JP2003122016A - Photocurable organopolysiloxane composition - Google Patents

Abstract

(57) Abstract: A photocurable organopolysiloxane composition which can be obtained practically and economically, using already industrialized raw materials, and having sensitivity, resolution and storage stability. Provided is a photocurable organopolysiloxane composition having excellent heat resistance, low adhesiveness in an uncured state after application, and excellent heat resistance after curing. (A) An average molecular weight obtained by substituting a trialkylsiloxy group for a silanol group contained in a cohydrolyzed polycondensation product of (meth) acryloyloxypropyltrimethoxysilane and phenyltrimethoxysilane, For example, if the weight average molecular weight is 3,000-100,0
A photocurable organopolysiloxane composition containing (meth) acryloyloxyl group-containing organopolysiloxane having a value of 00 (in terms of polystyrene by GPC) and (B) a photosensitizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable organopolysiloxane composition which is useful as a photosensitive heat-resistant material for semiconductors which is used, for example, in semiconductor pattern formation and passivation.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive heat-resistant material for semiconductors, a silicone ladder polymer-based photosensitive heat-resistant material (JP-A-60-108839, JP-A-60-1088).
40, JP-A-60-108841, JP-A-59-193925, JP-A-60-76739, JP-A-60-80851, etc.), but the sensitivity is known. Is low and the manufacturing process is complicated, which is not practical.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocurable organopolysiloxane composition which can be obtained practically and economically, and which uses already industrialized raw materials and has sensitivity, It is an object of the present invention to provide a photocurable organopolysiloxane composition which is excellent in resolution and storage stability, has little tackiness in an uncured state after coating, and has excellent heat resistance after curing.

[0004]

The first aspect of the present invention is (A)
Average composition formula (1): (CH ₂ = CR ¹ COOC ₃ H _6- ) _a (Ph) _b R ² _c (R ³ ₃ SiO) _d SiO _{(4-abcd) / 2} (1) (wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms, Ph represents a phenyl group, and R ³ represents 1 to 1 carbon atoms. 8 represents an alkyl group having 8 or an alkenyl group having 1 to 8 carbon atoms, and a satisfies 0.05 <a <0.9,
b satisfies 0.1 <b <0.9, and c satisfies 0 ≦ c <0.2
Is satisfied, d satisfies 0 <d ≦ 0.5, and 0.8 ≦
a (meth) acryloyloxyl group-containing organopolysiloxane having an average molecular weight of 3,000 to 100,000 (polystyrene conversion value by GPC), and a + b + c + d ≦ 1.5.

(B) A photocurable organopolysiloxane composition containing a photosensitizer. A second aspect of the present invention is a method for producing a cured product, which comprises irradiating the photocurable organopolysiloxane composition with light to cure the composition.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

(A) Component (meth) acryloyloxyl
Group-Containing Organopolysiloxane The (A) component (meth) acryloyloxyl group-containing organopolysiloxane used in the present invention is represented by the general formula (1), and is generally an organopolysiloxane having a branched structure. In the formula (1), a represents the proportion of a (meth) acryloyloxyl group which plays an important role in showing the photosensitivity of the composition, and 0.05 <a <0.9.
And b represents the amount of phenyl groups that impart heat resistance to the obtained cured product, satisfying 0.1 <b <0.9, c satisfying 0 ≦ c <0.2, and d Satisfies 0 <d ≦ 0.5, preferably 0 <d ≦ 0.1, and 0.8 ≦ a + b + c
+ D ≦ 1.5, preferably 1 ≦ a + b + c + d ≦ 1.1
Is a number that satisfies.

The (meth) acryloyloxyl group-containing organopolysiloxane has an average molecular weight, for example, a weight average molecular weight of 3,000 to 100,000 (polystyrene equivalent by GPC), and preferably 5,000 to.
It is 50,000 (polystyrene conversion value by GPC). If this average molecular weight is too small, the surface tack in the unhardened state may easily remain after coating the composition of the present invention. On the other hand, if it is too large, the component (A) may be difficult to dissolve in the solvent. This (meth) acryloyloxyl group-containing organopolysiloxane can be prepared, for example, by the following general formula (2):

CH ₂ ═CR ¹ COO—C ₃ H ₆ —Si (OR ⁴ ) ₃ (2) (In the formula, R ¹ is the same as defined above, and R ⁴ represents an unsubstituted or alkoxy-substituted alkyl group.) And a (meth) acryloyloxypropyltrialkoxysilane represented by the following general formula (3) in an amount of 0.7 to 20 mol per mol of the silane:

PhSi (OR ⁵ ) ₃ (3) (wherein Ph is the same as above, R ⁵ represents an unsubstituted or alkoxy-substituted alkyl group) and optionally a phenyltrialkoxysilane For example, a general formula (4) having an amount of 0 to 4 mol per mol of the silane of the general formula (2) (in the composition formula (1), it is preferable that R ² is not much):

An organotrialkoxysilane represented by R ² Si (OR ⁶ ) ₃ (4) (wherein R ² is the same as defined above, R ⁶ represents an unsubstituted or alkoxy-substituted alkyl group), for example, It is obtained by subjecting an alkyltrialkoxysilane and an alkenyltrialkoxysilane to cohydrolysis and polycondensation to convert the silanol group contained in the obtained polycondensation product into a trialkylsiloxy group.

[0011] The alkyl or alkenyl group having 1 to 8 carbon atoms represented by R ³ in the general formula (1) or (4) R ² and general formula (1), for example, a methyl group, an ethyl group , Propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, cyclohexyl group, cycloheptyl group, octyl group, α-ethylhexyl group,
Examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group and a butenyl group. Of these, a methyl group is preferable.

The unsubstituted or alkoxy-substituted alkyl group represented by R ⁴ in the general formula (2) generally has 1 carbon atom.
To 12 and preferably those having 1 to 4 carbon atoms, and examples of such an unsubstituted or alkoxy-substituted alkyl group include a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, Examples thereof include ethoxyethyl group. Of these, a methyl group is preferable.

Examples of the unsubstituted or alkoxy-substituted alkyl group represented by R ⁵ in the general formula (3) include the same as the unsubstituted or alkoxy-substituted alkyl group represented by R ⁴ . Examples of the unsubstituted or alkoxy-substituted alkyl group represented by R ⁶ in the general formula (4) include those similar to the unsubstituted or alkoxy-substituted alkyl group represented by R ⁴ .

In the above manufacturing method, first, the general formula (2) is used.
The (meth) acryloyloxypropyltrialkoxysilane and the phenyltrialkoxysilane of the general formula (3) in a molar ratio of silane of the general formula (2): silane of the general formula (3) 1: 0.7 to 20, Preferably, from 1: 1 to 5,
The cohydrolysis reaction is preferably carried out in the presence of an acid catalyst to obtain a cohydrolysis condensate having a silanol group.

Specific examples of the (meth) acryloyloxypropyltrialkoxysilane represented by the general formula (2) include acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane and acryloyloxypropyltripropoxysilane. , (2-methyl) acryloyloxypropyltrimethoxysilane, (2-methyl) acryloyloxypropyltriethoxysilane, acryloyloxypropyltri (methoxyethoxy) silane and the like.

Specific examples of the phenyltrialkoxysilane represented by the general formula (3) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane and the like.

Specific examples of the organotrialkoxysilane represented by the general formula (4) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane,
Examples thereof include ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, vinyltriethoxysilane, and vinyltri (methoxyethoxy) silane. The above-mentioned cohydrolysis is preferably carried out in the presence of an acid catalyst.
As the acid catalyst, known acid catalysts such as inorganic acids and organic acids can be used, and specific examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as acetic acid and oxalic acid.
Of these, hydrochloric acid is preferred.

The amount of the acid catalyst used is determined by the above general formula (2),
It is usually 0.001 to 1.0 part by weight based on 100 parts by weight of the total amount of the alkoxysilanes represented by (3) and (4). Co-hydrolysis may be normally performed at 0 to 50 ° C.
The cohydrolyzate thus obtained is then subjected to polycondensation. The conditions of this polycondensation reaction are as shown in the general formula (1)
Is important in controlling the molecular weight of the organopolysiloxane. The reaction temperature is preferably 50 to 100 ° C, particularly preferably 80 to 100 ° C.

The reaction time is preferably 30 minutes or more under the above reaction temperature conditions. In particular, in order to obtain the organopolysiloxane having an average molecular weight, for example, a weight average molecular weight of 3,000 or more (polystyrene-equivalent value by GPC), the silanol groups produced by the above cohydrolysis and the alkoxy remaining after the cohydrolysis are used. The groups need to be polycondensed under the above reaction conditions. In the co-hydrolyzed polycondensation product obtained through the co-hydrolysis and poly-condensation in this way, the alkoxy groups have almost completely disappeared, but some silanol groups remain unreacted. .

In the next silylation step of the co-hydrolyzed polycondensate, the co-hydrolyzed polycondensate is reacted with a silylating agent to silylate the remaining silanol groups. Examples of the silylating agent include the following general formula (5): R ⁷ ₃ Si—NH—SiR ⁷ ₃ (5) (In the formula, R ⁷ is independently an alkyl group having 1 to 8 carbon atoms or a carbon atom. Hexaorganodisilazane represented by the formula 1 to 8), for example, hexaalkyldisilazane, tetraalkyldialkenyldisilazane, tetraalkenyldialkyldisilazane, and the like. Examples of the alkyl or alkenyl group having 1 to 8 carbon atoms represented by R ⁷ in the general formula (5) include those similar to the above R ² and R ^3, and preferably a methyl group and a vinyl group. Specific examples of the hexaorganodisilazane of the general formula (5) include hexamethyldisilazane, tetramethyldibutyldisilazane, hexaethyldisilazane, tetramethyldivinyldisilazane, tetravinyldimethyldisilazane and the like. Examples of the silylating agent other than the general formula (5) include N-trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide, N-trimethylsilylimidazole and the like. Among the above silylating agents, hexaalkyldisilazane, especially hexamethyldisilazane is preferred.

This silylation reaction is usually carried out in an organic solvent, and examples of such an organic solvent include methyltributylketone, toluene, xylene and the like.
The amount of the silylating agent to be used cannot be unconditionally determined depending on the amount of silanol groups remaining in the cohydrolyzed polycondensate, but is usually preferably 5% by weight or more based on the cohydrolyzed polycondensate. The temperature of the silylation reaction is preferably 80 ° C. or higher, particularly preferably 80 to 160 ° C., and the reaction time may be about 0.5 to 3 hours. By this silylation, the silanol group remaining in the cohydrolysis condensate is almost completely converted to a trialkylsiloxy group and becomes inactive.

Thus, the (meth) acryloyloxyl group-containing organopolysiloxane represented by the general formula (1) is obtained. The (meth) acryloyloxyl group-containing organopolysiloxane has low hydrophilicity and high lipophilicity because the silanol group does not remain in the molecule, so it can be easily washed by washing with water in a state of being dissolved in an organic solvent immiscible with water. Water-soluble impurities can be removed. Therefore, high purification is easy, and since it does not contain a silanol group, it has excellent storage stability. Further, it has excellent curability, and has little tackiness in an uncured state after application.

(B) Component Photosensitizer Examples of the (B) component photosensitizer used in the present invention include 2,6-bis (p-azidobenzal) -4-tert-
Amir cyclohexanone, 2,6-bis (p-azidobenzal) -4-methylcyclohexanone, 4,4'-
Bisazide compounds such as diazidobenzalacetone; 3,
3-carbonylbis (7-diethylaminocoumarin),
Coumarin-based dyes such as 6-methylcoumarin; benzophenone and derivatives thereof, for example, tetra (tert-butylperoxycarbonyl) benzophenone; benzoin,
And derivatives thereof, for example, benzoin ethyl ether, benzoin methyl ether, and the like. Among them, 2,6-bis (p-azidobenzal)-is preferable.
4-tert-amylcyclohexanone, 3,3-carbonylbis (7-diethylaminocoumarin), tetra (te
rt-butylperoxycarbonyl) benzophenone and benzophenone.

The amount of the photosensitizer as the component (B) is 0.0001 based on 100 parts by weight of the (meth) acryloyloxyl group-containing organopolysiloxane as the component (A).
-20 parts by weight is preferable, and 0.1-1 is more preferable.
0 parts by weight.

Other Components In addition to the components (A) and (B) described above, the photocurable organopolysiloxane composition of the present invention may optionally contain a solvent,
For example, hydroquinone monomethyl ether, 2,6-
A polymerization inhibitor such as di (tert-butyl) -4-methylphenol and other additives usually used in photocurable organopolysiloxane compositions can be added.

Examples of the solvent include toluene, xylene, methyl isobutyl ketone, 1-methoxy-2-
Propanol and the like can be mentioned. The amount of the solvent used is preferably 40 to 80% by weight based on the whole composition.

Photocurable Organopolysiloxane Composition The composition of the present invention can be obtained by uniformly mixing the components (A) and (B) and other necessary components.

The composition of the present invention thus obtained is used, for example, as follows. That is, a predetermined substrate is coated with a coating device such as a spinner, and the solvent contained in the composition is air-dried, preferably 0.1 to 10 μm.
After forming the composition film of (the thickness after drying), a mask aligner or the like is used, and the surface of the composition film is shielded directly or with a photomask, and then the composition film is irradiated with light to form a film of the composition film. Cure the exposed areas. Examples of the light to be irradiated include ultraviolet rays such as deep ultraviolet rays (wavelengths: examples 193 nm and 253 nm), i rays (wavelength: 365 nm), g rays (wavelength: 436 nm), h rays (wavelength: 405 nm).

The uncured composition coating film shielded by the photomask can be dissolved and removed using a solvent such as methyltributylketone to form a pattern corresponding to the photomask. When the composition film is used for passivation of a semiconductor, it is preferable that the volatile components such as a solvent remaining in the cured composition film are completely heated by heating at 200 ° C. to 300 ° C. for 1 to 4 hours. A film having excellent heat resistance and adhesiveness is obtained.

[0030]

EXAMPLES The present invention will be described more specifically below by showing Examples and Comparative Examples. In addition, in this example, an average molecular weight is a polystyrene conversion value by GPC (gel permeation chromatograph), and symbol M _W means a weight average molecular weight.

Example 1 Acryloyloxypropyltrimethoxysilane ()
468 parts by weight, and phenyltrimethoxysilane ()
Charge 792 parts by weight to the flask (molar ratio of: =
1: 2), and a solution obtained by mixing 534.2 parts by weight of water and 2 parts by weight of hydrochloric acid (36% by weight) as an acid catalyst was added dropwise with stirring over 10 minutes to carry out a hydrolysis reaction. Next, the reaction mixture was heated to 100 ° C., and a condensation polymerization reaction was carried out for 5 hours while distilling off methyl alcohol produced as a by-product.

Next, after dissolving the obtained hydrolyzed polycondensate in methyltributylketone, the hydrolyzed polycondensate 1
25 parts by weight of hexamethyldisilazane were added to 00 parts by weight and heated at 100 ° C. for 1 hour. Then, methyltributylketone was distilled off under reduced pressure at 100 ° C./5 mmHg to obtain a (meth) acryloyloxyl group-containing organopolysiloxane as the component (A) as a resinous solid.
Incidentally, the (meth) acryloyl Luo hexyl group containing an average molecular weight of the organopolysiloxane (M _W) results were measured was 7,000.

Next, 100 parts by weight of the obtained (meth) acryloyloxyl group-containing organopolysiloxane,
(B) Component 2,6-bis (p-azidobenzal) -4
A solution obtained by dissolving 5 parts by weight of -tert-amyl cyclohexanone in 233.4 parts by weight of methyl isobutyl ketone was filtered through a membrane filter having a pore size of 0.5 μm to obtain a composition of the present invention. The obtained composition was applied onto a silicon wafer by a spin coating method and air-dried to form a composition coating film having a film thickness of 2.5 μm. The composition coating was not tacky in the uncured state.

Using a mask aligner, a photomask on which a pattern was previously formed according to the semiconductor circuit was brought into close contact with this composition film, exposed (180 mJ), and developed with xylene to give a thick film on a silicon wafer. Saga is 1.
A resolution pattern of 20 μmL / S was obtained at 8 μm. The 20 μmL / S resolution pattern means a striped pattern in which a composition film having a width of 20 μm and a space having a width of 20 μm are alternately arranged on a silicone wafer (hereinafter the same).

Example 2 Acryloyloxypropyltrimethoxysilane ()
468 parts by weight, and phenyltrimethoxysilane ()
Charge 594 parts by weight to the flask (molar ratio of: =
1: 5), a solution in which 446 parts by weight of water and 1.7 parts by weight of hydrochloric acid (36% by weight) as an acid catalyst were mixed was added dropwise to carry out a hydrolysis reaction. Next, this was heated to 80 ° C., and a condensation polymerization reaction was carried out while distilling off methyl alcohol produced as a by-product.

Next, the obtained hydrolysis-condensation polymer is dissolved in methyltributylketone, and then the hydrolysis-condensation polymer 1
Hexamethyldisilazane (25 parts by weight) was added to 100 parts by weight, and the mixture was heated at 100 ° C. for 1 hour, and then methyl tributyl ketone was distilled off under reduced pressure at 100 ° C. and 5 mmHg to obtain a resinous solid (A) component. Thus, (meth) acryloyloxyl group-containing organopolysiloxane was obtained. The average molecular weight (M _W ) of this (meth) acryloyloxyl group-containing organopolysiloxane was measured.
It was 000.

Next, 100 parts by weight of the obtained acryloxy group-containing organopolysiloxane, 4 parts by weight of tetra (tert-butylperoxycarbonyl) benzophenone as the component (B) and 3,3-carbonylbis (7-diethylaminocoumarin). ) 0.005 parts by weight was dissolved in 233.4 parts by weight of methyl isobutyl ketone, and the solution was filtered through a membrane filter having a pore size of 0.5 μm to obtain a composition of the present invention.

The composition obtained was applied onto a silicon wafer by a spin coating method and air-dried to give a film thickness of 2.5.
A μm composition coating was formed. The composition coating was not tacky in the uncured state. Using a mask aligner, a photomask on which a pattern was previously formed according to a semiconductor circuit was brought into close contact with this composition film and exposed (7
08 mJ), developed using methyl isobutyl ketone,
20μmL with 1.7μm thickness on silicon wafer
A resolution pattern of / S was obtained.

Example 3 Hydrolysis and polycondensation were carried out in the same manner as in Example 2 to obtain a hydrolyzed polycondensate.

The resulting hydrolyzed polycondensate was treated with hexamethyldisilazane in the same manner as in Example 1 to obtain the (meth) acryloyloxyl group-containing organopolysiloxane as the component (A). . The average molecular weight (M _W ) of this (meth) acryloyloxyl group-containing organopolysiloxane was measured and found to be 12,000.
Met.

Next, 100 parts by weight of this (meth) acryloyloxyl group-containing organopolysiloxane was dissolved in 200 parts by weight of toluene, and this was dissolved in 2 parts by weight of 600 parts by weight of pure water.
It was washed with water twice. The electric conductivity of the separated wastewater at this time was measured and found to be 3 μs / cm.

Next, the toluene solution of the organopolysiloxane containing (meth) acryloyloxyl group washed with water was purified by azeotropic dehydration and toluene distillation. Next, 100 parts by weight of the (meth) acryloyloxyl group-containing organopolysiloxane thus purified, 4 parts by weight of tetra (tert-butylperoxycarbonyl) benzophenone as the component (B), and 3,3-carbonylbis (7- Diethylaminocoumarin) 0.005 parts by weight was dissolved in 233.4 parts by weight of methyl isobutyl ketone, and the solution was filtered through a membrane filter having a pore size of 0.5 μm to obtain a composition of the present invention. As a result of measuring the impurity concentration in this composition, Na ⁺ is 1 ppm or less, K ⁺ is 1 ppm or less,
Cl ⁻ was 1 ppm or less. The obtained composition was applied onto a silicon wafer by a spin coating method and air-dried to form a composition coating film having a film thickness of 2.5 μm. The composition coating was not tacky in the uncured state.

A photomask on which a pattern was previously formed according to a semiconductor circuit was adhered to this composition film by using a mask aligner, and after exposure (708 mJ), methyl isobutyl ketone was used to form the composition film. The cured part is dissolved and removed, and the thickness is 1.7 on the silicon wafer.
In μm, a resolution pattern of 20 μmL / S was obtained.

Comparative Example 1 Acryloyloxypropyltrimethoxysilane ()
468 parts by weight, and phenyltrimethoxysilane ()
Charge 198 parts by weight into a flask (molar ratio of: =
1: 0.5), and a solution prepared by mixing 334 parts by weight of water and 1.3 parts by weight of hydrochloric acid (36% by weight) as an acid catalyst was added dropwise to carry out the hydrolysis reaction. Next, the reaction liquid was heated to 80 ° C., and a condensation polymerization reaction was performed while distilling off methyl alcohol produced as a by-product.

Next, after dissolving the obtained hydrolyzed polycondensate in methyl isobutyl ketone, the hydrolyzed polycondensate 1
Hexamethyldisilazane (25 parts by weight) was added to 100 parts by weight, the mixture was heated at 100 ° C. for 1 hour, and then methyl isobutyl ketone was distilled off under reduced pressure at 100 ° C./5 mmHg to obtain a highly viscous resin. This resin is sticky,
It was unsuitable as a photocurable organopolysiloxane composition using a photomask. The average molecular weight (M _W ) of this resin was measured and found to be 9,000.

Comparative Example 2 The same composition as in Example 1, that is, 468 parts by weight of acryloyloxypropyltrimethoxysilane () and 792 parts by weight of phenyltrimethoxysilane () were charged in a flask (molar ratio = 1: 2), water 53
4.2 parts by weight and hydrochloric acid (36% by weight) as acid catalyst 2
A solution obtained by mixing parts by weight was added dropwise under stirring for 10 minutes to carry out a hydrolysis reaction. The reaction mixture is then added to 1
The mixture was heated to 00 ° C., and a condensation polymerization reaction was carried out for 1 hour while distilling off by-produced methyl alcohol.

Next, after dissolving the obtained hydrolyzed polycondensation product in methyltributylketone, the hydrolyzed polycondensation product 1
Hexamethyldisilazane (25 parts by weight) was added to 00 parts by weight, and the mixture was heated at 100 ° C. for 1 hour, and then methyltributylketone was distilled off under reduced pressure at 100 ° C./5 mmHg to obtain a high-viscosity starch syrup-like resin. This resin was tacky and was unsuitable as a photocurable organopolysiloxane composition using a photomask. The average molecular weight (M _W ) of this resin was measured and found to be 2,000.

Comparative Example 3 The same composition as in Example 1, that is, 468 parts by weight of acryloyloxypropyltrimethoxysilane () and 792 parts by weight of phenyltrimethoxysilane () were charged into a flask (molar ratio of 1: = 1. 2), water 53
4.2 parts by weight and hydrochloric acid (36% by weight) as acid catalyst 2
A solution obtained by mixing parts by weight was added dropwise under stirring for 10 minutes to carry out a hydrolysis reaction.

Then, the reaction mixture was heated to 100 ° C., the methyl alcohol produced as a by-product was distilled off, and the temperature was further raised to carry out a polycondensation reaction at 150 ° C. for 10 hours. Next, it was tried to dissolve the obtained hydrolyzed condensate in methyltributylketone, but it was difficult to uniformly dissolve the condensate. Result 1 of measuring the average molecular weight (M _W ) of the condensate
It was 10,000.

Comparative Example 4 Acryloyloxypropyltrimethoxysilane ()
468 parts by weight, and phenyltrimethoxysilane ()
Charge 9900 parts by weight to the flask (molar ratio of: =
1:25), a solution prepared by mixing 4450 parts by weight of water and 16.6 parts by weight of hydrochloric acid (36% by weight) as an acid catalyst was added dropwise with stirring over 10 minutes to carry out a hydrolysis reaction.
Next, the reaction mixture was heated to 100 ° C., and a condensation polymerization reaction was carried out for 5 hours while distilling off methyl alcohol produced as a by-product.

Next, the resulting hydrolyzed condensate was dissolved in methyltributylketone, and then the hydrolyzed polycondensation product 100 was prepared.
25 parts by weight of hexamethyldisilazane was added to parts by weight and heated at 100 ° C. for 1 hour. Then, methyl tributyl ketone was distilled off under reduced pressure at 100 ° C./5 mmHg to obtain a resin solid. The average molecular weight (M _W ) of the resin solid matter was measured and found to be 6,000.

Next, 100 parts by weight of the obtained resin solid and 2,6-bis (p-azidobenzal) -4-tert-
A solution of 5 parts by weight of Amir cyclohexanone and 233.4 parts by weight of methyl isobutyl ketone was dissolved in a solution having a pore size of 0.
It was filtered with a 5 μm membrane filter to obtain a photocurable composition. The obtained photocurable composition was applied on a silicon wafer by a spin coating method and air-dried to form a composition coating film having a film thickness of 2.5 μm. This composition coating was not tacky in the uncured state.

A mask aligner was used for this composition film, and a photomask on which a pattern was previously formed according to the circuit of the semiconductor was brought into close contact with the composition, exposed to light (708 mJ), and developed with xylene. Due to low photosensitivity and insufficient curing, the composition coating film was dissolved in xylene and a pattern corresponding to the photomask could not be obtained on the silicon wafer.

Storage stability test of the present invention The composition obtained in Example 2 was sealed in a container and kept at 5 ° C. and 25 ° C.
It was stored at 40 ° C. and 40 ° C., and the change in viscosity (cSt) with time was measured. The results are shown in Fig. 1. In addition, in FIG. 1, the vertical axis represents
It is the viscosity (cSt) of the composition at 25 ° C., and the horizontal axis is the storage period (days).

Heat Resistance Test The cured products of the compositions obtained in Examples 1 and 2 were treated with a thermobalance at 300 ° C. for 4 hours, and the weight loss during that time was measured over time. The results are shown in Figure 2.

[0056]

The composition of the present invention is excellent in sensitivity, resolution and storage stability, has little tackiness in an uncured state after coating, and has excellent heat resistance after curing. This composition is useful as a photosensitive heat-resistant material for semiconductor lithography and a photosensitive heat-resistant material for semiconductor passivation.

[Brief description of drawings]

FIG. 1 is a graph showing the results of a storage stability test.

FIG. 2 is a graph showing the results of a heat resistance test.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tsutomu Kashiwagi             Gunma Prefecture Usui District, Matsuida Town             Shin-Etsu Chemical Co., Ltd. Silicone electronic materials             Inside the technical laboratory (72) Inventor Shinsuke Yamaguchi             Gunma Prefecture Usui District, Matsuida Town             Shin-Etsu Chemical Co., Ltd. Silicone electronic materials             Inside the technical laboratory F term (reference) 2H025 AA01 AA02 AA10 AA11 AB16                       AC01 AD01 BC14 BC78 BC83                       CA00                 4J027 AF05 CB10 CC03 CD10                 4J035 BA11 BA12 CA01M CA01U                       CA05U CA051 CA14U CA141                       FB05 FB07 FB10 GA02

Claims (2)

[Claims] (A) The following general formula (2): CH ₂ = CR ¹ COO-C ₃ H ₆ -Si (OR ⁴ ) ₃ (2) (In the formula, R ¹ represents a hydrogen atom or a methyl group. , R ⁴ represents an unsubstituted or alkoxy-substituted alkyl group) and a (meth) acryloyloxypropyltrialkoxysilane represented by the following general formula (3): PhSi ( OR ⁵ ) ₃ (3) (in the formula, Ph represents a phenyl group, R ⁵ represents an unsubstituted or alkoxy-substituted alkyl group) and optionally a phenyltrialkoxysilane represented by the general formula (2) Of the following general formula (4): R ² Si (OR ⁶ ) ₃ (4) (wherein R ² is an alkyl group having 1 to 8 carbon atoms or 1 carbon atom). indicates 8 alkenyl group, R ⁶ is unsubstituted or Al And organotrialkoxysilane represented by showing a carboxy substituted alkyl group), subjected to cohydrolysis and polycondensation, a silanol group contained in the polycondensation product obtained by the following general formula (6): R ⁷ ₃ SiO- (6) (wherein, R ⁷ independently represents an alkyl group or an alkenyl group having 1 to 8 carbon atoms), and an average molecular weight of 3,000 to 100,000 (GP
A photocurable organopolysiloxane composition comprising a (meth) acryloyloxyl group-containing organopolysiloxane (in terms of polystyrene by C) and (B) a photosensitizer. 2. A cured product obtained by irradiating the composition of claim 1 with light to cure it.