilane. Two or more of these may be used in combination. Of these, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and tridecafluorooctyltriethoxysilane are particularly preferably used.

  The polysiloxane having a phenyl group (A) used in the siloxane resin composition of the present invention may be synthesized using an organosilane compound other than the above. Specific examples of the organosilane compound used include methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxy Silane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropi Lutriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyl Trimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyl Triethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Tripropoxy silane , Γ-glycidoxypropyl triisopropoxy silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltri (methoxyethoxy) silane, α-glycidoxybutyltrimethoxysilane, α-glycid Xylbutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycid Xylbutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltripropoxysilane 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) ) Butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- A Nopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldi Ethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypro Rumethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane and the like. Two or more of these may be used in combination.

  In the siloxane resin composition of the present invention, (A) the content of the polysiloxane having a phenyl group is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application, but with respect to the total amount of the siloxane resin composition 0.1 to 80% by weight is common. Moreover, 10 weight% or more in solid content is preferable.

  The weight average molecular weight (Mw) of the polysiloxane having a phenyl group (A) used in the siloxane resin composition of the present invention is not particularly limited, but preferably in terms of polystyrene measured by gel permeation chromatography (GPC). 1,000 or more, more preferably 2,000 or more. Moreover, Preferably it is 100,000 or less, More preferably, it is 50,000 or less. By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.

  The (A) phenyl group used in the siloxane resin composition of the present invention can be obtained by polysiloxane hydrolyzing an organosilane compound and then subjecting the hydrolyzate to a condensation reaction in the presence or absence of a solvent. it can.

  Various conditions for the hydrolysis reaction, for example, acid concentration, reaction temperature, reaction time, etc., can be appropriately set in consideration of the reaction scale, reaction vessel size, shape, etc. For example, in a solvent, an organosilane compound After adding an acid catalyst and water over 1 to 180 minutes, the reaction is preferably carried out at room temperature to 110 ° C. for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 105 ° C.

  The hydrolysis reaction is preferably performed in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferable. The preferred content of these acid catalysts is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total organosilane compound used during the hydrolysis reaction. By controlling the amount of the acid catalyst within the above range, it can be easily controlled so that the hydrolysis reaction proceeds as necessary and sufficiently.

  After obtaining the silanol compound by the hydrolysis reaction of the organosilane compound, it is preferable to carry out the condensation reaction by heating the reaction solution as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. In order to increase the degree of polymerization of the polysiloxane, reheating or a base catalyst may be added.

  The solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent. Specific examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3- Alcohols such as methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol di Ethers such as chill ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; dimethylformamide, dimethylacetamide Amides such as; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, lactic acid Acetates such as ethyl and butyl lactate; toluene, xylene, hexane, cyclohexane, etc. Aromatic or aliphatic hydrocarbons, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, and the like dimethyl sulfoxide. Diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono t-butyl ether, propylene glycol monopropyl ether, propylene glycol in terms of the transmittance and crack resistance of the cured film Monobutyl ether, γ-butyrolactone and the like are also preferably used.

  When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the reaction. Further, after hydrolysis according to the purpose, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

  The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the total organosilane compound. By making the quantity of a solvent into the said range, it can control easily so that a hydrolysis reaction may progress sufficiently and necessary.

  The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of silane atoms.

  The siloxane resin composition of the present invention contains (B) a radical photopolymerization initiator. (B) Any radical photopolymerization initiator may be used as long as it is decomposed and / or reacted by light (including ultraviolet rays and electron beams) to generate radicals. Specific examples include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine- 4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoylphenylphosphine oxide, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide, 1-phenyl-1,2-propanedione -2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-ben) Iloxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, ethanone, 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-Isopropylphenyl) -2-hydroxy-2- Tylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ', 4 4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemeta Minium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propaminium chloride monohydrate, 2-isopropylthioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N , N-trimethyl-1-propanaminium chloride, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole, 10-butyl-2- Chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, can Furquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η5-2,4-cyclopentadiene-1- Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, di Benzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl Acetal, Anne Laquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2 , 6-Bis (p-azidobenzylidene) -4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabrominated, tribromophenylsulfone, peroxy Examples thereof include a combination of a photoreducible dye such as benzoyl oxide, eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. Two or more of these may be contained.

  Among these, in order to further increase the hardness of the cured film, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having amino groups, or benzoic acid ester compounds having amino groups are preferable. These compounds are involved not only in the crosslinking reaction of radical polymerizable groups but also in crosslinking of siloxane as a base or acid during light irradiation and thermal curing, and the cured film hardness is further improved.

  Specific examples of the α-aminoalkylphenone compound include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like. Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-( 2,4,4-trimethylpentyl) -phosphine oxide and the like. Specific examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O -Benzoyloxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like. Specific examples of the benzophenone compound having an amino group include 4,4-bis (dimethylamino) benzophenone and 4,4-bis (diethylamino) benzophenone. Specific examples of the benzoic acid ester compound having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like.

  (B) 0.01 weight% or more is preferable in solid content of a siloxane resin composition, and, as for content of radical photopolymerization initiator, 0.1 weight% or more is more preferable. Moreover, 20 weight% or less is preferable and 10 weight% or less is more preferable. By setting it as the said range, radical hardening can fully be advanced and elution of the residual radical polymerization initiator etc. can be prevented and solvent resistance can be ensured.

  The siloxane resin composition of the present invention comprises (C) at least one radical polymerization selected from the group consisting of tripentaerythritol poly (meth) acrylate, tetrapentaerythritol poly (meth) acrylate, and pentapentaerythritol poly (meth) acrylate. Contains a functional monomer. Here, (meth) acrylate is a general term for acrylate or methacrylate. Further, “poly (meth) acrylate” refers to those having a total of 7 or more acrylate groups or methacrylate groups, and preferably 14 or less.

  The cured film having high hardness and scratch resistance can be obtained by polymerizing the (C) radical polymerizable monomer and (A) the polysiloxane having a phenyl group by the action of the (B) photo radical polymerization initiator. Since the (C) radical polymerizable monomer has a larger number of functional groups and a higher molecular weight than conventional polyfunctional (meth) acrylates, it can be said to be a compound in which partial crosslinking has proceeded. Therefore, it is considered that the crosslink density of the cured film can be improved, and the hardness and scratch resistance of the obtained cured film are improved. Further, since the crosslinking has already progressed, it is considered that the volume shrinkage due to the crosslinking at the time of light irradiation can be suppressed and the crack resistance is improved. Furthermore, (A) the polysiloxane having a phenyl group is considered to have a small volume shrinkage at the time of thermosetting and to improve crack resistance. Therefore, by combining (A), (B), and (C), a cured film having high hardness and good scratch resistance and crack resistance can be obtained.

  The content of the (C) radical polymerizable monomer is preferably 5% by weight to 85% by weight and more preferably 20% by weight to 70% by weight in the solid content of the siloxane resin composition.

  Specific examples of the (C) radical polymerizable monomer include tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate. , Tripentaerythritol hepta methacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate and the like.

  The siloxane resin composition of the present invention may further contain other radical polymerizable monomers. By containing other radically polymerizable monomers, processability can be improved according to the purpose, such as peeling during development, resolution, and reduction in developed film, particularly in applications requiring pattern processing.

  Specific examples of other radical polymerizable monomers include acrylic monomers. The radical polymerizable monomer may be monofunctional or polyfunctional, and may contain two or more of these.

  Specific examples of the monofunctional radical polymerizable monomer include acrylic acid, methacrylic acid, glycidyl methacrylate, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, p-hydroxystyrene, phenethyl acrylate, N- Methylolacrylamide, 9-decanoic acid, 2- (methacryloyloxy) ethyl isocyanate, 2- (α-chloroacryloyloxy) ethyl isocyanate, isobornyl acrylate, tetrahydrofurfuryl acrylate, 2-acryloyloxyethyl succinic acid, etc. Can be mentioned.

  Specific examples of the polyfunctional radical polymerizable monomer include trimethylolpropane triacrylate, dimethyloltricyclodecane diacrylate, ethoxylated bisphenol A dimethacrylate glycerin triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, Mention may be made of compounds such as pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, and ethoxylated isocyanuric acid triacrylate.

  The siloxane resin composition of the present invention preferably further contains (D) an organosilane compound having a radical polymerizable group. The organosilane compound here does not contain a hydrolysis condensate. (D) By containing the organosilane compound which has a radically polymerizable group, a crosslinking point increases and the hardness of a cured film improves more. Moreover, when it has an organic group having 3 or more carbon atoms between the radical polymerizable group and the silane atom, it enters between the (meth) acrylic part and the siloxane part and plays a role as a spacer, so that the crack resistance is further improved.

  (D) Although there is no restriction | limiting in particular in content of the organosilane compound which has a radically polymerizable group, 0.1 weight% or more is preferable in solid content of a siloxane resin composition, and the hardness of a cured film can be improved more. . More preferably, it is 1% by weight or more. On the other hand, from the viewpoint of crack resistance of the cured film, it is preferably 30% by weight or less, and more preferably 15% by weight or less.

  (D) Specific examples of the organosilane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styryltriacetoxysilane, γ- Acryloylpropyltrimethoxysilane, gamma-acryloylpropyltriethoxysilane, gamma-methacryloylpropyltrimethoxysilane, gamma-methacryloylpropyltriethoxysilane, gamma-methacryloylpropylmethyldimethoxysilane, gamma-methacryloylpropylmethyldiethoxysilane, gamma-acryloyl Examples thereof include propylmethyldimethoxysilane and γ-acryloylpropylmethyldiethoxysilane. Two or more of these may be used in combination. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are used from the viewpoint of the hardness of the cured film, and γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, and γ-methacryloylpropyl are used from the viewpoint of crack resistance. Trimethoxysilane and γ-methacryloylpropyltriethoxysilane are particularly preferably used.

  The siloxane resin composition of the present invention may further contain (E) metal compound particles. (E) By containing metal compound particles, the refractive index can be adjusted to a desired range. Further, the hardness, scratch resistance and crack resistance of the cured film can be further improved. (E) The number average particle diameter of the metal compound particles is preferably 1 nm to 200 nm. In order to obtain a cured film having a high transmittance, the number average particle diameter is more preferably 1 nm to 70 nm. Here, the number average particle diameter of the metal compound particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a transmission electron microscope, or a scanning electron microscope.

  Examples of the metal compound particles (E) include silicon compound particles, aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, barium compound particles, and the like, and an appropriate one can be selected depending on the application. For example, titanium compound particles such as titanium oxide particles and zirconium compound particles such as zirconium oxide particles are preferably used to obtain a cured film having a high refractive index. In order to obtain a cured film having a low refractive index, it is preferable to contain hollow silica particles and the like.

  Examples of commercially available metal compound particles include silicon oxide-titanium oxide composite particles “OPTRAIK (registered trademark)” TR-502, “OPTRAIK” TR-503, “OPTRAIK” TR-504, “OPTO”. "Lake" TR-513, "Optlake" TR-520, "Optlake" TR-527, "Optlake" TR-528, "Optrake" TR-529, "Optrake" TR-505 (Titanium oxide particles) (Above, trade name, manufactured by Catalyst Chemical Industry Co., Ltd.), zirconium oxide particles (manufactured by High Purity Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (produced by Catalyst Chemical Industry Co., Ltd.), tin oxide particles (Manufactured by Kojundo Chemical Laboratory Co., Ltd.).

Further, as silica particles, IPA-ST, MIBK-ST having a number average particle diameter of 12 nm, IPA-ST-L having a number average particle diameter of 45 nm, IPA-ST-ZL having a number average particle diameter of 100 nm, and 15 nm of the number average particle diameter. PGM-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), “Oscar (registered trademark)” 101 having a number average particle diameter of 12 nm, “Oscar” 105 having a number average particle diameter of 60 nm, “ “Oscar” 106, “Cataloid (registered trademark)”-S (trade name, manufactured by Catalytic Kasei Kogyo Co., Ltd.) having a number average particle diameter of 5 to 80 nm, “Quarton (registered trademark)” PL- having a number average particle diameter of 16 nm 2L-PGME, “Quortron” PL-2L-BL with a number average particle diameter of 17 nm, “Quartron” PL-2L-DAA, “Quoron with a number average particle diameter of 18-20 nm Ron "PL-2L, GP-2L ( trade names, Fuso Chemical Co., Ltd.), number average particle diameter of 100nm of silica _(SiO 2) SG-SO100 _(trade name, Kyoritsu made Materials Co., Ltd.), number Examples include “Lerosil (registered trademark)” (trade name, manufactured by Tokuyama Corporation) having an average particle diameter of 5 to 50 nm. Examples of the hollow silica particles include “Optlake” TR-113.

  There is no restriction | limiting in particular in content of metal compound particle | grains, Although it can be made into a suitable quantity with a use, it is common to set it as about 1-70 weight% in solid content of a siloxane resin composition.

  The siloxane resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability of the composition is improved, and the resolution after development is improved in applications requiring pattern processing. The content of the polymerization inhibitor is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more in the solid content of the siloxane resin composition. On the other hand, from the viewpoint of keeping the hardness of the cured film high, it is preferably 5% by weight or less, and more preferably 1% by weight or less.

  Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.

  The siloxane resin composition of the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the light resistance of the resulting cured film is improved, and the resolution after development is improved in applications that require pattern processing. The ultraviolet absorber is not particularly limited and known ones can be used, but benzotriazole compounds, benzophenone compounds, and triazine compounds are preferably used in terms of transparency and non-coloring properties.

  Examples of ultraviolet absorbers for benzotriazole compounds include 2- (2Hbenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 'Hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole.

  Examples of the ultraviolet absorber of the benzophenone compound include 2-hydroxy-4-methoxybenzophenone.

  Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  The siloxane resin composition of the present invention may contain a solvent. A compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used in that each component can be dissolved uniformly and the transparency of the resulting coating film can be improved. Two or more of these may be combined. Moreover, the compound whose boiling point under atmospheric pressure is 110-250 degreeC is more preferable. By setting the boiling point to 110 ° C. or higher, drying proceeds moderately at the time of coating, and a good coating without uneven coating can be obtained. On the other hand, when the boiling point is 250 ° C. or lower, the amount of residual solvent in the film can be reduced, and film shrinkage during thermosetting can be further reduced, so that better flatness can be obtained.

  Specific examples of the compound having an alcoholic hydroxyl group and a boiling point of 110 to 250 ° C. under atmospheric pressure include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2- Butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl Examples include ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol. Among these, diacetone alcohol is preferable from the viewpoint of storage stability, and propylene glycol mono t-butyl ether is particularly preferably used from the viewpoint of step coverage.

  Specific examples of the cyclic compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, And cycloheptanone. Among these, γ-butyrolactone is particularly preferably used.

  Moreover, the siloxane resin composition of this invention may contain solvents other than the above. For example, (A) Various solvents such as acetates, ketones and ethers exemplified as the solvent used in the hydrolysis and condensation reaction of polysiloxane having a phenyl group may be mentioned.

  There is no restriction | limiting in particular in content of a solvent, According to the application | coating method etc., arbitrary amounts can be used. For example, when film formation is performed by spin coating, the amount of solvent is generally 50 to 95% by weight of the entire siloxane resin composition.

  The siloxane resin composition of the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing. The curing agent is not particularly limited and known ones can be used. Specific examples include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, and methylolated melamine. There are derivatives, methylolated urea derivatives and the like, and these may be contained singly or in combination of two or more. Of these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used because of the stability of the curing agent and the processability of the obtained coating film.

  Since curing of polysiloxane is accelerated by acid, the siloxane resin composition of the present invention may contain a curing catalyst such as a thermal acid generator. The thermal acid generator is not particularly limited and known ones can be used. Various onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenium salts, and sulfonic acids Examples thereof include esters and halogen compounds.

  The siloxane resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve flow properties during coating. There is no restriction | limiting in particular in the kind of surfactant, For example, a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Two or more of these may be used.

  Among the commercially available fluorosurfactants, “Megafac (registered trademark)” F142D, F172, F173, F183, F445, F470, F475, F477 (above, Dainippon Ink and Chemicals, Inc.) NBX-15, FTX-218 (manufactured by Neos Co., Ltd.) are preferably used.

  Among the commercially available silicone surfactants, BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by Big Chemie Japan Co., Ltd.) are preferably used.

  The siloxane resin composition of the present invention may contain additives such as a dissolution inhibitor, a stabilizer, and an antifoaming agent as necessary.

  There is no restriction | limiting in particular in the solid content density | concentration of the siloxane resin composition of this invention, Arbitrary quantities of a solvent and solute can be used according to a coating method. For example, when a film is formed by spin coating as described later, the solid content concentration is generally 5 to 50% by weight.

  An example is given and demonstrated about the formation method of the cured film using the siloxane resin composition of this invention.

The siloxane resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, oven, etc. Pre-bake with a heating device. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm. After pre-baking, using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA), light of about 10 to 4000 J / m ² (wavelength 365 nm exposure equivalent) is passed through the desired mask. Irradiate with or without intervention. The exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used. Thereafter, this film is heated in a range of 150 to 450 ° C. for about 1 hour with a heating device such as a hot plate or oven.

For applications that require patterning through a mask, the siloxane resin composition of the present invention preferably has a sensitivity of 100 to 4000 J / m ² when exposed to PLA. If the sensitivity is lower than 4000 J / m ² , the radiation exposure time at the time of pattern formation becomes longer, resulting in a decrease in productivity, and the amount of radiation exposure increases, resulting in an increase in the amount of reflection from the base substrate and a deterioration in the pattern shape. To do. In this process, post-exposure baking may be performed as necessary after exposure.

  The sensitivity in the patterning exposure by the PLA is determined by the following method, for example. The composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 120 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 2 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ) With a 2.38 wt% aqueous tetramethylammonium hydroxide solution for an arbitrary period of time, followed by a 30 second rinse with water. In the formed pattern, an exposure amount for resolving a 30 μm line-and-space pattern with a one-to-one width is obtained as sensitivity.

  After patterning exposure, the exposed portion is dissolved by development, and a negative pattern can be obtained. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.

  Thereafter, this film is thermally cured in a range of 120 to 280 ° C. for about 1 hour with a heating device such as a hot plate or oven to obtain a cured film. The resolution is preferably 20 μm or less. Although there is no restriction | limiting in particular in the film thickness of a cured film, It is preferable to set it as 0.1-15 micrometers.

  The cured film of the present invention preferably has a hardness of 4H or more and a transmittance of 90% or more when the film thickness is 1.5 μm. The transmittance refers to the transmittance at a wavelength of 400 nm. The hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.

  The cured film obtained by curing the siloxane resin composition of the present invention is used as a touch panel protective film, various hard coat materials, an antireflection film, and an optical filter. Further, since it has negative photosensitivity, it is suitably used for TFT flattening films, insulating films, antireflection films, color filter overcoats, column materials, etc. for liquid crystal and organic EL displays. Among these, since it has high hardness and scratch resistance, it can be suitably used as a touch panel protective film. Examples of the touch panel system include a resistive film type, an optical type, an electromagnetic induction type, and a capacitance type. Since especially high hardness is calculated | required by an electrostatic capacitance type touch panel, the cured film of this invention can be used suitably.

  The present invention will be described below with reference to examples thereof, but the embodiment of the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of Polysiloxane Solution (i) In a 500 mL three-necked flask, 108.96 g (0.80 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, diacetone alcohol (DAA) Was added in an oil bath at 40 ° C., and an aqueous solution of phosphoric acid in which 0.297 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 54.0 g of water while stirring was added with a dropping funnel. Added over minutes. After stirring at 40 ° C. for 1 hour, the oil bath temperature was set to 70 ° C. and stirred for 1 hour, and the oil bath was further heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, 110 g in total of methanol and water as by-products were distilled out. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (i). The phenyl group content relative to Si atoms was 20 mol% as measured by ²⁹ Si-nuclear magnetic resonance spectrum (NMR) of polysiloxane. In addition, it was 8000 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC.

Synthesis Example 2 Synthesis of Polysiloxane Solution (ii) A 500 mL three-necked flask was charged with 81.72 g (0.60 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, and 138.57 g of DAA. Then, an aqueous phosphoric acid solution in which 0.322 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 54.0 g of water was added over 10 minutes with a dropping funnel while being immersed in an oil bath at 40 ° C. with stirring. . Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 110 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (ii). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 6000 (polystyrene conversion).

Synthesis Example 3 Synthesis of polysiloxane solution (iii) A 500 mL three-necked flask was charged with 54.48 g (0.40 mol) of methyltrimethoxysilane, 118.98 g (0.60 mol) of phenyltrimethoxysilane, and 149.26 g of DAA. Then, an aqueous solution of phosphoric acid in which 0.347 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 54.0 g of water was added over 10 minutes with a dropping funnel while being immersed in an oil bath at 40 ° C. with stirring. . Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, 110 g in total of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (iii). The phenyl group content relative to the Si atoms was 60 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, it was 5500 (polystyrene conversion) when the weight average molecular weight of the obtained polymer was measured by GPC.

Synthesis Example 4 Synthesis of polysiloxane solution (iv) In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, 29 of vinyltrimethoxysilane .61 g (0.20 mol) and 140.61 g of DAA were added, and 0.327 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 54.0 g of water while being immersed in an oil bath at 40 ° C. and stirred. The phosphoric acid aqueous solution was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 110 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (iv). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, it was 7500 (polystyrene conversion) when the weight average molecular weight of the obtained polymer was measured by GPC.

Synthesis Example 5 Synthesis of polysiloxane solution (v) In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, γ-acryloylpropyltrimethoxy 46.88 g (0.20 mol) of silane and 155.47 g of DAA were charged, and immersed in an oil bath at 40 ° C. while stirring, 5617 g of water and 0.3617 g of phosphoric acid (0.2% by weight based on the charged monomer) The phosphoric acid aqueous solution which melt | dissolved this was added over 10 minutes with the dropping funnel. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 110 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (v). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, it was 7500 (polystyrene conversion) when the weight average molecular weight of the obtained polymer was measured by GPC.

Synthesis Example 6 Synthesis of Polysiloxane Solution (vi) In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, M silicate 51 (Tama Chemical) Kogyo Co., Ltd. 23.50 g (0.20 mol in terms of Si atom) and DAA 135.50 g were charged, immersed in an oil bath at 40 ° C. and stirred with water 52.2 g and phosphoric acid 0.315 g (charged monomer) The phosphoric acid aqueous solution in which 0.2 wt% was dissolved was added with a dropping funnel over 10 minutes. Next, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 100 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (vi). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 8000 (polystyrene conversion).

Synthesis Example 7 Synthesis of Polysiloxane Solution (vii) In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, silica particles PL-2L- DAA (solid content concentration 21.9% by weight, manufactured by Fuso Chemical Industry Co., Ltd.) 54.87 g (0.20 mol in terms of Si atom) and DAA 92.42 g were charged and immersed in an oil bath at 40 ° C. and stirred. However, an aqueous phosphoric acid solution in which 0.292 g of phosphoric acid (0.2% by weight based on the charged monomer) was dissolved in 43.20 g of water was added with a dropping funnel over 10 minutes. Next, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 95 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (vii). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 6000 (polystyrene conversion).

Synthesis Example 8 Synthesis of Polysiloxane Solution (viii) In a 500 mL three-necked flask, 27.24 g (0.20 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, 29.32 g of vinyltrimethoxysilane. 61 g (0.2 mol), silica particle PL-2L-DAA (solid content concentration 21.9% by weight, manufactured by Fuso Chemical Industry Co., Ltd.) 54.87 g (0.20 mol in terms of Si atom), DAA 94. A solution of phosphoric acid in which 0.296 g of phosphoric acid (0.2% by weight with respect to the charged monomer) was dissolved in 43.20 g of water was added with a dropping funnel over 10 minutes. Added. Next, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 95 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (viii). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 6000 (polystyrene conversion).

Synthesis Example 9 Synthesis of polysiloxane solution (ix) In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, trifluoropropyltrimethoxysilane Was charged with 43.64 g (0.20 mol) and DAA 152.68 g, immersed in an oil bath at 40 ° C. and stirred with water 54.0 g and phosphoric acid 0.327 g (0.2% by weight based on the charged monomer). An aqueous phosphoric acid solution in which was dissolved was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 110 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (ix). The phenyl group content relative to Si atoms was 40 mol% as measured by ²⁹ Si-NMR of polysiloxane. In addition, it was 7500 (polystyrene conversion) when the weight average molecular weight of the obtained polymer was measured by GPC.

Synthesis Example 10 Synthesis of Polysiloxane Solution (x) In a 500 mL three-necked flask, 198.3 g (1.0 mol) of phenyltrimethoxysilane and 170.63 g of DAA were charged, immersed in an oil bath at 40 ° C. and stirred under water 54 A phosphoric acid aqueous solution in which 0.394 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 0.000 g was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 120 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (x). In addition, when the weight average molecular weight of the obtained polymer was measured by GPC, it was 6000 (polystyrene conversion).

Synthesis Example 11 Synthesis of polysiloxane solution (xi) In a 500 mL three-necked flask, 40.86 g (0.30 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, M silicate 51 (Tama Chemical) 35.25 g (manufactured by Kogyo Co., Ltd.) (0.30 mol in terms of Si atom) and 168.32 g of DAA were charged and immersed in an oil bath at 40 ° C. and stirred to 51.3 g of water and phosphoric acid 0.311 g (charged monomer) The phosphoric acid aqueous solution in which 0.2 wt% was dissolved was added with a dropping funnel over 10 minutes. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 110 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (xi). In addition, it was 7000 (polystyrene conversion) when the weight average molecular weight of the obtained polymer was measured by GPC.

Synthesis Example 12 Synthesis of Polysiloxane Solution (xii) In a 500 mL three-necked flask, 108.96 g (0.80 mol) of methyltrimethoxysilane, 46.88 g (0.20 mol) of γ-acryloylpropyltrimethoxysilane, and 134 of DAA were added. .10g, immersed in an oil bath at 40 ° C. and stirred, an aqueous phosphoric acid solution prepared by dissolving 0.312g of phosphoric acid (0.2% by weight with respect to the charged monomer) in 54.00g of water was added with a dropping funnel over 10 minutes. Added. Subsequently, when the mixture was heated and stirred under the same conditions as in Synthesis Example 1, a total of 120 g of methanol and water as by-products were distilled out during the reaction. DAA was added to the obtained polysiloxane DAA solution so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (xii). In addition, it was 9000 (polystyrene conversion) when the weight average molecular weight of the obtained polymer was measured by GPC.

Synthesis Example 13 Synthesis of Acrylic Resin Solution (a) A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred with heating at 5 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (a). Got. PGMEA was added to the obtained acrylic resin solution (a) so that the solid concentration was 40% by weight. The acrylic resin had a weight average molecular weight of 10,000 and an acid value of 118 mgKOH / g.

The evaluation methods in each example and comparative example are shown below.
(1) Measurement of transmittance For a cured film having a film thickness of 1.5 μm produced on a 5 cm square glass substrate, a UV-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation) is used to transmit 400 nm. The rate was measured. The film thickness was measured at a refractive index of 1.50 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. The same applies to the film thickness described below.
(2) Evaluation of crack resistance After a 1.5 μm thick cured film produced on a 5 cm square glass substrate was further heated in air at 250 ° C. for 3 hours, the surface was observed with an optical microscope to check for cracks. Was observed. Evaluation was determined in the following 5 stages, and 4 or more was judged as acceptable.
5: No cracks are generated in the film.
4: A crack is generated at one of the four corners of the substrate.
3: Cracks occurred in the range of 2 to 4 locations in the four corners of the substrate.
2: A crack has occurred in the periphery of the substrate.
1: Cracks are generated on the entire surface of the substrate.
(3) Measurement of hardness Pencil hardness was measured in accordance with “JIS K5600-5-4 (1999)” for a cured film having a thickness of 1.5 μm prepared on a 5 cm square glass substrate. However, the load weight was 500 g.
(4) Evaluation of scratch resistance For a cured film having a film thickness of 1.5 μm produced on a glass substrate of 5 cm × 7 cm, a steel wool of # 0000 was subjected to a load of 200 g on the cured film and reciprocated 10 times in the long side direction. The condition of the wound was observed. Evaluation was determined in the following 5 stages, and 4 or more was judged as acceptable.
5: The film is not damaged at all.
4: There are 1 to 10 scratches on the membrane.
3: There are 11-30 scratches on the membrane.
2: There are 31-50 scratches on the membrane.
1: There are 51 or more scratches on the membrane.
(5) Sensitivity The exposure amount that forms a 30 μm line-and-space pattern with a one-to-one width after exposure and development (hereinafter referred to as the optimum exposure amount) was defined as sensitivity. The exposure amount was measured with an I-line illuminometer.
(6) Resolution The minimum pattern size after development at the optimum exposure amount was measured.
(7) Pattern processability After patterning on a silicon wafer, it was observed whether unmelted portions were generated in the unexposed areas. Those with no undissolved residue were marked with “◯”, and those with undissolved residue were marked with “x”.

Example 1
Under a yellow light, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals) 0.5166 g, 4,4-bis (diethylamino) ) 0.0272 g of benzophenone was dissolved in 2.9216 g of DAA and 2.4680 g of PGMEA, and a mixture of tripentaerythritol polyacrylate, tetrapentaerythritol polyacrylate and pentapentaerythritol polyacrylate (trade name “T-PE-A”, Guangei Chemical Industry Co., Ltd.) PGMEA 50 wt% solution PGMEA 50 wt% solution, 4-t-butylcatechol PGMEA 1 wt% solution 1.4958 g polysiloxane solution (i) 6.7974 g, BYK-333 (BIC The PGMEA1 weight percent solution of Me Japan Ltd.) was added 0.2000 g (corresponding to a concentration 100 ppm), and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained the siloxane resin composition A. FIG.

  The produced siloxane resin composition A was rotated for 10 seconds at 500 rpm using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) on a Tempax glass plate (Asahi Techno Glass plate Co., Ltd.). And then spin-coated at 1000 rpm for 4 seconds), and prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 2 μm. . The produced film was exposed using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) as a light source of an ultrahigh pressure mercury lamp, and air was then used using an oven (IHPS-222 manufactured by ESPEC Corporation). A cured film was prepared by curing at 220 ° C. for 1 hour. About the obtained cured film, the transmittance | permeability, crack resistance, hardness, and scratch resistance were evaluated by the said method.

  Similarly, a prebaked film having a thickness of 2 μm was formed on a silicon wafer. The obtained pre-baked film was exposed with a gap of 100 μm through a gray scale mask for sensitivity measurement using PLA as an ultrahigh pressure mercury lamp as a light source. Then, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 90 seconds with 2.38 wt% tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Then rinsed with water for 30 seconds. After development, pattern processability, sensitivity and resolution were evaluated.

Example 2
A siloxane resin composition B was obtained in the same manner as in Example 1 except that the polysiloxane solution (ii) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition B.

Example 3
A siloxane resin composition C was obtained in the same manner as in Example 1 except that the polysiloxane solution (iii) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition C.

Example 4
A siloxane resin composition D was obtained in the same manner as in Example 2 except that tripentaerythritol octaacrylate was used instead of “T-PE-A”. The obtained composition was evaluated in the same manner as in Example 1.

Example 5
A siloxane resin composition E was obtained in the same manner as in Example 2 except that tetrapentaerythritol decaacrylate was used instead of “T-PE-A”. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition E.

Example 6
A siloxane resin composition F was obtained in the same manner as in Example 1 except that the polysiloxane solution (iv) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition F.

Example 7
A siloxane resin composition G was obtained in the same manner as in Example 1 except that the polysiloxane solution (v) was used instead of the polysiloxane solution (i). Using the obtained siloxane resin composition G, evaluation was performed in the same manner as in Example 1.

Example 8
A siloxane resin composition H was obtained in the same manner as in Example 1 except that the polysiloxane solution (vi) was used instead of the polysiloxane solution (i). The obtained siloxane resin composition H was used and evaluated in the same manner as in Example 1.

Example 9
A siloxane resin composition I was obtained in the same manner as in Example 1 except that the polysiloxane solution (vii) was used instead of the polysiloxane solution (i). Using the obtained siloxane resin composition I, evaluation was performed in the same manner as in Example 1.

Example 10
A siloxane resin composition J was obtained in the same manner as in Example 1 except that the polysiloxane solution (viii) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition J.

Example 11
A siloxane resin composition K was obtained in the same manner as in Example 1 except that the polysiloxane solution (ix) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition K.

Example 12
Under a yellow light, 0.4737 g of “Irgacure 907” and 0.0249 g of 4,4-bis (diethylamino) benzophenone were dissolved in 3.2606 g of DAA and 2.8283 g of PGMEA, and a 50% by weight PGMEA solution of “T-PE-A” 4 9859 g, 1.810 g of 1 wt% PGMEA solution of 4-t-butylcatechol, 0.4986 g of vinyltriethoxysilane, 6.2323 g of polysiloxane solution, BYK-333 (BIC Chemie Japan) which is a silicone surfactant 0.2000 g (corresponding to a concentration of 100 ppm) of PGMEA 1 wt. Subsequently, it filtered with the 0.45 micrometer filter and the siloxane resin composition L was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition L.

Example 13
Under a yellow lamp, 0.4373 g of “Irgacure 907” and 0.0230 g of 4,4-bis (diethylamino) benzophenone were dissolved in 0.2644 g of DAA and 3.1332 g of PGMEA, and a PGMEA 50 wt% solution 4 of “T-PE-A” .6032 g, 1.810 g of 1% by weight PGMEA solution of 4-t-butylcatechol, silica particle PL-2L-DAA (solid content concentration 21.9% by weight, manufactured by Fuso Chemical Industry Co., Ltd.), 4.2039 g, polysiloxane 0.2000 g (corresponding to a concentration of 100 ppm) of PGMEA 1% by weight of solution (ii) 5.7540 g and BYK-333 (by Big Chemie Japan Co., Ltd.) which is a silicone surfactant was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and the siloxane resin composition M was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition M.

Example 14
A siloxane resin composition N was obtained in the same manner as in Example 1 except that the polysiloxane solution (x) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition N.

Example 15
A siloxane resin composition O was prepared in the same manner as in Example 12 except that the polysiloxane solution (iv) was used instead of the polysiloxane solution (ii), and γ-methacryloylpropyltrimethoxysilane was used instead of vinyltriethoxysilane. Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition O.

Example 16
A siloxane resin composition P was obtained in the same manner as in Example 13 except that the polysiloxane solution (iv) was used instead of the polysiloxane solution (ii). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition P.

Example 17
A siloxane resin composition Q was obtained in the same manner as in Example 1 except that the polysiloxane solution (xi) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition Q.

Comparative Example 1
A siloxane resin composition R was obtained in the same manner as in Example 1 except that the polysiloxane solution (xii) was used instead of the polysiloxane solution (i). Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition R.

Comparative Example 2
DAA 2.5150 g, PGMEA 2.0259 g, “T-PE-A” PGMEA 50 wt% solution 5.9801 g, 4-tert-butylcatechol PGMEA 1 wt% solution 1.7940 g, polysiloxane solution (ii) 7.4751 g, silicone 0.2000 g (corresponding to a concentration of 100 ppm) of a 1% by weight PGMEA solution of BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), a system surfactant, was added and stirred. Subsequently, it filtered with the 0.45 micrometer filter and obtained the siloxane resin composition S. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition S.

Comparative Example 3
A siloxane resin composition T was obtained in the same manner as in Example 2 except that dimethylol tricyclodecane diacrylate was used instead of “T-PE-A”. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition T.

Comparative Example 4
A siloxane resin composition U was obtained in the same manner as in Example 2 except that dipentaerythritol hexaacrylate (trade name “DPHA”, manufactured by Nippon Kayaku Co., Ltd.) was used instead of “T-PE-A”. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition U.

Comparative Example 5
An acrylic resin composition X was prepared in the same manner as in Example 1 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i), and PGMEA was used instead of DAA (total PGMEA was 5.3896 g). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained acrylic resin composition X.

  The compositions of Examples 1 to 17 and Comparative Examples 1 to 5 are shown in Tables 2 to 3, and the evaluation results are shown in Tables 4 and 5.

  The cured film obtained by curing the siloxane resin composition of the present invention includes various hard coat films such as a protective film for touch panels, flattening films for TFTs of liquid crystal and organic EL displays, insulating films, antireflection films, and reflective films. It is suitably used for prevention films, optical filters, overcoats for color filters, pillar materials, and the like.

Claims (9)

(A) a polysiloxane having a phenyl group, (B) a photoradical polymerization initiator and (C) tripentaerythritol poly (meth) acrylate, tetrapentaerythritol poly (meth) acrylate and pentapentaerythritol poly (meth) acrylate A siloxane resin composition comprising at least one radical polymerizable monomer selected from the group. The siloxane resin composition according to claim 1, wherein the (A) polysiloxane has a radical polymerizable group. The siloxane resin composition according to claim 1 or 2, further comprising (D) an organosilane compound having a radical polymerizable group. The siloxane resin composition according to claim 2, wherein the radically polymerizable group of the (A) polysiloxane is a (meth) acryloyl group. The (A) polysiloxane is obtained by hydrolyzing an organosilane compound containing an organosilane compound represented by the following general formula (1), and condensing the hydrolyzate. 4. The siloxane resin composition according to any one of 4 above.

(In the formula, R ^{1 to} R ⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a substituted product thereof. n represents an integer of 2 to 8. The plurality of R ² and R ⁴ may be the same or different. The (A) polysiloxane is a polysiloxane obtained by hydrolyzing an organosilane compound containing an organosilane compound having a phenyl group in the presence of metal compound particles and condensing the hydrolyzate. The siloxane resin composition according to any one of claims 1 to 5. The siloxane resin composition according to any one of claims 1 to 6, further comprising (E) metal compound particles. The siloxane resin composition according to claim 1, wherein the (A) polysiloxane has fluorine. A cured film obtained by curing the siloxane resin composition according to claim 1.