JP2008297490A - Curable resin composition with excellent etching resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysilsesquioxane improved in ion etching resistance and heat resistance, and a curable resin composition including the polysilsesquioxane. <P>SOLUTION: The silicon compound having aromatic ring and vinyl group is obtained by hydrolyzing a mixture including a silicon compound R<SP>1a</SP>Si(OR<SP>2</SP>)<SB>3</SB>represented by the formula (1a) and one or more silicon compounds selected from the group consisting of a silicon compound R<SP>1b</SP>Si(OR<SP>3</SP>)<SB>3</SB>represented by the formula (1b) and a silicon compound R<SP>1c</SP>R<SP>1d</SP>Si(OR<SP>4</SP>)<SB>2</SB>represented by the formula (c) followed by condensing. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a silicon compound having an aromatic ring and a vinyl group, and a curable resin composition. More specifically, the present invention relates to a resist having reactive ion etching resistance, various electrical / electronic component insulating materials, and a laminate (printed wiring). Plate) and various composite materials such as FRP (fiber reinforced plastic), adhesives, and curable resin compositions suitable for paints.

  Polysilsesquioxane resin is a general term for silicone resins having 1.5 oxygen atoms relative to the number of silicon atoms. Among them, polyphenylsilsesquioxane resin having a ladder structure is heat resistant, Due to its excellent insulating properties, it has been proposed to be used for coating materials, sealing materials, interlayer insulating films and others. Such resins are usually synthesized by hydrolyzing silane compounds having hydrolyzable groups such as phenyltrichlorosilane and phenyltrialkoxysilane, followed by a condensation reaction using a basic catalyst in an organic solvent. Is done.

  In Patent Document 1, by producing polyphenylsilsesquioxane having a specific range of molecular weight under mild conditions, the resulting polyphenylsilsesquioxane has a melting point and can be used as a thermoplastic resin. Although disclosed, the polyphenylsilsesquioxane thus obtained has good moldability but is insufficient in heat resistance because it is a thermoplastic resin. If the condensation is advanced in order to increase the molecular weight forcibly, the three-dimensional cross-linking proceeds, resulting in a solvent-insoluble gel.

Patent Document 2 discloses a ladder-type silsesquioxane compound partially having a styryl group, but when used as a resist for reactive ion etching with an organic fluorine compound such as tetrafluoromethane, There is a problem that the disappearance rate by etching is too fast and the performance is not sufficient for use as a resist.
JP 20032266753 A JP 2002-88157 A

  An object of the present invention is to provide a polysilsesquioxane having improved ion etching resistance and heat resistance and a curable resin composition comprising the polysilsesquioxane.

  As a result of intensive studies to achieve the above object, the present inventors have found that polysilsesquioxane obtained by crosslinking an organosilicon compound having an aromatic ring and a vinyl group by radical polymerization or hydrosilylation reaction is resistant. The inventors found that the etching property is excellent and completed the present invention.

That is, the present invention includes the following matters.
[1] A silicon compound represented by the following formula (1a), or
One or more silicon compounds selected from the group consisting of a silicon compound represented by the following formula (1a), a silicon compound represented by the following formula (1b) and a silicon compound represented by the following formula (1c); The silicon compound which has an aromatic ring and a vinyl group obtained by condensing after condensing the mixture containing this.

R ^1a Si (OR ² ) ₃ (1a)
(In formula (1a), R ^1a represents a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.)
R ^1b Si (OR ³ ) ₃ (1b)
(In formula (1b), R ^1b represents an alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an unsaturated aliphatic residue having 2 to 14 carbon atoms, and R ³ represents 1 carbon atom. Represents an alkyl group of ~ 4.)
R ^1c R ^1d Si (OR ⁴ ) ₂ (1c)
(In the formula (1c), R ^1c and R ^1d are an aromatic ring having 6 to 20 carbon atoms, a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms, An unsaturated aliphatic residue or an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.
[2] In the formula (1a), R ^1a is an aryl group having 8 to 14 carbon atoms having a phenyl group to which a vinyl group is bonded or an aryl group having 12 to 14 carbon atoms having a naphthyl group to which a vinyl group is bonded. ,
In the formula (1b), R ^1b is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
In the formula (1c), R ^1c and R ^1d are each independently an aryl group having 8 to 14 carbon atoms having a phenyl group to which a vinyl group is bonded and a 12 to 14 carbon atoms having a naphthyl group to which a vinyl group is bonded. The silicon compound having an aromatic ring and a vinyl group according to [1], which is an aryl group, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
[3] In the formula (1a), R ^1a is a styryl group, in the formula (1b), R ^1b is a methyl group or a phenyl group, and in the formula (1c), R ^1c and R ^1d are a methyl group or A silicon compound having an aromatic ring and a vinyl group according to [1] or [2], which is a phenyl group.
[4] The aromatic ring having a vinyl group and the silicon compound having a vinyl group according to any one of [1] to [3], wherein the content of the aromatic ring is 40% by mass or more.
[5] The silicon compound having an aromatic ring and a vinyl group according to any one of [1] to [3], wherein the content of the aromatic ring is 60% by mass or more.
[6] (A) A silicon compound having an aromatic ring and a vinyl group according to any one of [1] to [5], (B) a thermal or ultraviolet radical polymerization initiator, and, if necessary, (D) an organic solvent A curable resin composition containing
[7] The curable resin composition according to [6], further comprising (C) a compound having a vinyl group.
[8] (A) A silicon compound having an aromatic ring and a vinyl group according to any one of [1] to [5], (E) a silicon compound having a Si—H bond, and, if necessary, (D) organic A curable resin composition containing a solvent and (F) a Pt compound.
[9] The curable resin composition according to [8], further comprising (C) a compound having a vinyl group.
[10] The curable resin composition according to any one of [6] to [9], wherein the aromatic ring content in the composition is 40% by mass or more.
[11] The curable resin composition according to any one of [6] to [9], wherein the aromatic ring content in the composition is 60% by mass or more.
[12] A cured product obtained by curing the curable resin composition according to any one of [6] to [11] with heat or ultraviolet rays.

  According to the present invention, a silicon compound having an aromatic ring and a vinyl group excellent in etching resistance and heat resistance, and a curable resin composition containing the silicon compound are obtained.

The silicon compound (A) having an aromatic ring and a vinyl group according to the present invention and the curable resin containing the silicon compound (A) will be described.
The silicon compound (A) having an aromatic ring and a vinyl group of the present invention is
A silicon compound represented by the following formula (1a), or
One or more silicon compounds selected from the group consisting of a silicon compound represented by the following formula (1a), a silicon compound represented by the following formula (1b) and a silicon compound represented by the following formula (1c); It is obtained by hydrolyzing and condensing a mixture containing.

R ^1a Si (OR ² ) ₃ (1a)
(In formula (1a), R ^1a represents a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.)
R ^1b Si (OR ³ ) ₃ (1b)
(In formula (1b), R ^1b represents an alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an unsaturated aliphatic residue having 2 to 14 carbon atoms, and R ³ represents 1 carbon atom. Represents an alkyl group of ˜4.)
R ^1c R ^1d Si (OR ⁴ ) ₂ (1c)
(In the formula (1c), R ^1c and R ^1d are an aromatic ring having 6 to 20 carbon atoms, a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms, An unsaturated aliphatic residue or an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.
Examples of the silicon compound represented by the formula (1a) include compounds represented by the following formulas (1) to (3). Here, the “hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms” means that the “substituted” group portion of the substituted trialkoxysilicon compound is a vinylphenyl group, a vinylnaphthyl group, and A hydrocarbon group such as a vinylbenzyl group.

As a silicon compound represented by the formula (1a), R ^1a in the formula (1a) is a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms. The aryl group having 8 to 14 carbon atoms having a bonded phenyl group or the aryl group having 12 to 14 carbon atoms having a naphthyl group having a vinyl group bonded thereto is more preferable, and a styryl group is particularly preferable. R ² in the formula (1a) represents an alkyl group having 1 to 4 carbon atoms. It is preferable that the number of carbon atoms is 4 or less because the hydrolysis and condensation reactions are fast. On the other hand, if the number of carbon atoms exceeds 4, the rate of hydrolysis and condensation reaction is slow, and the boiling point of the alcohol to be produced becomes high, which makes it difficult to remove. Here, “styryl” refers to vinylphenyl.

As a silicon compound represented by the formula (1b), R ^1b in the formula (1b) represents an alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an unsaturated fat having 2 to 14 carbon atoms. The group residue is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group or a phenyl group. As the silicon compound represented by the formula (1b), for example, aryltrialkoxysilane is preferably used, but is not particularly limited.

As a silicon compound represented by the formula (1c), R ^1c in the formula (1c) is an aromatic ring having 6 to 20 carbon atoms and a carbonized structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms. It is a hydrogen group or an unsaturated aliphatic residue having 2 to 20 carbon atoms, but an aryl group having 8 to 14 carbon atoms having a phenyl group to which a vinyl group is bonded, or 12 to 12 carbon atoms having a naphthyl group to which a vinyl group is bonded. It is more preferably a 14 aryl group, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and particularly preferably a methyl group or a phenyl group. As the silicon compound represented by the formula (1c), for example, aryl dialkoxysilane is preferably used, but is not particularly limited.

  In order to adjust the ratio of the aromatic ring contained in the silicon compound (A) having an aromatic ring and a vinyl group of the present invention, the silicon compound represented by the formula (1b) and the formula (1c) may be used as necessary. it can.

By carrying out condensation after hydrolysis of the silicon compounds (1a) to (1c), a silicon compound (A) having an aromatic ring and a vinyl group is obtained.
For the hydrolysis and condensation, acid catalysts and alkali catalysts generally used in the synthesis of alkylsilsesquioxanes and organic polysilicone compounds can be used. In particular, when it is desired to increase the molecular weight, it is effective to proceed the condensation under mild conditions after performing a hydrolysis reaction to some extent with an acid catalyst. The acid catalyst is not particularly limited, and includes an inorganic acid such as hydrochloric acid, nitric acid and phosphoric acid, and an organic acid such as acetic acid and citric acid. However, it is preferable to use an inorganic acid for sufficient hydrolysis. When hydrolysis is performed, a condensation reaction occurs at the same time, but it is preferable to minimize the condensation reaction.

As temperature which performs a hydrolysis, the range of 0 to 50 degreeC is preferable, and the range of 10 to 30 degreeC is more preferable.
In the hydrolysis reaction, a solvent may or may not be used.

  The alkoxysilane hydrolyzate obtained by the above reaction may be subjected to a condensation reaction using a basic catalyst in an organic solvent in which the hydrolyzed product is dissolved to synthesize a high molecular weight silsesquioxane and an organosilicone compound to some extent. it can. The reaction can also be performed in a two-phase separation state using an organic solvent that is not uniformly mixed with water.

The basic catalyst can be added after being dissolved in water. Basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate and disodium hydrogen phosphate. Among them, sodium carbonate and sodium hydrogen carbonate are preferable, but not limited thereto. The amount of the catalyst is desirably 0.3 mol or less with respect to 1 mol of the alkoxysilane, and is particularly preferably used in the range of 0.1 to 0.001 mol. If the amount exceeds 0.3 mol, an insoluble gel tends to be formed, and if it is less than 0.001 mol, the reaction time becomes long. The amount of water used is preferably in the range of 20 to 300 parts by mass with respect to 100 parts by mass of the hydrolyzate solution.

  As catalysts for the condensation reaction, tin compounds such as tin dioctylate, tin dilaurate, dibutyltin diacetate, dibutyltin dioctylate, dibutyltin dilaurate, bis (acetoxydibutyltin) oxide and bis (lauroxydibutyltin) oxide Can be used as a catalyst for the condensation reaction. The amount to be used is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the silicon compound (A) having an aromatic ring and a vinyl group.

  The condensation reaction is desirably carried out with stirring, and the reaction temperature is preferably in the range of 0 ° C to 60 ° C, more preferably in the range of 10 to 30 ° C. When the reaction temperature exceeds 60 ° C., hydrolysis of the formed siloxane bond also occurs, so that the ladder structure is disturbed and becomes indefinite, and as a result, an insoluble gel is easily formed. The condensation reaction can be stopped by adding acid and neutralizing the basic catalyst.

  Organic solvents used in the condensation reaction include ketone solvents such as methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as diethyl ether, ester solvents such as ethyl acetate and butyl acetate, butanol And alcohol solvents such as hexanol, and halogenated hydrocarbon solvents such as chloroform, trichloroethylene, and carbon tetrachloride, but are not limited to these. Among them, methyl isobutyl ketone and toluene are preferable. Two or more kinds may be mixed and used. The amount of the organic solvent to be used is not particularly limited, but is preferably 50 to 3,000 parts by mass, more preferably 200 parts per 100 parts by mass of the silicon compound (A) having an aromatic ring and a vinyl group of the present invention. It is the range of -1,000 mass parts.

  The silicon compound (A) having an aromatic ring and a vinyl group of the present invention preferably has a polystyrene-equivalent weight average molecular weight in the range of 500 to 1,000,000 and a melting point in the range of 50 ° C to 250 ° C. . When the molecular weight is 500 or less, it is often fragile and cannot maintain its shape when used as a resist. When the molecular weight exceeds 1,000,000, the solubility and fluidity of the resulting compound are problematic. Become. When the melting point is 50 ° C. or less, there are many stickiness after solvent drying at the time of molding, and it can be applied only to a special molding method. When the melting point is 250 ° C. or more, the fluidity at the time of molding becomes a problem.

When the silicon compound obtained in this way is subjected to a heat treatment, the condensation reaction further proceeds to increase the molecular weight. The high molecular weight is obtained by heat treatment in the range from the melting point, which is the temperature at which the solid organosilicon compound is liquefied, to 400 ° C. At this time, a catalyst for promoting condensation may be added, but it is preferable not to add it. Below the melting point, since the molten state does not occur, contact between silanol groups hardly occurs and the reaction hardly proceeds. On the other hand, if it exceeds 400 ° C., thermal decomposition occurs, which is not preferable. When not adding a catalyst, the range of 250 to 380 degreeC is more preferable.

The heat treatment can be performed in an air atmosphere, but the heat treatment is preferably performed in an inert gas atmosphere such as nitrogen and argon. In the case of using a catalyst, tin compounds such as tin dioctylate, tin dilaurate, dibutyltin diacetate, dibutyltin dioctylate and dibutyltin dilaurate, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-isopropoxytitanium ,
Titanium compounds such as tetra-n-butoxytitanium, di-isopropoxybis (ethylacetoacetate) titanium and di-isopropoxybis (acetylacetonato) titanium, lead diacetate, zinc diacetate and bis (2-ethylhexanoic acid) And the like, and amine compounds such as ethanolamine and diethanolamine are used as curing catalysts. The curing catalyst is usually used in the range of 0.01 to 1 part by mass with respect to 100 parts by mass of the organosilicon compound.

Such a curing reaction at a high temperature is effective for patterning by a special molding method such as thermal imprinting. However, resists used in the field of semiconductors and hard disks that require an accuracy of 1 μm or less are not preferable because the dimensional accuracy is reduced by shrinkage during cooling.

  Therefore, in order to carry out curing at a lower temperature, the following two polymerization methods can be employed. One is a method in which a vinyl group is radically polymerized by heat or ultraviolet rays, and the other is a method in which a vinyl group and Si—H are cured by a hydrosilylation reaction.

Each curing reaction will be described below.
The curable resin composition of the present invention suitable for radical polymerization comprises a silicon compound (A) having an aromatic ring and a vinyl group, a thermal or ultraviolet radical polymerization initiator (B), and an organic solvent (D) as necessary. contains.

If the radical polymerization method is used, the organosilicon compound can be polymerized alone. When the ratio of the aromatic ring is increased, other compounds are used for the purpose of improving mechanical properties, optical properties, electrical properties and curability. And may be copolymerized.
As a polymerization initiator (B) used by this invention, what generate | occur | produces a radical by a heat | fever or an ultraviolet-ray can be used. Examples of such a polymerization initiator (B) include an azo-based or organic peroxide initiator.
For example, azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile),
Ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide, isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide Diacyl peroxides such as oxide and p-chlorobenzoyl peroxide, hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide and t-butyl peroxide , Dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide and tris (t-butylperoxy) triazi Dialkyl peroxides such as 1,1-di-t-butylperoxycyclohexane and peroxyketals such as 2,2-di (t-butylperoxy) butane, t-butylperoxypivalate, t- Butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3.5 , 5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate and alkyl peresters such as di-t-butylperoxytrimethyladipate and diisopropyl peroxydicarbonate, di-s -Butyl peroxydicarbonate and t-butyl percarbonate Percarbonates such can be mentioned, such as carboxymethyl isopropyl carbonate.

Examples of the polymerization initiator used for ultraviolet radical polymerization include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4′-bis (diethylamino) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, Carbonyl compounds such as benzyl, benzyldimethyl ketal, benzyldiethyl ketal and diacetyl, sulfur compounds such as anthraquinone or thioxanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, diphenyl disulfide and dithiocarbamate Is mentioned.

  The curable resin composition of the present invention has a vinyl group that can be copolymerized with a silicon compound (A) having an aromatic ring and a vinyl group in order to improve mechanical properties, optical properties, electrical properties, and curability. The compound (C) may be contained.

  Examples of the compound (C) having a vinyl group used in the present invention include (meth) acrylic acid ester derivatives, styryl derivatives, (meth) acrylamide derivatives, vinyl ester derivatives, allyl compounds, fumaric acid ester derivatives, maleic acid esters. Derivatives and N-vinylamide derivatives.

  Examples of (meth) acrylic acid ester derivatives include simple substances such as methyl (meth) acrylate, ethyl (meth) alkylate, butyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate. In addition to functional compounds, neopentyl glycol, alkylene oxide adducts of bisphenol-A, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol polyfunctional (meth) acrylates and epoxy resins ( An epoxy acrylate to which (meth) acrylic acid is added may be mentioned. In particular, an epoxy acrylate obtained by adding (meth) acrylic acid to a (cresol) novolac resin-based or bisphenol-A based epoxy resin is preferable.

Examples of styryl derivatives include styrene, vinyltoluene, α-methylstyrene, 4-vinylbiphenyl, 1,1′-diphenylethylene, vinylnaphthalene, acenaphthylene, divinylbenzene, divinylbiphenyl, diisopropenylbenzene, and divinylnaphthalene. Use of these compounds is preferable because the mass fraction of the aromatic ring is increased.

Examples include (meth) acrylamide derivatives, (meth) acrylamide, and N, N′-dimethylmethacrylamide.
Examples of vinyl ester derivatives include vinyl acetate and vinyl benzoate.

  Examples of allyl compounds include diallyl phthalate prepolymer, diallyl isophthalate prepolymer, triallyl isocyanurate, allyl ester resin, allyl benzoate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate, diallyl naphthalate and triallyl isocyanurate. It is done.

Examples of the fumarate derivative include dibenzyl fumarate and diphenyl fumarate.
Examples of maleic acid ester derivatives include dibenzyl maleate and diphenyl maleate.

Examples of the N-vinylamide derivative include N-vinylacetamide, N-vinyl fumarate, N-vinylpyrrolidone and the like.
Among these, a compound having a (meth) acryl group is preferable for increasing the ultraviolet curability, and a compound having an aromatic ring is desirable for increasing the etching resistance.

Examples of the organic solvent (D) include ketone solvents such as methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as diethyl ether, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate. System solvents, alcohol solvents such as butanol and hexanol, and halogenated hydrocarbon solvents such as chloroform, trichlorethylene and carbon tetrachloride. Although the quantity of the organic solvent (D) to be used is not specifically limited, Preferably it is 100-100,000 mass parts with respect to 100 mass parts of thermosetting resin compositions, More preferably, it is the range of 200-10,000. It is.
The thermosetting resin composition of the present invention includes a silicon compound (A) having an aromatic ring and a vinyl group, a silicon compound (E) having a Si—H bond, and, if necessary, a compound (C) having a vinyl group. An organic solvent (D) and a Pt compound (F).

  The silicon compound (E) (hereinafter also referred to as “hydrosilane”) having a Si—H bond used in the hydrosilylation reaction is preferably a compound having at least two Si—H groups in the molecule. Here, when two hydrogen atoms are bonded to one silicon atom, two SiH groups are counted. These compounds may be used alone or in combination of two or more.

Specifically, hydrosilanes represented by the following formulas (4) to (8) and three or more hydrogen atoms on the aromatic ring are substituted with SiR ⁵ ₂ H, SiR ⁵ H ₂ and / or SiH _3. A hydrosilane etc. can be illustrated.

In the above formula, R ⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different. Y represents a divalent organic group having 2 to 10 carbon atoms. a represents an integer of 2 or 3, l and m each represents an integer of 1 to 200, and n represents an integer of 3 to 8.

The “hydrogen or monovalent organic group having 1 to 20 carbon atoms” of R ⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms or a trialkylsiloxy group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isoamyl group, n-octyl group, n-nonyl group, phenyl group, naphthyl group, trimethylsiloxy Group and triphenylsiloxy group. Of these, hydrogen, a methyl group and a phenyl group are preferable.

  The divalent group represented by Y is not particularly limited as long as it is a group that can be stably bonded to a silicon atom. Specifically, it is a C2-C20 hydrocarbon group or a silicone compound represented by the following formula.

o represents an integer of 1 to 20.
Moreover, you may use the vinyl compound which reacts with these Si-H. In particular, polyallyl compounds having high hydrosilylation activity are diallyl phthalate prepolymer, diallyl isophthalate prepolymer, triallyl isocyanurate, allyl ester resin, diallyl terephthalate, diallyl isophthalate. Diallyl phthalate, triallyl isocyanurate, trimethylolpropane triallyl ether, pentaerythritol triallyl ether and pentaerythritol tetraallyl ether. However, these uses are not preferable unless the mass fraction is at least smaller than that of the silicon compound having an aromatic ring and a vinyl group, because the performance such as the thermal weight reduction rate is lowered.

The ratio of Si—H / vinyl group in the hydrosilylation reaction in the curable composition is preferably 0.5 to 5, more preferably 0.6 to 3, and particularly preferably 0.8 to 2.
As the hydrosilylation catalyst, generally known ones can be used without any particular limitation. Among them, the neutral platinum catalyst does not produce unwanted by-products, and the hydrosilylation reaction and the hydrolysis / silanol condensation reaction are performed. It is preferable because it can be made in a single pot with a good yield.

  Examples of such neutral platinum catalysts include platinum-organic compound complexes, platinum-organofunctional siloxane complexes, and platinum-diolefin compound complexes. Of these, platinum-vinylsiloxane complexes, platinum-acetylacetonate complexes, and platinum-decadiene complexes are preferred.

Although there is no particular limitation on the amount of the Pt compound is preferably employed in the range of proportions of 10 ^-2 to 10 ^-9 mol relative to SiH groups 1 mol, the ratio of more preferably 10 ^-3 to 10 ^-7 mol It is desirable to use within this range.

About the compound (C) and organic solvent (D) which have a vinyl group, the same thing as radical polymerization can be used.
When used as a resist for reactive ion etching using tetrafluoromethane, it is preferable that the mass fraction of the aromatic ring in the resin composition is high. If the mass fraction of the aromatic ring is low, the etching rate becomes high, which is not preferable. Therefore, it is desirable that the mass fraction of the aromatic ring is at least 40% by mass or more, more preferably 60% by mass or more.

  An aromatic ring is a compound that exhibits aromaticity according to the Hückel rule, and is an unsaturated cyclic ring having 4n + 2 (n = 1, 2, 3,...) Electrons contained in a cyclic π-electron system. Refers to a compound. The π-electron system is not limited to π-electrons derived from double bonds, and does not need to be a six-membered ring and need not be composed of only hydrocarbons. It is preferable that it is what is called a benzene ring comprised by these.

  Here, the mass fraction of the aromatic ring is obtained by calculating the ratio of the total atomic weight of the elements constituting the aromatic ring to the total molecular weight of the molecules constituting the polymer (formula weight in the case of the polymer). It is done.

For example, in the case of a compound of the following formula (10):
Formula weight = Si (28.086) × 4 + C (12.010) × 32 + H (1.00079) × 2
8 + O (15.9994) × 6 = 620.91,
Molecular weight of aromatic ring = C (12.010) × 24 + H (1.0079) × 16 = 304.39,
The mass fraction of the aromatic ring = 304.39 / 620.91 × 100 = 49 mass%.

  Moreover, when calculating the mass fraction of an aromatic ring with respect to the compound obtained by condensing after hydrolysis, it is represented by the compound used as the raw material hydrolyzed, for example, Formula (1a), Formula (1c). Assuming that each compound is completely hydrolyzed and condensed in theory, it is calculated by calculating the compound. In the case of Expression (1a) and Expression (1c), the following (1a ′) and (1c ′)) are calculated.

Therefore, when the compound represented by the formula (1a) is a compound of the following formula (11), calculating the aromatic ring mass fraction,
Formula weight = Si (28.086) × 1 + C (12.010) × 8 + H (1.0079) × 7 + O (15.9994) × 1.5 = 155.22
Molecular weight of aromatic ring = C (12.010) × 6 + H (1.0079) × 4 = 76.10.
The mass fraction of the aromatic ring = 76.10 / 155.22 × 100 = 49 mass%.

  Moreover, when calculating the mass fraction of an aromatic ring with respect to the composition which mixed the compound obtained by hydrolyzing the compound of Formula (11), and divinylbenzene by 4: 1, the mass fraction of each compound is calculated. The rate is calculated as a weighted average of the mixing ratio of the composition.

<Mass fraction of aromatic ring of compound of formula (11)>
Formula weight = Si (28.086) × 1 + C (12.010) × 8 + H (1.0079) × 7 + O (15.9994) × 1.5 = 155.22
Molecular weight of aromatic ring = C (12.010) × 6 + H (1.0079) × 4 = 76.10.
Mass fraction of aromatic ring = 76.10 / 155.22 × 100 = 49 mass%
<Mass fraction of aromatic ring of divinylbenzene>
Formula weight = C (12.010) × 10 + H (1.0079) × 10 = 130.19
Molecular weight of aromatic ring = C (12.010) × 6 + H (1.0079) × 4 = 76.10.
Mass fraction of aromatic ring = 76.10 / 130.19 = 58 mass%
<Aromatic ring mass fraction of the composition obtained by mixing the compound of the formula (11) after hydrolysis and a compound obtained by condensation with divinylbenzene in a ratio of 4: 1>
Mass fraction of aromatic ring = (49 mass% × 4 + 58 mass% × 1) ÷ 5 = 51 mass%
It becomes.

  As described above, the content of the aromatic ring in the composition is not only derived from (A) a silicon compound having an aromatic ring and a vinyl group, but also (C) a compound having a vinyl group, (E) silicon having a Si—H bond. It can also be increased by allowing a compound to coexist. And the mass fraction of the aromatic ring in the composition is blended among (A) a silicon compound having an aromatic ring and a vinyl group, (C) a compound having a vinyl group and (E) a silicon compound having a Si—H bond. The mass fraction of the aromatic ring in each of the components is calculated by weighted averaging with the blending ratio of each component.

〔Example〕
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

<Synthesis Example 1>
To a three-necked flask equipped with a thermometer and a condenser tube, diphenyldimethoxylane (9.05 g, 37.0 mmol), p-styryltrimethoxysilane (2.77 g, 12.3 mmol) and triethoxysilane (2.57 g, 12. 3 mmol) was weighed and 90.0 g of propylene glycol monomethyl ether acetate was added. While stirring at room temperature, 2.89 g of a 2500 ppm nitric acid aqueous solution was added dropwise over 1 hour, and the mixture was stirred at room temperature for 3 hours. Thereafter, it was left at room temperature for 12 hours. Using an evaporator, heat in a 50 ° C water bath and pressure 7
The alcohol produced by the reaction and the remaining water were distilled off at kPa. The average molecular weight of weight in terms of polystyrene obtained by gel permeation chromatography (GPC) was 800.

<Synthesis Examples 2-5>
Synthesis was performed in the same manner as in Synthesis Example 1 except that the silicon compound and propylene glycol monomethyl ether acetate were used in the amounts shown in Table 2.

<Synthesis Example 6>
Phenyltrimethoxysilane (34.3 g, 0.173 mol) and p-styryltrimethoxysilane (9.7 g, 0.043 mol) were added to a three-necked flask equipped with a thermometer and a condenser tube. At room temperature, 11.7 g of diluted nitric acid prepared to a concentration of 0.25% by mass was added little by little. The mixture was stirred at room temperature for 30 minutes and then heated at 60 ° C. for 2 hours. Using an evaporator, it was heated in a 50 ° C. water bath, and methanol produced by the reaction was distilled off at a pressure of 7 kPa. Thereafter, 145.2 g of propylene glycol monomethyl ether acetate and 0.30 g of 1,1,3,3-tetrabutyl-1,3-dilauryloxydistanoxane were added and stirred at room temperature for 1 hour, then at 60 ° C. Heated for 2 hours. It was found by gel permeation chromatography (GPC) that the obtained polymer had a polystyrene-reduced weight average molecular weight of 1,400.

<Synthesis Example 7>
To a three-necked flask equipped with a thermometer and a condenser tube, p-styryltrimethoxysilane (8.4 g, 0.037 mol) and 5.0 g of propylene glycol monomethyl ether acetate were added. 2.3 g of diluted nitric acid prepared to 25 mass% was added little by little. After stirring at room temperature for 30 minutes, the mixture was heated at 60 ° C. for 3 hours. Thereafter, 55.0 g of propylene glycol monomethyl ether acetate was added, and the methanol produced by the reaction was distilled off by heating in a water bath at 50 ° C. using an evaporator at a pressure of 7 kPa. It was found by gel permeation chromatography (GPC) that the obtained polymer had a polystyrene-equivalent weight average molecular weight of 1,200.

<Synthesis Example 8>
In a three-necked flask equipped with a thermometer and a condenser tube, p-styryltrimethoxysilane (1.38 g, 0.006 mol), phenyltrimethoxysilane (2.45 g, 0.012 mol), diphenyldimethoxysilane (3.02 g, 0 0.012 mol) and 45 g of propylene glycol monomethyl ether acetate, and 1.45 g of dilute nitric acid prepared to a concentration of 0.25% by mass at room temperature were added little by little while stirring with a stirrer. After stirring at room temperature for 30 minutes, the mixture was heated at 60 ° C. for 3 hours. Using an evaporator, it was heated in a 50 ° C. water bath, and methanol produced by the reaction was distilled off at a pressure of 7 kPa. The weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) was 900.

<Synthesis Example 9>
To a three-necked flask equipped with a thermometer and a condenser tube, p-styryltrimethoxysilane (2.24 g, 0.01 mol) and 1.02 g of dilute nitric acid having a concentration of 0.25% by mass were added and stirred at room temperature for 6 hours. . 6.40 g of methyl isobutyl ketone, 0.11 g of sodium carbonate and 4.0 g of water were added, and the mixture was further stirred at room temperature for 96 hours. The organic phase was washed with water until neutral, and then the organic phase was concentrated using an evaporator. This was reprecipitated in methanol to recover a white solid, which was dried under vacuum for 6 hours. It was found by gel permeation chromatography (GPC) that the obtained polymer had a weight average molecular weight in terms of polystyrene of 8,900.

<Measurement method of etching rate>
A small piece of glass was affixed on the cured thin film, and an etching process was performed with a reactive ion etching apparatus under the following conditions. The glass piece was removed, and the thin film portion protected by the glass piece and the etched thin film portion step were measured.

Etching rate (nm / sec) = step difference (nm) ÷ processing time (sec)
Conditions for reactive ion etching Etching gas: Carbon tetrafluoride Pressure: 0.5 Pa
Gas flow rate: 20sccm
Plasma voltage: 100W
Bias voltage: 100W
Processing time: 20 sec
[Example 1]
The polymerization initiator 1,1-di (t-hexylperoxy) -3,3 was added to the solution synthesized in Synthesis Example 9.
, 5-Trimethylcyclohexane (Perhexa TMH, manufactured by Nippon Oil Chemical Co., Ltd.) was added to and dissolved in 100 parts of solid content, and then filtered through a 0.2 μm filter, and 0.5 ml was placed in a spin coater. It was dripped on the set glass substrate. A thin film was formed on the glass substrate by rotating the glass substrate at 500 rpm for 5 seconds, then rotating at 3000 rpm for 2 seconds, and further rotating at 5000 rpm for 20 seconds. The glass substrate coated with the resin was heated at 120 ° C. for 1 hour under a nitrogen stream, and further heated at 250 ° C. for 1 hour. The reactive ion etching rate with CF ₄ gas of the obtained resin thin film was measured.

[Examples 2 to 9] [Comparative Examples 1 to 3]
Using a solution prepared with the composition shown in Table 3, the CF ₄ etching rate was measured in the same manner as in Example 1.

Table 4 shows the relationship between the mass fraction of the aromatic ring and the etching rate. The etching rate is a ratio when the etching rate of Comparative Example 2 is 1, and is shown as an etching rate ratio. When the etching rate is low, the etching resistance is high. That is, in the present invention, the etching rate ratio is 1
A smaller value means higher etching resistance.

Claims (12)

A silicon compound represented by the following formula (1a), or
One or more silicon compounds selected from the group consisting of a silicon compound represented by the following formula (1a), a silicon compound represented by the following formula (1b) and a silicon compound represented by the following formula (1c); The silicon compound which has an aromatic ring and a vinyl group obtained by condensing after condensing the mixture containing this.
R ^1a Si (OR ² ) ₃ (1a)
(In formula (1a), R ^1a represents a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.)
R ^1b Si (OR ³ ) ₃ (1b)
(In formula (1b), R ^1b represents an alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an unsaturated aliphatic residue having 2 to 14 carbon atoms, and R ³ represents 1 carbon atom. Represents an alkyl group of ˜4.)
R ^1c R ^1d Si (OR ⁴ ) ₂ (1c)
(In the formula (1c), R ^1c and R ^1d are an aromatic ring having 6 to 20 carbon atoms, a hydrocarbon group having a structure in which a vinyl group is bonded to an aromatic ring having 6 to 20 carbon atoms, An unsaturated aliphatic residue or an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms. In the formula (1a), R ^1a is an aryl group having 8 to 14 carbon atoms having a phenyl group to which a vinyl group is bonded or an aryl group having 12 to 14 carbon atoms having a naphthyl group to which a vinyl group is bonded;
In the formula (1b), R ^1b is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
In the formula (1c), R ^1c and R ^1d are each independently an aryl group having 8 to 14 carbon atoms having a phenyl group to which a vinyl group is bonded and a 12 to 14 carbon atoms having a naphthyl group to which a vinyl group is bonded. The silicon compound having an aromatic ring and a vinyl group according to claim 1, which is an aryl group, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. In the formula (1a), R ^1a is a styryl group, in the formula (1b), R ^1b is a methyl group or a phenyl group, and in the formula (1c), R ^1c and R ^1d are a methyl group or a phenyl group. A silicon compound having an aromatic ring and a vinyl group according to claim 1 or 2. Content of an aromatic ring is 40 mass% or more, The silicon compound which has an aromatic ring and vinyl group which have a vinyl group in any one of Claims 1-3. Content of an aromatic ring is 60 mass% or more, The silicon compound which has an aromatic ring and vinyl group in any one of Claims 1-3.   (A) A curable composition containing the aromatic ring and vinyl group-containing silicon compound according to any one of claims 1 to 5, (B) a heat or ultraviolet radical polymerization initiator, and (D) an organic solvent as required. Resin composition.   (C) The curable resin composition of Claim 6 which further contains the compound which has a vinyl group.   (A) A silicon compound having an aromatic ring and a vinyl group according to any one of claims 1 to 5, (E) a silicon compound having a Si-H bond, and (D) an organic solvent and (F) if necessary A curable resin composition containing a Pt compound.   (C) The curable resin composition of Claim 8 which further contains the compound which has a vinyl group.   The curable resin composition according to any one of claims 6 to 9, wherein the content of the aromatic ring in the composition is 40% by mass or more.   The curable resin composition according to any one of claims 6 to 9, wherein the content of the aromatic ring in the composition is 60% by mass or more.   A cured product obtained by curing the curable resin composition according to claim 6 with heat or ultraviolet rays.