KR20090113183A - Polyorganosiloxane compound, resin composition comprising the same, and pattern forming method thereof - Google Patents

Abstract

PURPOSE: A polyorganosiloxane compound is provided to obtain good film characteristics and high reliability as a protective coating so that they are widely applicable for the protection of various circuit boards. CONSTITUTION: A polyorganosiloxane compound has the average compositional formula (1): R1aSi(OR2)b(OH)cO(4-a-b-c)/2 which is modified such that some hydrogen atoms of silicon-bonded hydroxyl groups are substituted by acid labile groups of the general formula (2) and/or are crosslinked within the molecule or between molecules with a crosslinking group having a C-O-C linkage represented by the general formula (3), the polyorganosiloxane compound having a weight average molecular weight of 300 to 200,000 as measured by GPC versus polystyrene standards.

Description

POLYORGANOSILOXANE COMPOUND, RESIN COMPOSITION COMPRISING THE SAME, AND PATTERN FORMING METHOD THEREOF}

The present invention relates to a novel polyorganosiloxane compound, a photosensitive resin composition and a thermosetting resin composition containing the same, and a pattern forming method. Protective films such as substrates, circuits, wirings, etc. using the above-described compositions are particularly suitable for insulating films for semiconductor devices, insulating films for semiconductor devices, insulating films for multilayer printed circuit boards, and solder protective films due to heat resistance, chemical resistance, insulation, and flexibility. Iii), it is useful for coverlay film, base adhesive film, etc.

It is known that siloxane polymers are excellent in dry etching resistance and plasma resistance conventionally, and the technique which uses a siloxane polymer as a resist material is also reported.

As an example, in a composition composed of an organosiloxane containing a large amount of silanol groups and a compound which generates an acid by light, the silanol group can be used as an alkali-soluble group, and the acid generated by light irradiation acts as a silanol condensation catalyst. , The light irradiation portion can be condensed and cured to form a negative pattern [Non-patent Document 1: Proc. SPIE 1672, 56 (1992).

On the other hand, as a positive resist material, it is also known that the organic polysiloxane whose main chain consists of siloxane bonds has a hydroxyl group in the organic group couple | bonded with the silicon, and some hydrogen atoms were substituted by the acid labile group. As an example, the resist resin composition (patent document 1: Unexamined-Japanese-Patent No. 11-60733) using polyorganosilsesquioxane which has an acid dissociative ester group in the side chain, and poly (2-hydroxycar A resist material (Patent Document 2: Japanese Patent No. 3175514) is proposed which contains a polymer in which the hydroxyl group of the carbonyl siloxane is partially protected by an acid dissociable group. However, resist materials using these conventional siloxane polymers do not sufficiently satisfy characteristics required for resist materials such as resolution, sensitivity, and developability.

In addition, as materials for forming interlayer insulating films and patterns currently used in LCD TFTs, properties such as high heat resistance, high transparency, low dielectric constant, solvent resistance, and the like are required. Conventionally, in order to realize these characteristics, the positive type thermosetting photosensitive material which combined the phenolic alkali-soluble resin, the quinonediazide compound, the thermosetting agent, and the acetate ester type solvent whose boiling point is 150 degrees C or less (patent document 3: Unexamined-Japanese-Patent application) No. 7-98502) or a positive photosensitive resin composition comprising a phenolic alkali-soluble resin, a quinonediazide compound, a crosslinking agent and a thermosensitive acid generator (Patent Document 4: Japanese Patent Application Laid-open No. 2004-240144 Publications). However, these materials may not have sufficient heat resistance or transparency or may be inferior in chemical resistance.

On the other hand, a photosensitive composition comprising a polysiloxane compound and a quinonediazide compound containing a siloxane unit derived from a product of a cycloaddition reaction, which is generally a material focused on the heat resistance and low dielectric constant characteristic of a siloxane polymer. (Patent Document 5: Japanese Patent No. 2648969), Positive type resist composition containing alkali-soluble siloxane aggregate and quinonediazide compound which has a phenolic hydroxyl group (Patent Document 6: Japanese Patent Application Publication No. 2003-255546) And photosensitive resin compositions (Patent Document 7: Japanese Patent Application Laid-open No. 2007-41361) containing a siloxane polymer, a quinonediazide compound, silica fine particles, and a solvent are proposed. However, these materials may be colored by decomposition of the quinonediazide compound contained in the thermosetting, which may lower the transparency of the cured film.

[Non-Patent Document 1] Proc. SPIE 1672, 56 (1992)

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-60733

[Patent Document 2] Japanese Patent No. 3175514

[Patent Document 3] Japanese Patent Application Laid-Open No. 7-98502

[Patent Document 4] Japanese Patent Application Publication No. 2004-240144

[Patent Document 5] Japanese Patent No. 2648969

[Patent Document 6] Japanese Patent Application Publication No. 2003-255546

[Patent Document 7] Japanese Patent Application Publication No. 2007-41361

The present invention relates to a polyorganosiloxane compound suitable as a base resin of a photosensitive resin composition to ultraviolet rays represented by g-ray, i-ray, KrF excimer laser or ArF excimer laser, a photosensitive resin composition and a thermosetting resin composition having high sensitivity and excellent process adaptability, and It is an object to provide a pattern formation method. In the thermosetting resin composition of the present invention, a fine pattern can be formed, and after the pattern is formed, a film excellent in transparency in the visible light region can be obtained by relatively low temperature heat treatment at around 200 ° C. Since it is excellent in the characteristic and reliability as a protective film, it can be applied widely for various board | substrate circuit protection.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the objective mentioned above, and, as a result, some hydrogen atoms of the hydroxyl group couple | bonded directly with the silicon atom contained in the polyorganosiloxane represented by the following average composition formula (1), the following general formula (2) Intramolecular or intermolecular crosslinked by a crosslinking group having a COC group represented by the following general formula (3) and / or substituted with an acid labile group represented by the, characterized in that the weight average molecular weight in terms of polystyrene standard in the measurement by The polyorganosiloxane compound which is -200,000 was found to be useful, and the present invention was completed.

Therefore, this invention provides the following polyorganosiloxane compound, the photosensitive resin composition, the thermosetting resin composition, and the pattern formation method.

[Claim 1]:

Some hydrogen atoms of the hydroxyl group directly bonded to the silicon atom contained in the polyorganosiloxane represented by the following average composition formula (1) are substituted with an acid labile represented by the following general formula (2) and / or the following general formula ( Polyorganosiloxanes which are crosslinked intramolecularly or intermolecularly by a crosslinking group having a COC group represented by 3) and have a weight average molecular weight of 300 to 200,000 in terms of a polystyrene standard measured by gel permeation chromatography (GPC). compound.

R ¹ _a Si (OR ² ) _b (OH) _c O _{(4-abc) / 2} ... … (One)

(In formula (1), R <^1> is 1 type, or 2 or more types of group chosen from a hydrogen atom or a C1-C18 organic group, and R <^2> is chosen from a C1-C6 linear or branched alkyl group. One or two or more groups having a range of 0.3 ≦ a ≦ 1.6, 0 ≦ b ≦ 0.3, and 0.001 ≦ c ≦ 2).

[Formula 1]

(In formula (2), R <^3> and R <^4> is a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group independently of each other, R <^5> is C1-C30 linear, branched or A cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ³ and R ⁴ , R ³ and R ⁵ , R ⁴ and R ⁵ are bonded to each other and a carbon atom to which they are bonded, or carbon A ring may be formed together with an atom and an oxygen atom, and in the case of forming a ring, R ³ , R ⁴ , and R ⁵ , which are involved in the formation of a ring, are a linear or branched alkylene group having 1 to 18 carbon atoms)

[Formula 2]

(In formula (3), R <^6> , R <^7> , R <^9> , R <^10> is a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group independently of each other, R <^6> , R <^7> , R <^9> And R ¹⁰ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. When the ring is formed, R ⁶ , R ⁷ , R ⁹ , and R ¹⁰ which are involved in the formation of a ring have 1 to 17 carbon atoms. Linear or branched alkylene group, R ⁸ is a divalent hydrocarbon group having 1 to 6 carbon atoms which may contain oxygen atoms)

[Claim 2]:

(A) the polyorganosiloxane compound according to claim 1, and

(B) a photo-acid-generating agent that generates an acid by light irradiation in the wavelength range of 150 to 450 nm.

Photosensitive resin composition comprising a.

[Claim 3]:

(A) the polyorganosiloxane compound according to claim 1,

(B) a light-induced acid generator that generates an acid by light irradiation in a wavelength range of 150 to 450 nm, and

(C) thermosetting agent

Thermosetting resin composition comprising a.

[Claim 4]:

(i) forming a resist film of the photosensitive resin composition according to claim 2 on a substrate,

(ii) exposing the resist film to light including a light source having a wavelength of 150 to 450 nm through a photomask;

(iii) developing the resist film after light exposure with an aqueous alkali solution developer;

Pattern forming method comprising a.

[Claim 5]:

(i) forming a resist film of the thermosetting resin composition according to claim 3 on a substrate,

(ii) exposing the resist film to light including a light source having a wavelength of 150 to 450 nm through a photomask;

(iii) developing the resist film after light exposure with an aqueous alkali solution developer;

(iiii) A step of curing the resist pattern film patterned by development at a temperature in the range of 100 to 50 ° C.

Pattern forming method comprising a.

By using the radiation-sensitive resin composition (photosensitive resin composition, thermosetting resin composition) of the present invention, a high resolution pattern can be formed, and the cured film obtained by thermal curing is heat resistant, transparent, and low dielectric constant. And since it is excellent in solvent resistance, it is used suitably as an interlayer insulation film for TFT substrates.

The polyorganosiloxane compound of this invention is the following average composition formula (1)

R ¹ _a Si (OR ² ) _b (OH) _c O _{(4-abc) / 2} ... … (One)

(In formula (1), R <^1> is 1 type or 2 or more types selected from a hydrogen atom or a C1-C18 organic group, R <^2> is 1 type chosen from a C1-C6 linear or branched alkyl group. Or two or more groups, and 0.3 ≦ a ≦ 1.6, 0 ≦ b ≦ 0.3, 0.001 ≦ c ≦ 2, especially 1 ≦ c ≦ 2).

It is synthesize | combined by making the compound represented by the precursor into a precursor, and then substituting a part of silanol group contained in polyorganosiloxane with an acid labile group. Hereinafter, the polyorganosiloxane before replacing with an acid labile group is called "precursor polysiloxane".

First, precursor polysiloxane is demonstrated. R ¹ in the average composition formula of the precursor polysiloxane is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, for example, a hydrogen atom; a methyl group, an ethyl group, and propyl. Alkyl groups such as group, butyl group, pentyl group, hexyl group, heptyl group, octyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and norbornyl group; alkenyl groups such as vinyl group and allyl group; phenyl group and naphthyl group Aryl groups such as chloromethyl group, γ-chloropropyl group, halogen substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group; γ- (meth) acryloxypropyl group, γ-glycidoxy propyl group And hydrocarbon groups substituted with (meth) acryloxy, epoxy, mercapto, amino groups such as 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, and γ-aminopropyl group. Among these, a methyl group, a propyl group, a cyclohexyl group, a norbornyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group are preferable, and it is preferable that especially a phenyl group is essential in order to raise the flexibility of hardened | cured material.

When the content a of R ¹ is smaller than 0.3, the content of the tetrafunctional siloxane unit increases, which is not suitable because cracks easily occur in the film. On the other hand, when a is larger than 1.6, the content of the bifunctional siloxane unit increases, while the flexibility is imparted to the membrane, while the content of silanol groups essential for expressing adhesion to the substrate and alkali solubility is low. It is not suitable.

R ² is a linear or branched alkyl group having 1 to 6 carbon atoms, and OR ² group is other than silanol group (Si-OH) at the siloxane end group, and an alkoxy residue or precursor polysiloxane synthesis derived from alkoxysilane which is a raw material of precursor polysiloxane It is produced by the introduction of an alcohol into the siloxane which is used as the reaction solvent. Specifically, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are mentioned. As the raw material of the polyorganosiloxane, inexpensive methoxysilane and ethoxysilane are suitably used. Therefore, the OR ² group is often a methoxy group or an ethoxy group, but is not limited thereto.

Introduction of the acid labile group into the precursor polysiloxane is carried out by reaction of the silanol group and the acid labile group raw material. Since the alkoxy moiety is not involved, the content b may contain 0 (zero). When b is larger than 0.3, the proportion of alkoxy residues in the end groups is increased, so that the total amount of silanol groups is relatively decreased, which lowers the amount of acid labile groups introduced, thereby obtaining sufficient resolution.

The quantity of these alkoxy residues can be quantified by infrared absorption spectrum or alcohol quantification by alkali cracking. In practice, even an amount below the measurement limit can be applied.

The silanol group content c can be calculated | required by measuring ²⁹ Si-NMR of precursor polysiloxane, and calculating the average chemical structure of siloxy acid. That is, for example, in the T unit (R ¹ Si-0 _3/2 ) synthesized from the trifunctional hydrolyzable silane, the four structural units (T0 to T3) shown below have different chemistries in the ²⁹ Si-NMR spectrum. The signal is observed by the shift. Since the area of this signal shows the abundance ratio of this structure, the molar amount% of terminal group OX can be calculated from the abundance ratio of T0, T1, and T2. From the molar amount, the molar amount of the silanol group contained in the polyorganosiloxane can be calculated by subtracting the remaining amount of the alkoxy group determined separately from the IR spectrum or the like.

[Formula 3]

Wherein X = H or R ² , R ¹ is the same as described above

When content c of silanol group (Si-OH) exceeds 2, it will contain many tetrafunctional siloxane units (Q), or if it is trifunctional siloxane unit (T) alone, it will be a dimer structure, and the whole terminal will be a silanol group This is the case. Such polyorganosiloxanes are not suitable because they are low molecular weight and lack the film forming ability and lack the crack resistance of the cured film. When c is less than 0.001, the content of the acid labile group introduced by the substitution of the present invention is extremely low, which is not suitable because it is not possible to obtain radioactive-sensitivity as expected.

The molecular weight of this precursor polysiloxane can be measured by gel permeation chromatography (GPC). It is preferable that the weight average molecular weight obtained from the analytical curve created based on standard polystyrene exists in the range of 300-200,000. If it is less than 300, the film formability and crack resistance may be insufficient, and if it is larger than 200,000, the solubility of the developer during development may be significantly reduced.

Precursor polysiloxane can be synthesize | combined by the method known conventionally. As a hydrolyzable silicon compound of a raw material, what is enumerated below can be used. Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxyoxytriethoxysilane, 3-glycidoxyoxymethylmethyldimethoxysilane, 3-glycidoxyoxymethylmethylethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl Ethyl diethoxymethylsilane, 3- (4-vinylphenyl) propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxy Silane, 4-vinylphenyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- ( 2-aminoethyl) aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxy In addition to so-called silane coupling agents such as silanes, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxy Silane, methyltributoxysilane, methyltriisopropenoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, Butyl Chlorosilane, Butyltrimethoxysilane, Hexyltrichlorosilane, Hexyltrimethoxysilane, Decyltrichlorosilane, Decyltrimethoxysilane, Phenyltrichlorosilane, Phenyltrimethoxysilane, Cyclohexyltrichlorosilane, Cyclohexyl Trimethoxysilane, propylmethyldichlorosilane, propylmethyldimethoxysilane, hexylmethyldichlorosilane, hexylmethyldimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane Etc. can be mentioned. In addition, in addition, hydrogen silanes such as trichlorohydrogensilane, trimethoxyhydrogensilane, and triethoxyhydrosilane and organic groups having an unsaturated bond can be bonded by hydrosilylation to form desired silicon. A compound can also be synthesize | combined and used.

The hydrolyzable silicon compound may be used alone or in combination of two or more.

The hydrolyzable group contained in this silicon compound is preferably a methoxy group and an ethoxy group. This is because the ease of reaction control and the remaining of halogen ions are inadequate for the use of the present invention, so the use of chlorosilanes is not preferred.

As for the organic group, as described above, a methyl group, a propyl group, a cyclohexyl group, a norbornyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group are preferable, and a phenyl group and a 3,4-epoxycyclohexylethyl group are most suitable. Do. It is preferable to use the silicon compound which has these hydrolysable groups and organic groups for a raw material.

As a method of hydrolyzing and condensing the said hydrolyzable silane compound and obtaining the hydrolyzable condensate which can be used for this invention, the method of hydrolyzing a hydrolyzable silane compound in water or water and an organic solvent is mentioned.

As for the quantity of water used for hydrolysis, 1 mol or more and 1.2 mol or more are preferable with respect to 1 mol of hydrolysable groups Y. If the amount of water is less than 1 mole, the hydrolysis of the hydrolyzable group proceeds only partially, and the hydrolyzable group remains relatively large in an unreacted state. If a large amount of unreacted hydrolyzable groups remain, the amount of silanol groups is reduced by that amount, which is not suitable for the purpose of the present invention.

The organic solvent can be widely used irrespective of water solubility and non-water solubility. In particular, it is preferable to use a polar solvent because of its high solubility in siloxane containing silanol groups. Specific examples include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, diacetone alcohol, ethylene glycol, monoethylene glycol monoether, propylene glycol, propylene glycol monoether and the like. In particular, as the polysiloxane suitable for the present invention, low boiling alcohols such as methanol and ethanol which are easily distilled off are preferable.

In the case of hydrolysis and subsequent condensation reaction, a conventionally well-known hydrolysis catalyst and a condensation catalyst can be used. Particularly preferred are acidic hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, solid acids such as ion exchange resins, and the like. Examples thereof include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as acetic acid, maleic acid, oxalic acid and methanesulfonic acid, and cation exchange resins having a sulfonic acid group or a carboxylic acid group on the surface thereof. As for the quantity of a hydrolysis catalyst, 0.001-10 mol% is preferable with respect to 1 mol of hydrolysable groups Y. For the use of the present invention, organic acids such as acetic acid and oxalic acid obtained by decomposition by heating are preferable.

The hydrolysis reaction and the condensation reaction cannot be separated strictly, and some condensation proceeds even during the hydrolysis reaction. Therefore, the acidic catalyst functions as a catalyst in both reactions, but when it is desired to increase the degree of condensation, a separate condensation catalyst may be added. Examples of these condensation catalysts include alkaline compounds such as ammonia and amines and metal compounds such as ammonium salts, titanium, zinc, zirconium and tin, in addition to the acidic compounds described above.

Next, the method to replace the silanol group of this precursor polysiloxane with an acid labile group is demonstrated. As for the polyorganosiloxane compound which concerns on this invention, the partial hydrogen atom of the hydroxyl group couple | bonded with the silicon atom contained in the polyorganosiloxane (precursor polysiloxane) represented by said average composition formula (1) is the following general formula (2) It is made to bridge | crosslink in the molecule | numerator or intermolecularly by the bridge | crosslinking group which substitutes with the acid labile group represented by and / or has a COC group represented by following General formula (3).

[Formula 4]

(In formula (2), R <^3> , R <^4> is a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group each independently, and R <^5> is C1-C30 linear, branched or A cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ³ and R ⁴ , R ³ and R ⁵ , R ⁴ and R ⁵ are bonded to each other and a carbon atom to which they are bonded, or carbon A ring may be formed together with an atom and an oxygen atom, and in the case of forming a ring, R ³ , R ⁴ , and R ⁵ , which are involved in the formation of a ring, are a linear or branched alkylene group having 1 to 18 carbon atoms)

[Formula 5]

(In formula (3), R <^6> , R <^7> , R <^9> , R <^10> is a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group independently of each other, R <^6> , R <^7> , R <^9> And R ¹⁰ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and when forming a ring, R ⁶ , R ⁷ , R ⁹ , and R ¹⁰ which are involved in the formation of a ring may have 1 to 17 carbon atoms. Linear or branched alkylene group, R ⁸ is a divalent hydrocarbon group having 1 to 6 carbon atoms which may contain oxygen atoms)

As an acid labile group of said Formula (2), as an example of a C1-C6 alkyl group of R <^3> and R <^4> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- A butyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

Examples of the linear, branched or cyclic alkyl group having 1 to 30 carbon atoms for R ⁵ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and n-pen Tyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexyl group, palmityl group, n-stearyl group, cyclo A propyl group, a cholesteryl group, tetrahydropyranyl group, tetrahydropranyl group, etc. are mentioned. Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, tolyl group, ethylphenyl group, propylphenyl group, dimethylphenyl group, methylethylphenyl group, naphthyl group, furyl group, and biphenyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, methylbenzyl group, propylbenzyl group, and dimethylbenzyl group.

In addition, in Formula (3), as an example of a C1-C6 linear, branched or cyclic alkyl group of R <^6> , R <^7> , R <^9> , R <^10> , a methyl group, an ethyl group, a propyl group, isopropyl group, n- Butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group, cyclopentyl group, etc. are mentioned. In addition, as an example of the bivalent hydrocarbon group which may contain a C1-C6 oxygen atom in R <^8> , the following are mentioned besides an alkylene group.

[Formula 6]

In the formulas (2) and (3), when R ³ , R ⁴ , R ⁵ or R ⁶ , R ⁷ , R ⁹ , and R ¹⁰ form a ring, examples of the ring include a tetrahydropyranyl group and tetrahydro Pranyl group is mentioned.

The novel polyorganosiloxane of the present invention uses the precursor polysiloxane under an acid catalyst, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl Ether, sec-butyl vinyl ether, ethyl-1-propenyl ether, cyclohexyl vinyl ether, methyl-1-propenyl ether, isopropenyl methyl ether, isopropenyl ethyl ether, dihydrofuran, dihydropyran, etc. Alkenyl ether compounds, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, neopentyl glycol Of dialkenyl ether compounds such as divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol divinyl ether and ethylene glycol diethylene vinyl ether It can be obtained by addition reaction.

In addition, as reaction conditions when introducing an acid labile group, an aprotic polar solvent, such as dimethylformamide, dimethylacetamide, tetrahydrofuran, 1, 4- dioxane, and ethyl acetate, is mixed individually or 2 types or more as a solvent. Can be used. As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium and the like can be used.

The polyorganosiloxane compound of the present invention is effective as a base resin of the following photosensitive resin composition and thermosetting resin composition (hereinafter, collectively referred to as "radiosensitive sensitive resin composition"), and the polyorganosiloxane compound and the photo-induced acid generation The radiosensitive resin composition which melt | dissolved the agent in the solvent is provided.

[Essential Component of Photosensitive Resin Composition]

(A) the polyorganosiloxane compound

(B) a light-induced acid generator that generates an acid by light irradiation in a wavelength range of 150 to 450 nm.

(D) solvent

[Essential Component of Thermosetting Resin Composition]

(A) the polyorganosiloxane compound

(B) a light-induced acid generator that generates an acid by light irradiation in a wavelength range of 150 to 450 nm.

(C) thermosetting agent

(D) solvent

Next, the photo-inducible acid generator of (B) is demonstrated. Specific examples of photo-inducible acid generators include trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyl Iodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium , Trifluoromethanesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluene Sulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, Nonafluorobutanesulfonic acid triphenylsulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-tolu Sulfonic acid trimethylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid dimethylphenylsulfonium, p-toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, di Onium salts such as phenyl (4-thiophenoxyphenyl) sulfonium hexafluoroantimonate;

Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) Diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane , Bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec -Amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl- ( Diazomethane derivatives such as 1-tert-amylsulfonyl) diazomethane and 1-tert-amylsulfonyl- (1-tert-butylsulfonyl) diazomethane;

Bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α -Dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedioneglyoxime, bis- (p-toluenesulfonyl) -2-methyl-3,4-pentanedioneglyoxime , Bis-o- (n-butane sulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl)- α-dicyclohexylglyoxime, bis-o- (n-butane sulfonyl) -2,3-pentanedioneglyoxime, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentane Dionglyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1- Trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime , Bis-o- (cyclohexanesulfonyl) -α-dimethylgly Shim, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesul Glyoxime derivatives such as poly (yl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime and bis-o-camphorsulfonyl-α-dimethylglyoxime;

oxime sulfonate derivatives such as α- (benzenesulfoniumoxyimino) -4-methylphenylacetnitrile;

Β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane;

Disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone;

nitrobenzylsulfonate derivatives such as p-toluenesulfonic acid 2,6-dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl;

1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, etc. Sulfonic acid ester derivatives;

Putimide-yl-triplate, putimide-yl-tosylate, 5-norbornene 2,3-dicarboxyimide-yl-triplate, 5-norbornene 2,3-dicarboxyimide-yl Imide-yl-sulfonate derivatives such as tosylate, 5-norbornene 2,3-dicarboxyimide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide; Can be mentioned.

Furthermore, (5- (4-methylphenyl) sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetnitrile, (5- (4- (4-methylphenylsulfonyloxy) phenylsul Iminosulfonates such as polyvinyloxyimino) -5H-thiophen-2-ylidene)-(2-methylphenyl) -acetonitrile and 2-methyl-2 [(4-methylphenyl) sulfonyl] -1- [ (4-methylthio) phenyl] -1-propane etc. are mentioned.

Among these, imide-yl- sulfonates, imino sulfonates, oxime sulfonates, etc. are used preferably.

The said photo-inducible acid generator can be used individually by 1 type or in mixture of 2 or more types. As for the compounding quantity of a photo-induced acid generator, 0.05-20 mass parts and 0.2-5 mass parts are especially preferable with respect to 100 mass parts of polyorganosiloxane compounds of this invention. If the blending amount is less than 0.05 parts by mass, sufficient contrast (dissolution rate difference between the developer of the light exposed part and the unexposed part may not be obtained), and if it exceeds 20 parts by mass, the resolution may deteriorate due to light absorption of the acid generator itself. .

Next, the thermosetting agent of (C) is demonstrated. The thermosetting agent is not particularly limited as long as it is cured by crosslinking by condensation or addition reaction between silanol groups or thermosetting agents in the polyorganosiloxane of the present invention, and for example, melamine compounds, glycoluril compounds, urea compounds or And compounds selected from epoxy compounds having an average of two or more epoxy groups per molecule.

As an example of a melamine type compound, hexamethylol melamine hexamethyl ether, hexamethylol melamine hexabutyl ether, tetramethoxymethylbenzoguanamine, tetrabutoxymethylbenzoguanamine, etc. are mentioned, for example.

As a glycoluril type compound, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. are mentioned, for example.

Examples of the urea-based compound include tetramethoxymethyl urea, dimethoxymethylethylene urea and dimethoxymethylpropylene urea.

As an epoxy compound which has an average of 2 or more epoxy groups per molecule, Bisphenol-A epoxy resins, such as a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, diglycidyl bisphenol A, diglycidyl bisphenol F, etc. Cyclic aliphatic epoxy resins such as triphenylmethane type epoxy resins such as bisphenol F type epoxy resin and triphenylolpropane triglycidyl ether, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Glycidyl ester resins such as diglycidyl phthalate, diglycidyl hexahydrophthalate, dimethylglycidyl phthalate, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, and diglycidyl Glycidyl amine resins, such as cydyl aniline, diglycidyl toluidine, and tetraglycidyl bisamino methyl cyclohexane, etc. are mentioned.

The said thermosetting agent can be used individually by 1 type or in mixture of 2 or more types. As for the compounding quantity of a thermosetting agent, 0.1-20 mass parts and 2-10 mass parts are especially preferable with respect to 100 mass parts of polyorganosiloxane compounds of this invention. If the blending amount is less than 0.1 part by mass, sufficient crosslinking density may not be obtained. If the blending amount is more than 20 parts by mass, transparency may deteriorate or storage stability may be degraded due to light absorption of the thermosetting agent itself.

As a solvent of (D), if it is a solvent which has sufficient solubility with respect to (A) polyorganosiloxane of this invention, (B) photo-inducible acid generator, and (C) thermosetting agent, and provides favorable coating film property, it will be special. Can be used without limitation. For example, ketones, such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; 3-methoxy butanol, 3-methyl-3- methoxy butanol, 1-methoxy-2-propanol, 1 Alcohols such as ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl propionate, tert-butyl propionate, Ester, such as a propylene glycol mono- tert- butyl ether acetate and (gamma) -butyrolactone, etc. are mentioned, One type is used individually or two or more types are bottled. And it can be used. Among these, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl having the highest solubility with respect to (A) polyorganosiloxane, (B) light-induced acid generator and (C) thermosetting agent, among others. Ether acetate, γ-butyrolactone and mixed solvents thereof are preferable. As for the usage-amount of the above-mentioned organic solvent, 50-2,000 mass parts and 100-1,000 mass parts are especially preferable with respect to 100 mass parts of total solids of components (A)-(C). If it is less than 50 parts by mass, the compatibility of each of the above-mentioned components (A) to (C) may become insufficient. On the contrary, even if it exceeds 2,000 parts by mass, the compatibility will not be largely changed, but the viscosity will be too low. There is a possibility of becoming unsuitable.

Moreover, in addition to each component mentioned above, the polyorganosiloxane of this invention can further mix | blend an addition component.

As one of the additive components, the surfactant usually used in order to improve applicability, for example, can be added in a ratio of 0.01 to 1 part by mass based on 100 parts by mass of the component (A). As the surfactant, nonionic surfactants are preferable, and for example, fluorine-based surfactants, specifically, perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, fluorine-containing organosiloxane compounds, and the like. Can be mentioned.

These can use a commercially available thing, For example, Florade "FC-4430" (manufactured by Sumitomo 3M Co., Ltd.), Supron "S-141", and "S-145" (both Asahi Glass Co., Ltd.) Products], Units "DS-401", "DS-4031" and "DS-451" [All Daikin Industries Co., Ltd.], Mega Pack "F-8151" [Products by Dainippon Inkie Co., Ltd.] And "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Florade "FC-4430" (manufactured by Sumitomo 3M Co., Ltd.) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) can be preferably used.

As another additive component, a nitrogen-containing compound may be added to improve environmental stability, pattern shape, or storage stability over time. Nitrogen-containing compounds include amines, in particular secondary or tertiary aliphatic amines. Examples of this secondary or tertiary amine include diethylamine, di-n-propylamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, triethanolamine, tripropanolamine and the like. Can be mentioned.

Next, the pattern formation method using the radiosensitive resin composition of this invention is demonstrated. The radioactive susceptible resin composition of the present invention is applied to a substrate by a known method such as a dipping method, a spin coating method, a roll coating method, and is usually 50 to 300 at a heating device such as a hot plate or an oven at 80 to 120 ° C. Prebaking is performed for a minute, and the resist film of 0.5-20 micrometers is formed. Subsequently, using radiation generating apparatuses such as a reduced projection type exposure apparatus and a mask aligner, light having various wavelengths in the range of 150 to 450 nm, for example, ultraviolet light such as g line and i line, ultraviolet light (248 nm, 193 nm) or the like. After light exposure, you may heat-process after light exposure for 50 to 300 minutes normally at 90-130 degreeC, in order to raise image development sensitivity further as needed.

After the light exposure or heating by light exposure, development is carried out with a developer. As a developing solution, the well-known alkaline developing solvent represented by tetramethylammonium hydroxide aqueous solution etc. is used. The development can be carried out by immersing a conventional method, for example, a pattern formation. Thereafter, if desired, washing, rinsing, drying, and the like can be performed to obtain a desired pattern.

Thereafter, in the case of the thermosetting resin composition, the obtained pattern is further heated at 100 to 250 ° C. for about 10 minutes to 10 hours using an oven or a hot plate to increase the crosslinking density to remove the remaining volatile components, thereby providing heat resistance, A cured film excellent in transparency, low dielectric constant and solvent resistance can be formed.

As mentioned above, the film obtained from the said resin composition is excellent in adhesiveness with a base material, heat resistance, electrical insulation, and mechanical characteristics, and is used suitably as a protective film of electrical components, an electronic component, a semiconductor element, etc., and fine pattern formation is carried out. In addition, the formed film is excellent in adhesiveness to the substrate, electrical properties, mechanical properties, and the like, and is preferably used for a protective film, a wiring protective film, a coverlay film, a solder resist, and the like of a semiconductor element.

EXAMPLE

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

Synthesis Example 1

Synthesis of Polysiloxane A

In a 1 L three-necked flask equipped with a thermometer, a stirrer and a cooler, 89.2 g (0.45 mol) of phenyltrimethoxysilane, 110.9 g (0.45 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Methanol 360g was added and ice-cooled at 10 degrees C or less, stirring. 90 g of 0.1 M acetic acid aqueous solution was added to the dropping route, and the mixture was dropped while ice-cooling, thereby proceeding with the hydrolysis condensation reaction with exothermic heat. After raising the internal temperature to room temperature, stirring and aging for 2 hours, an ester adapter was installed and methanol was distilled off by heating at atmospheric pressure.

The disiloxane was continuously distilled off until the internal temperature exceeded the boiling point of methanol, thereby obtaining a polysiloxane solution having a white turbid viscosity. At this time, the amount of methanol captured was 382 g. 300 g of ethyl acetate was added to this polysiloxane solution, and the dissolved solution was washed twice with pure water. By concentrating this polysiloxane solution by the rotary evaporator, 233 g of colorless transparent polysiloxane solutions A (solid content concentration 62.2 mass%) were obtained.

The weight average molecular weight (GPC polystyrene standard) of this polysiloxane was 4.2x10 <^3> . In the alkali crushing method, no residual methoxy group was detected. The abundance ratio of T0-T3 was calculated | required by ²⁹ Si-NMR, and the following average composition formula was computed.

_{Ph 0 .5 (EP) 0.5 Si} (OH) 0.72 O 1 .14

EP: 2- (3,4-epoxycyclohexyl) ethyl group

Ph: phenyl group

[Ph group, EP group both correspond to R ₁ group. Average composition formula (1) notation: a = 1.0, b = 0, c = 0.72]

Synthesis Example 2

Synthesis of Polysiloxane B

Into a 1 L three-necked flask equipped with a thermometer, a stirrer, and a cooler, 99.1 g (0.5 mol) of phenyltrimethoxysilane, 60.1 g (0.5 mol) of dimethyldimethoxysilane, and 277 g of methanol were ice-cooled to 10 DEG C or lower while stirring. It was. 84 g of 0.1 M aqueous methanesulfonic acid solution was added to the dropping route, and the resultant was dripped while ice-cooling to proceed the hydrolysis condensation reaction with exothermic heat. After raising internal temperature to room temperature, stirring and aging for 2 hours, ester adapter was installed and methanol was distilled off by the normal pressure of heating. Distillation was continued until the internal temperature exceeded the boiling point of methanol, thereby obtaining a polysiloxane solution showing a white cloudy viscosity. At this time, the amount of captured metaol was 280g. 200 g of ethyl acetate was added to this polysiloxane solution, and the dissolved solution was washed with pure water twice. By concentrating this polysiloxane solution by the rotary evaporator, 185 g of colorless transparent polysiloxane solutions B (solid content concentration 60.5 mass%) were obtained.

The weight average molecular weight (GPC polystyrene standard) of this polysiloxane was 3.8x10 <^3> . In addition, the residual methoxy group was not detected by the alkali grinding method. The abundance ratio of T0-T3 was calculated | required by ²⁹ Si-NMR, and the following average composition formula was computed.

_{Ph 0 .5 Me 1 .0 Si (} OH) 0.6 O 0 .95

[Ph group (phenyl group), Me group (methyl group) both correspond to R <^1> group. Average composition formula (1) notation: a = 1.5, b = 0, c = 0.6]

Synthesis Example 3

Synthesis of Polysiloxane C

Into a 1 L three-necked flask equipped with a thermometer, a stirrer, and a cooler, 98.9 g (0.65 mol) of tetramethoxysilane, 69.4 g (0.35 mol) of phenyltrimethoxysilane, and 360 g of methanol were ice-cooled to 10 DEG C or lower while stirring. It was. 122 g of 0.1 M aqueous hydrochloric acid solution was added to the dropping route, and the mixture was dropped while ice-cooling, thereby proceeding with the hydrolysis reaction with exothermic heat. After raising the internal temperature to room temperature, stirring and aging for 2 hours, an ester adapter was installed and methanol was distilled off by heating at atmospheric pressure. The polysiloxane solution was obtained by continuing distillation until the internal temperature exceeded the boiling point of methanol. Ethyl acetate 200g was added to this polysiloxane solution, and the obtained polysiloxane solution was washed with pure water twice. By concentrating this polysiloxane solution by the rotary evaporator, 491 g of colorless transparent polysiloxane solutions C (solid content concentration 20.2 mass%) were obtained.

The weight average molecular weight (GPC polystyrene standard) of this polysiloxane was 5.5x10 <^3> . In addition, 1.0 mass% of residual methoxy groups were detected by the alkali grinding method. By calculating the abundance ratio of T0 to T3 by ²⁹ Si-NMR, the average composition formula was calculated as follows.

_{Si (OMe) 0.03 (OH)} Ph 0 .35 1.03 O 1 .21

[Average composition formula (1) notation: a = 0.35, b = 0.03, c = 1.03]

Synthesis Example 4

Synthesis of Acetalized Polysiloxane D

80.4 g of the polysiloxane A obtained in Synthesis Example 1 was solvent-substituted in an ethyl acetate solution with a tetrahydrofuran solution (solid content concentration of 20 mass%), and then placed in a 1 L three-necked flask equipped with a thermometer, a stirrer, and a cooler, and methanesulfonic acid 1.0 g (0.01 mol) was added.

Next, 19.4 g (0.23 mol) of ethyl-1-propenyl ethers were dripped at the dropping route, maintaining the internal temperature at 10 degrees C or less, ice-cooling and stirring at 10 degrees C or less. After reacting at room temperature for 2 hours after the dropwise addition, 1.0 g (0.01 mol) of triethylamine was added to terminate the reaction. The reaction solution was transferred to a 1 L flask, tetrahydrofuran was distilled off by a rotary evaporator under reduced pressure at room temperature, 300 g of methyl isobutyl ketone and 250 ml of acetic acid aqueous solution of 0.01 N were added, and the reaction solution was washed with water. After this washing operation was repeated three times in total, the organic layer was separated and concentrated by a rotary evaporator to obtain 49.0 g of colorless transparent acetalized polysiloxane D.

The acetal substitution rate of this acetalized polysiloxane D was calculated at 32.5 mol% from the result of ¹³ C-NMR.

Synthesis Example 5

Synthesis of Acetalized Polysiloxane E

80.4 g of polysiloxane A obtained in Synthesis Example 1 was solvent-substituted in an ethyl acetate solution with a tetrahydrofuran solution (20 mass% siloxane concentration), and then placed in a 1 L three-necked flask equipped with a thermometer, a stirrer, and a cooler, and methanesulfonic acid 1.0 g (0.01 mol) was added.

Next, 7.3 g (0.10 mol) of ethyl vinyl ether and 1.6 g (0.01 mol) of 1,4-butanediol divinyl ether were added dropwise while maintaining the internal temperature at 10 ° C. or lower in the dropping route while ice-cooling and stirring at 10 ° C. or lower. It was. After dropping, the mixture was allowed to react at room temperature for 2 hours, and then triethylamine 1.0g (0.01 mol) was added to terminate the reaction. The reaction solution was transferred to a 1 L flask, tetrahydrofuran was distilled off in a rotary evaporator under reduced pressure at room temperature, 300 g of methyl isobutyl ketone and 250 ml of acetic acid aqueous solution of 0.01 N were added, and the reaction solution was washed with water. After this washing operation was repeated three times in total, the organic layer was separated and concentrated in a rotary evaporator to obtain 49.0 g of colorless transparent acetalized polysiloxane E.

The acetal substitution rate of this acetalized polysiloxane E was computed at 34.5 mol% from the result of ¹³ C-NMR.

Synthesis Example 6

Synthesis of Acetalized Polysiloxane F

82.6 g of polysiloxane B obtained in Synthesis Example 2 was solvent-substituted in an ethyl acetate solution with a tetrahydrofuran solution (20 mass% of siloxane concentration), and then placed in a 1 L three-necked flask equipped with a thermometer, a stirrer and a cooler, and methanesulfonic acid 1.0 g (0.01 mol) was added.

Next, 23.6 g (0.28 mol) of 3,4-dihydro-2H-pyrans were dripped at the root of dripping, keeping ice-cooling at 10 degrees C or less, and stirring. After dropping, the mixture was allowed to react at room temperature for 2 hours, and then triethylamine 1.0g (0.01 mol) was added to terminate the reaction. The reaction solution was transferred to a 1 L flask, tetrahydrofuran was distilled off in a rotary evaporator under reduced pressure at room temperature, 300 g of methyl isobutyl ketone and 250 ml of 0.01 N acetic acid aqueous solution were added, and the reaction solution was washed with water. After this washing operation was repeated three times in total, the organic layer was separated and concentrated in a rotary evaporator to obtain 48.4 g of colorless transparent acetalized polysiloxane F.

The acetal substitution rate of this acetalized polysiloxane F was calculated as 46.3 mol% from the result of ¹³ C-NMR.

Synthesis Example 7

Synthesis of Acetalized Polysiloxane G

Solvent substitution of 247.5 g of polysiloxane C obtained in Synthesis Example 3 with tetrahydrofuran solution (20 mass% of siloxane concentration) in ethyl acetate solution was carried out in the 1 L three-necked flask equipped with a thermometer, a stirrer, and a cooler, and methanesulfonic acid 1.0 g (0.01 mol) was added.

Next, 21.7 g (0.40 mol) of isobutyl vinyl ether and 10.6 g (0.1 mol) of 1,4-cyclohexanedimetholdivinyl ether were dripped at the inside of a dropping route, ice-cooling and stirring to 10 degrees C or less. It was dripped keeping it as. After dropping, the mixture was allowed to react at room temperature for 2 hours, and then triethylamine 1.0g (0.01 mol) was added to terminate the reaction. The reaction solution was transferred to a 1 L flask, tetrahydrofuran was distilled off in a rotary evaporator under reduced pressure at room temperature, 400 g of methyl isobutyl ketone and 250 ml of acetic acid aqueous solution of 0.01 N were added, and the reaction solution was washed with water. After this washing operation was repeated three times in total, the organic layer was separated and concentrated by a rotary evaporator to obtain 48.2 g of a colorless transparent acetalized polysiloxane G.

The acetal substitution rate of this acetalized polysiloxane G was computed at 58.8 mol% from the result of ¹³ C-NMR.

Example 1

10 g of acetalized polysiloxane D obtained in Synthesis Example 4 was dissolved in 14 g of cyclopentanone, and [5- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H-thiophene-2 as an acid generator. 0.10 g of -ylidene]-(2-methylphenyl) -acenitrile was mixed with 0.01 g of surfactant X-70-093, dissolved, and filtered through a cell filter having pores having a diameter of 0.2 μm to prepare a resist liquid. .

Next, the resist liquid was applied on a 6-inch silicon wafer with a spinner, and prebaked at 100 ° C./120 seconds on a hot plate to form a resist film having a thickness of 4.0 μm. Furthermore, patterning exposure was carried out using an i-line stepper [NSR-1755i7A, NA = 0.5, manufactured by Nikon Corporation], paddle developed for 120 seconds using a developer solution of tetramethyl ammonium hydroxide, and washed with pure water. The pattern evaluation was performed by Hitachi, Ltd. product SEM: S-4100. The pattern evaluation was conducted by observing a line / space pattern of 0.5 to 5.0 µm, and determining the resolution by sensitivity, verticality of the pattern sidewalls, presence or absence of a resist scum in the space portion, and minimum resolution dimension (line / space). It was.

[Example 2 to Example 4]

In the same manner as in Example 1, a resist liquid was prepared, and patterning evaluation was performed. A composition is shown in Table 1 and a pattern evaluation result is shown in Table 2, respectively.

TABLE 1

PAG1; [5- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H-thiophen-2-ylidene]-(2-methylphenyl) -acetnitrile

PAG2; 4-methoxy-α-[[[(4-methylphenyl) sulfonyl] -oxy] imino] benzeneacetnitrile

TABLE 2

Example 5

10 g of acetalized polysiloxane D obtained in Synthesis Example 4 was dissolved in 16 g of cyclopentanone, and [5- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H-thiophene-2 as an acid generator. 0.10 g of -ylidene]-(2-methylphenyl) -acenitrile, 0.5 g of tetramethoxymethyl glycoluril and 0.01 g of surfactant X-70-093 as a curing agent were mixed and dissolved, A resist solution was prepared by filtration with a cell membrane filter having pores.

Next, similarly to Example 1, the resist liquid was applied on a 6-inch silicon wafer with a spinner, and prebaked at 100 ° C./120 seconds on a hot plate to form a resist film having a thickness of 4.0 μm. Furthermore, patterning exposure was carried out using an i-line stepper [NSR-1755i7A, NA = 0.5, manufactured by Nikon Corporation], paddle developed for 120 seconds using a developer solution of 2.38% by mass of tetramethylammonium hydroxide, and washed with pure water. The pattern evaluation was performed by Hitachi, Ltd. product SEM: S-4100. In the pattern evaluation, 0.5 to 5.0 μm line / space pattern was observed, and resolution was judged by sensitivity, verticality of the sidewall of the pattern, presence or absence of resist scum in the space portion, and minimum resolution dimension (line / space). .

<Evaluation of solvent resistance>

As above-mentioned, the resist liquid was apply | coated with the spinner on the silicon wafer, it prebaked at 100 degreeC / 120 second on the hotplate, and the resist film of 4.0 micrometers in thickness was formed. In addition, as above-mentioned, after exposure, it immersed for 120 second in the developing solution of 2.38 mass% of tetramethylammonium hydroxide, and wash | cleaned with pure water. The film remaining after this operation was further heated in oven at 220 degreeC for 1 hour, and the cured film with a film thickness of 3.5 micrometers was obtained. The formed wafer of the cured film was immersed in a mixed solution of 2-g ethanol 70 g-dimethylsulfoxide 30 g heated at 60 ° C. for 15 minutes, washed with pure water, and then the film thickness was measured. In comparison, the ratio of the residual film was measured to evaluate solvent resistance.

<Evaluation of transparency of film after hardening>

Except for using a quartz wafer, the resist liquid was applied by a spinner in the same manner as the evaluation of the solvent resistance, and prebaked at 100 ° C./120 seconds on a hot plate to form a resist film having a thickness of 4.0 μm. Furthermore, after exposure similarly to the above, it immersed for 120 second in the developing solution of 2.38 mass% of tetramethylammonium hydroxide, and wash | cleaned with pure water. The film remaining after this operation was further heated in oven at 220 degreeC for 1 hour, and the cured film with a film thickness of 3.5 micrometers was obtained. Next, after measuring the transmittance | permeability in the range of 200 nm-800 nm using the spectrophotometer U-3000 130-0018 (made by Hitachi Corporation), transparency was evaluated by the transmittance | permeability in 400 nm.

<Measurement of relative dielectric constant>

The above-mentioned resist liquid was further diluted with cyclopentanone to have a resin solid concentration of 10% by mass, spin-coated this solution on a 6-inch N-type silicon wafer, and then heated to 100 ° C./120 seconds on a hot plate for solvent removal. Prebaking was performed. Furthermore, after exposure similarly to the above, it immersed for 120 second in the developing solution of 2.38 mass% of tetramethylammonium hydroxide, and wash | cleaned with pure water. The remaining film after this operation was further heated in an oven at 220 ° C. for 1 hour to obtain a cured film having a film thickness of 0.8 μm. Using this hardened film, the dielectric constant was measured by the CV method using an automatic mercury probe using the automatic mercury CV measuring device 495-CV system (made by SSM, Japan).

[Example 6 to Example 8]

In the same manner as in Example 5, a resist liquid was prepared, and patterning and physical property evaluation were performed. Table 3 shows the composition, and Table 4 shows the pattern and the physical property evaluation results.

TABLE 3

PAG1; [5- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -5H-thiophen-2-ylidene]-(2-methylphenyl) -acetnitrile

PAG2; 4-methoxy-α-[[[(4-methylphenyl) sulfonyl] -oxy] imino] benzeneacetnitrile

CL1; Tetramethoxymethylglycoluril

CL2; Triphenylolpropanetriglycidyl ether

TABLE 4

From the above results, the compositions of Examples 1 to 8 can be formed vertically in a line / space pattern of 0.5 µm to 0.75 µm without debris, exhibit good resolution, and exhibit sufficient characteristics as a photosensitive material. Moreover, the cured film obtained from the composition of Examples 5-8 has the electrical property of insulation withstand voltage, and also excellent transparency and solvent resistance property, and can obtain the result useful as a protective film of a circuit or an electronic component. have.

Claims (5)

Some hydrogen atoms of the hydroxyl group directly bonded to the silicon atoms contained in the polyorganosiloxane represented by the following average composition formula (1) are substituted with an acid labile represented by the following general formula (2) and / or the following general formula ( A polyorganosiloxane compound which is crosslinked intramolecularly or intermolecularly by a crosslinking group having a COC group represented by 3) and has a weight average molecular weight of 300 to 200,000 in terms of a polystyrene standard measured by gel permeation chromatography (GPC). . R ¹ _a Si (OR ² ) _b (OH) _c O _{(4-abc) / 2} (1) (In formula (1), R <^1> is 1 type, or 2 or more types of group chosen from a hydrogen atom or a C1-C18 organic group, and R <^2> is chosen from a C1-C6 linear or branched alkyl group. One or two or more groups having a range of 0.3 ≦ a ≦ 1.6, 0 ≦ b ≦ 0.3, and 0.001 ≦ c ≦ 2). [Formula 1]

(In formula (2), R <^3> and R <^4> is a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group independently of each other, R <^5> is C1-C30 linear, branched or A cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ³ and R ⁴ , R ³ and R ⁵ , R ⁴ and R ⁵ are bonded to each other and a carbon atom to which they are bonded, or carbon A ring may be formed together with an atom and an oxygen atom, and in the case of forming a ring, R ³ , R ⁴ , and R ⁵ , which are involved in the formation of a ring, are a linear or branched alkylene group having 1 to 18 carbon atoms) [Formula 2]

(In formula (3), R <^6> , R <^7> , R <^9> , R <^10> is a hydrogen atom or a C1-C6 linear, branched or cyclic alkyl group independently of each other, R <^6> , R <^7> , R <^9> And R ¹⁰ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. When the ring is formed, R ⁶ , R ⁷ , R ⁹ , and R ¹⁰ which are involved in the formation of a ring have 1 to 17 carbon atoms. Linear or branched alkylene group, R ⁸ is a divalent hydrocarbon group having 1 to 6 carbon atoms which may contain oxygen atoms) (A) The polyorganosiloxane compound of Claim 1; And (B) a photo-acid-generating agent that generates an acid by light irradiation in the wavelength range of 150 to 450 nm. Photosensitive resin composition comprising a. (A) The polyorganosiloxane compound of Claim 1; (B) a light-induced acid generator that generates an acid by light irradiation in a wavelength range of 150 to 450 nm; And (C) thermosetting agent Thermosetting resin composition comprising a. (i) forming a resist film of the photosensitive resin composition according to claim 2 on a substrate; (ii) exposing the resist film to light comprising a light source having a wavelength of 150 to 450 nm through a photomask; And (iii) developing the resist film after light exposure with an aqueous alkali solution developer; Pattern forming method comprising a. (i) forming a resist film of the thermosetting resin composition according to claim 3 on a substrate; (ii) exposing the resist film to light including a light source having a wavelength of 150 to 450 nm through a photomask; (iii) developing the resist film after light exposure with an aqueous alkali solution developer; And (iiii) a step of curing the resist pattern film patterned by the above development at a temperature in the range of 100 to 250 ° C. Pattern forming method comprising a.