JP2005321667A - Formation material of original plate for fine pattern transfer, original plate for transfer, and method for making the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a formation material of an original plate for fine pattern transfer giving a film having excellent adhesiveness, releasability, mechanical properties, and solvent, heat and moisture resistances. <P>SOLUTION: The formation material of the original plate for fine pattern transfer comprises a photosetting organopolysiloxane composition containing (A) an alkali-soluble silicone resin having a molecular weight of 500-50,000 obtained by mixing (i) a silane compound of a formula (1): R<SP>1</SP><SB>X</SB>R<SP>2</SP><SB>Y</SB>Si(OR<SP>3</SP>)<SB>4-X-Y</SB>(where R<SP>1</SP>is a hydrolyzable epoxide-containing monovalent organic group; R<SP>2</SP>is an unsubstituted or substituted monovalent hydrocarbon group; R<SP>3</SP>is H or a monovalent hydrocarbon group; X is 1-3; Y is 0-2; and 1≤X+Y≤3), and (ii) a silane compound of a formula (2): R<SP>2</SP><SB>Z</SB>Si(OR<SP>3</SP>)<SB>4-Z</SB>(where Z is 0-3) in such a ratio that R<SP>1</SP>groups occupy ≥10 mol% of all organic groups except OR<SP>3</SP>groups and a total amount of a triorganoxysilane compound and a tetraorganoxysilane compound is ≥40 mol% of all silane compounds, and subjecting the resulting mixture to co-hydrolytic condensation, and (B) a photoacid generator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin material constituting a pattern portion of a fine pattern transfer original plate, and specifically, an alkali-soluble silicone resin as a main component, which can be photocured using a photoacid generator. Yes, it is soluble in polar solvents such as alkaline aqueous solution, alcohol, ketone, and ether in an uncured state, hardly soluble in these solvents after curing, and a transfer pattern can be easily formed on a substrate by photolithography, Photo-curable organopolysiloxane composition that provides a film with excellent sensitivity and resolution, adhesion to the substrate, releasability from the member to be transferred, mechanical strength, solvent resistance, heat resistance, and moisture resistance The present invention relates to a forming material for a fine pattern transfer original plate, a transfer original plate using the forming material, and a method for producing the transfer original plate.

  In recent years, for example, when a multilayer printed wiring board or the like is manufactured, a method of using a plurality of transfer plates as a method replacing the conventional method has been studied from the viewpoint of cost and reliability. As a material for forming such a pattern portion of the transfer plate, a plurality of resins can be mentioned. For example, in the case of silicone resin, JP-A-11-68294 (Patent Document 1) and JP-A-2001-168230 (Patent). Reference 2), Japanese Patent Application Laid-Open No. 2002-368386 (Patent Document 3), and the like. However, the use of resist materials improves the number of processes, finer resin patterns, mechanical strength of cured coatings, adhesiveness of coatings before exposure (before curing), development with organic solvents, etc. There are problems to be solved.

  On the other hand, even in the case of a silicone resin having high mechanical strength and excellent releasability and solvent resistance, few materials have excellent resolution in an aqueous solution system due to the characteristics of the resin. Examples of the alkali-soluble polysiloxane resin include resist materials described in JP-A-3-288857 (Patent Document 4), JP-A-4-070662 (Patent Document 5), and JP-A-4-338958 (Patent Document 6). Although there is a description that it is used, there is no material for forming a fine pattern transfer original plate that has good adhesion to the original plate, good releasability from the transferred material, and exhibits excellent patterning performance by alkali development.

JP-A-11-68294 JP 2001-168230 A JP 2002-368386 A JP-A-3-288857 JP-A-4-070662 JP-A-4-338958

  The present invention has been made in view of the above circumstances, and is a practical and economical silicone resin that can be used for photolithography. After forming a pattern by photolithography, the patterned resin itself is used as a mold for a transfer master. By using it, the number of steps can be reduced, and it has excellent patterning performance by alkali development, adhesion to the substrate, releasability from the transfer member, mechanical properties that can be used repeatedly, solvent resistance, To provide a forming material for a fine pattern transfer master comprising a photocurable organopolysiloxane composition that gives a film having excellent heat resistance and moisture resistance, a transfer master using the same, and a method for producing the transfer master With the goal.

  As a result of intensive studies to achieve the above object, the present inventor has (A) one or more silane compounds having an epoxide represented by the following general formula (1), and the following general formula (2 ) Is obtained by cohydrolyzing and condensing a silane mixture in which one or more of the silane compounds represented by formula (1) are mixed at a specific ratio, and has a hydroxyl group obtained as a result of part or all of the epoxide ring opening. A photo-curable organopolysiloxane composition comprising an alkali-soluble silicone resin having a weight average molecular weight of 500 to 50,000 (polystyrene converted value by GPC) and (B) a photoacid generator can be patterned by photolithography. Machine that can be used with alkali development and has high sensitivity and high resolution, and this cured film has adhesiveness to the substrate, releasability from the member to be transferred, and reusable machine. Strength, solvent resistance, excellent heat resistance and moisture resistance, found to be suitable as a material for forming the fine pattern transfer plate precursor, the present invention has been accomplished.

Accordingly, the present invention provides a forming material for a fine pattern transfer master shown below, a transfer master using the same, and a method for producing the transfer master.
[Claim 1] (A) (i) The following general formula (1):
R ¹ _X R ² _Y Si (OR ³ ) _4-XY (1)
(In the formula, R ¹ represents a monovalent organic group having 2 to 30 carbon atoms having at least one hydrolyzable epoxide, and R ² represents an unsubstituted or substituted monovalent carbon group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 1 to 3, and Y is an integer of 0 to 2. Yes, 1 ≦ X + Y ≦ 3 is satisfied.)
And (ii) the following general formula (2):
R ² _Z Si (OR ³ ) _4-Z (2)
(In the formula, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon having 1 to 10 carbon atoms. Z represents an integer of 0 to 3.)
1 type or 2 types or more of silane compounds represented by the formula ( ¹⁾ with a proportion of 10 mol% or more based on the total organic groups excluding the organoxy group in which the organic group represented by R ¹ is bonded to a silicon atom, The weight average molecular weight obtained by mixing and co-hydrolyzing and condensing the organotriorganoxysilane compound and the tetraorganoxysilane compound in a proportion of 40 mol% or more of the total silane compounds is 500 to 50,000. A material for forming an original for fine pattern transfer comprising an alkali-soluble silicone resin (polystyrene equivalent value by GPC) and (B) a photocurable organopolysiloxane composition containing a photoacid generator.
[Claim 2] The material for forming an original for fine pattern transfer according to claim 1, wherein the photocurable organopolysiloxane composition further contains a condensation catalyst.
[3] The material for forming a fine pattern transfer original plate according to [1] or [2], wherein the photocurable organopolysiloxane composition further contains a solvent and / or a reactive diluent.
[Claim 4] Furthermore, the photocurable organopolysiloxane composition comprises an epoxy curing agent, a photosensitizer, a light absorber, a dehydrating agent, inorganic oxide fine particles, a polymerization inhibitor, an antioxidant, an antifoaming agent, and the like. 4. The material for forming a fine pattern transfer original plate according to claim 1, comprising one or more selected from leveling agents. 5.
[Claim 5] A fine pattern transfer original plate on which a photocured film pattern of the forming material of the fine pattern transfer original plate according to any one of claims 1 to 4 is formed.
[Claim 6] A film of the forming material according to any one of claims 1 to 4 is formed on a substrate, and a desired portion of the film is exposed. A method for producing a fine pattern transfer master, comprising dissolving and removing with an organic solvent to form a photocured film pattern of the forming material having a shape corresponding to the exposed portion.

  As a forming material of a pattern transfer original plate using the photocurable organopolysiloxane composition of the present invention, an arbitrary fine transfer original plate can be produced by using only this material without using a resist material. In addition, the pattern transfer original plate forming material of the present invention can be developed with an alkaline aqueous solution without using an organic solvent in pattern formation by photolithography, and has excellent sensitivity and resolution, and the coating before curing is tack-free. Excellent in surface property and surface smoothness. The film after curing is adhesive to the substrate, releasable from the transfer target, mechanical properties that can be used repeatedly, film uniformity, surface smoothness, chemical resistance, heat resistance Excellent in moisture and moisture resistance. Therefore, the photocurable organopolysiloxane composition of the present invention is very effective as a material for forming an original plate for pattern transfer.

  The forming material for the fine pattern transfer master of the present invention comprises (A) an organoxysilane having a hydrolyzable epoxide, and 10 mol of all organic groups excluding the organoxy group in which the epoxide-containing organic group is bonded to a silicon atom. % Of a epoxide obtained by cohydrolyzing and condensing a silane mixture in such a proportion that the total amount of monoorganotriorganoxysilane compound and tetraorganoxysilane compound is 40 mol% or more of all silane compounds. Alternatively, a photocurable organopolysiloxane containing an alkali-soluble silicone resin having a hydroxyl group-containing weight-average molecular weight of 500 to 50,000 (polystyrene equivalent value by GPC) and (B) a photoacid generator, which is obtained as a result of ring-opening of all. It consists of a siloxane composition.

Alkali-soluble silicone resin The alkali-soluble silicone resin (A) of the present invention is (i) one type of epoxy-modified organoxysilane having one or more hydrolyzable epoxides represented by the following general formula (1). Or (ii) a silicone resin having a branched structure, which is a cohydrolysis condensate of one or more silane compounds represented by the following general formula (2).

R ¹ _X R ² _Y Si (OR ³ ) _4-XY (1)
R ² _Z Si (OR ³ ) _4-Z (2)
(In the formula, R ¹ represents a monovalent organic group having 2 to 30 carbon atoms having at least one hydrolyzable epoxide, and R ² represents an unsubstituted or substituted monovalent carbon group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 1 to 3, and Y is an integer of 0 to 2. Yes, 1 ≦ X + Y ≦ 3, Z is an integer of 0 to 3)

Here, one or two or more hydrolyzable epoxides having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, represented by R ¹ above. Although it does not restrict | limit especially as a valent organic group, Specifically, for example, glycidyl group, glycidoxymethyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2- (2,3-epoxycyclohexyl) ethyl group, 3- (N-allyl-N-glycidyl) aminopropyl group, 3- (N, N-diglycidyl) aminopropyl Group, 3- (N-glycidyl) aminopropyl group, 3- (N-methyl-N-glycidyl) aminopropyl group and the like.

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ² include an alkyl group or alkenyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or Aralkyl groups are preferred. Examples of the alkyl group and alkenyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and heptyl. Group, cyclohexyl group, cycloheptyl group, octyl group, α-ethylhexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and the like. Of these, a methyl group, an ethyl group, and a vinyl group are preferable, and deuterated ones can also be used. Examples of the aryl group and aralkyl group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group, and a styryl group. Of these, a phenyl group is preferred. Examples of the substituent include those substituted with a (meth) acryloxy group.

The unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ is preferably an alkyl group or alkenyl group having 1 to 10 carbon atoms, and is an alkoxy-substituted alkyl group. Also good. Specifically, for example, methyl group, 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, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like. Of these, a methyl group, an ethyl group, and a vinyl group are preferable.

  Specific examples of the epoxy-modified organoxysilane represented by the general formula (1) include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, 3- Glycidoxypropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, diethoxy-3-glycidoxypropylmethylsilane, 3- (glycidoxypropyl) methyldimethoxysilane, 3- (glycidoxypropyl) Examples include methyldiethoxysilane.

  Specific examples of the silane compound represented by the general formula (2) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxy Monoorganotriorganoxysilanes such as silane, phenyltripropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, p-styryltrimethoxysilane, Methyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, di Diorganodi such as propyldipropoxysilane, dipropyldibutoxysilane, divinyldiethoxysilane, divinyldi (methoxyethoxy) silane, diphenyldihydroxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane Organoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, trie Rumethoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, tripropylmethoxysilane, tripropylethoxysilane, tripropylpropoxysilane, tripropylbutoxysilane, trivinylethoxysilane, trivinyl (methoxyethoxy) silane, triphenyl Examples thereof include triorganomonoorganoxysilanes such as hydroxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-methacryloxypropyldimethylethoxysilane, and tetraorganoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

In the present invention, as the mixing ratio of the silane compounds represented by the general formulas (1) and (2), the organic group represented by R ¹ of the epoxy-modified organoxysilane represented by the general formula (1) is The amount is 10 mol% or more, preferably 20 to 90 mol%, more preferably 25 to 75 mol%, based on all organic groups excluding organoxy groups bonded to silicon atoms. Here, when the organic group represented by R ¹ is less than 10 mol% with respect to all organic groups excluding the organoxy group bonded to the silicon atom, the alkali solubility is deteriorated and the resolution is deteriorated.

  Moreover, in the silane compound represented by the general formula (2), in the case of monoorganotriorganoxysilane, it is preferable to mix at a ratio of 0 to 85 mol%, particularly 20 to 70 mol% of the total silane amount, In the case of diorganodiorganoxysilane, it is preferably mixed in a proportion of 0 to 40 mol%, particularly 0 to 20 mol% of the total amount of silane, and in the case of triorganomonoorganoxyxysilane, the general formula ( It is preferable to mix in a proportion of 0 to 50 mol%, particularly 0 to 25 mol%, relative to the molar amount of the silane compound 1). In the case of tetraorganoxysilane, 0 to 30 mol of the total silane amount. %, Particularly preferably in a proportion of 0 to 20 mol%.

  Furthermore, in the present invention, the total amount of the monoorganotriorganoxysilane compound and the tetraorganoxysilane compound in the silane compound used is 40 mol% or more, preferably 50 to 100 mol%, more preferably 60 to 100. It must be mol%. If it is less than 40 mol%, the tack-free property in an uncured state will deteriorate.

  Although it does not specifically limit as a manufacturing method of an alkali-soluble silicone resin, For example, the silane compound represented by General formula (2) is first mixed with the epoxy modified organoxysilane represented by General formula (1), and an acid catalyst is prepared. Is added together with a solvent as necessary, and a cohydrolyzed condensate having a hydroxyl group obtained by ring-opening part or all of the epoxide can be obtained by cohydrolysis and condensation polymerization under acidic conditions.

  As described above, the co-hydrolysis of the present invention is performed in the presence of an acid catalyst. As the acid catalyst, inorganic acids and organic acids which are known acid catalysts can be used. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid and hydrofluoric acid; organic acids such as acetic acid and oxalic acid. It is done. Of these, hydrochloric acid, acetic acid and oxalic acid are preferred.

  The acid cohydrolysis is usually preferably performed at 0 to 50 ° C. for 60 minutes or more. The cohydrolyzate thus obtained is then subjected to condensation polymerization. The conditions for this polycondensation reaction are important for controlling the molecular weight of the silicone resin. Since the hydrolysis rate is fast, the polycondensation reaction also proceeds during this hydrolysis reaction time. For example, in order to obtain the silicone resin having a weight average molecular weight of 1,000 or more (GPC polystyrene conversion value), In order to advance the polycondensation reaction, the reaction is carried out while distilling off the solvent and the alcohol to be produced. In this case, the polycondensation reaction is usually preferably performed at a temperature higher than the boiling point of the solvent for 120 to 180 minutes.

  Thus, organooxy groups such as alkoxy groups, silanol and carbinol remain in the cohydrolyzed polycondensation product obtained through cohydrolysis and condensation polymerization. In this case, the cohydrolysis polycondensation product having improved storage stability by converting only a part of the hydroxyl groups contained in the obtained cohydrolysis polycondensation product to a trialkylsiloxy group using a silylating agent. You can also get Examples of silylating agents include hexamethyldisilazane, tetramethyldibutyldisilazane, hexaethyldisilazane, tetramethyldivinyldisilazane, tetravinyldimethyldisilazane, N-trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide, N -Trimethylsilylimidazole and the like can be mentioned, and hexaalkyldisilazane is preferable, and hexamethyldisilazane is particularly preferable.

  In the alkali-soluble silicone resin obtained by cohydrolytic condensation of the silane compounds represented by the general formulas (1) and (2) by the above method, the use of the silane represented by the general formula (1) is a resin. Has increased alkali solubility.

R ¹ in the above general formula (1) contains an epoxide, and this epoxide undergoes ring cleavage by an acid or alkali during the hydrolysis condensation reaction to produce a hydroxyl group, which enhances the alkali solubility of the produced silicone resin. It works and improves patterning performance by photolithography.

The organic group in which the epoxide of R ¹ is opened is specifically represented by —CH (OH) CH (B) — (wherein B represents the base portion of the acid (HB) used or OH). Has a structure.

The organic group in which the epoxide in the organic group represented by R ¹ is ring-opened is contained in an amount of 10 mol% or more, preferably 15 to 90 mol% of all organic groups excluding the organoxy group bonded to the silicon atom. Is preferred. If it is less than 10 mol%, the solubility in an alkali developer may be deteriorated.

  The alkali-soluble silicone resin has a weight average molecular weight of 500 to 50,000 in terms of polystyrene by GPC, preferably 1,000 to 20,000. If the weight average molecular weight is too small, a film excellent in heat resistance and moisture resistance cannot be obtained, and if it is too large, alkali solubility is lowered. The molecular weight of the alkali-soluble silicone resin can be adjusted by changing the reaction time of the condensation polymerization reaction.

Photoacid generator The photoacid generator (B) used in the photocurable organopolysiloxane composition of the present invention is not particularly limited as long as it is usually used as a cationic photoacid generator. The generated acid is used for condensation of silanol remaining in the organopolysiloxane. Generally, examples include onium salts and sulfonium salts, and examples include phosphorus hexafluoride aromatic sulfonium salts and antimony hexafluoride aromatic sulfonium salts.

  As for the compounding quantity of a photo-acid generator, 0.1-20 mass parts is preferable with respect to 100 mass parts of said alkali-soluble organopolysiloxane, More preferably, it is 0.5-10 mass parts. When the blending amount of the photoacid generator is less than 0.1 parts by mass, the photocurability may be lowered and a sufficiently cured film may not be obtained. The above effect may not be obtained and may be uneconomical.

Condensation catalyst In the present invention, a condensation catalyst can be further used. The condensation catalyst is not particularly limited as long as it is usually used as a condensation catalyst for condensing silanol, alkoxy group or hydroxyl group. For example, tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate, etc. Titanium-based catalysts, dibutyltin dilaurate, dibutyltin maleate, dibutyltin acetate, tin octylate, tin naphthenate, dibutyltin acetylacetonate, etc. Aluminum catalysts such as acetate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethanolamine Tylene triamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methyl Silane coupling agents having amino groups such as morpholine, 2-ethyl-4-methylimidazole, DBU and other amine-based catalysts, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, etc. And known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more.

  When a condensation catalyst is used, the blending amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin. 1 to 3 parts by mass. If the amount of the condensation catalyst is too small, the effect of addition may not be obtained, for example, the curing rate may be slow. On the other hand, if the amount is too large, the physical properties such as strength of the resulting cured product may be reduced.

Solvent and Reactive Diluent A solvent and a reactive diluent can be added to the photocurable organopolysiloxane composition of the present invention. The solvent is not particularly limited as long as it is compatible with the alkali-soluble silicone resin described above. For example, ethers such as tetrahydrofuran, diglyme and triglyme, ketones such as methyl ethyl ketone and methyl isobutyl ketone, methanol, ethanol, propanol, butanol, 2-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 2-ethylhexyl Examples include alcohols, alcohols such as 1,4-butanediol, ethylene glycol, and propylene glycol. Examples of the reactive diluent include vinyl ethers, vinyl amides, epoxy resins, acrylic resins, modified silicone resins, oxetanes, allyl phthalates, and vinyl adipate.

  The amount of the solvent used is preferably 1,000 parts by mass or less (that is, 0 to 1,000 parts by mass), particularly 10 to 500 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin. Moreover, the usage-amount of a reactive diluent is 100 mass parts or less (namely, 0-100 mass parts) with respect to 100 mass parts of alkali-soluble silicone resins, and 10-50 mass parts is especially preferable.

Other Components Other components may be added to the photocurable organopolysiloxane composition of the present invention as necessary within a range not losing photolithography characteristics.

  For example, examples of the epoxy curing agent include amine compounds, imidazole compounds, carboxylic acids, phenols, and quaternary ammonium salts. Use of these epoxy group curing agents can improve the heat resistance, moisture resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, mechanical strength, and the like of the resulting film. The amount of the epoxy curing agent used may normally be 20 parts by mass or less (that is, 0 to 20 parts by mass), preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin. 01-10 mass parts is more preferable, and 0.1-5 mass parts is still more preferable.

  A photosensitizer is added in order to improve sensitivity. Specific examples of the photosensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, and 2,6-bis (4-dimethylaminobenzal) cyclohexanone. 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) ) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphtho Thiazole, 1,3-bis (4-dimethyl) Aminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N- Examples include tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole, and the like. Can do.

  The addition amount of the photosensitizer may be usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 0.01 to 10 parts by mass, more preferably 0 with respect to 100 parts by mass of the alkali-soluble silicone resin. .1 to 5 parts by mass. If the amount of the photosensitizer is small, the effect of increasing the sensitivity may not be obtained. If the amount of the photosensitizer is large, the resolution may be lowered.

  Specific examples of light absorbers include azo series, benzophenone series, amino ketone series, quinoline series, anthraquinone series, diphenyl cyanoacrylate series, triazine series, p-aminobenzoic acid series dyes, and organic dyes are often used. Used. Among these, azo dyes and benzophenone dyes are preferable.

  The addition amount of the light absorber may be usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 0.01 to 10 parts by mass, more preferably 0 with respect to 100 parts by mass of the alkali-soluble silicone resin. 0.1 to 3 parts by mass. If the amount added is too small, the effect of addition may not be obtained, and if the amount added is too large, the film properties after curing may be affected.

  A light absorber having a high ultraviolet and visible light absorption effect is useful for obtaining a high aspect ratio and high resolution. Further, an organic dehydrating agent such as an acid anhydride is blended in an amount of 20 parts by mass or less (that is, 0 to 20 parts by mass) with respect to 100 parts by mass of the alkali-soluble silicone resin, silica, alumina, titania, zirconia, calcium carbonate. Such inorganic oxide fine particles (<1 μm) can be blended in an amount of 100 parts by mass or less (that is, 0 to 100 parts by mass) with respect to 100 parts by mass of the alkali-soluble silicone resin.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of the antioxidant include BHT and vitamin B. Examples of the antifoaming agent and leveling agent include: Silicone surfactants, fluorosurfactants, acrylic resins, and the like can also be added. Moreover, various additives, such as an adhesive imparting agent and a plasticizer, can be appropriately added.

Photocurable organopolysiloxane composition The photocurable organopolysiloxane composition of the present invention comprises a photoacid generator, an optional condensation catalyst, a solvent, a reactive diluent, and an epoxy curing agent. And other necessary components such as a photosensitizer can be added and mixed uniformly, and can be used as a material for forming a negative type fine pattern transfer master.

Fine pattern transfer original plate The material for forming the fine pattern transfer original plate of the present invention thus obtained is soluble in a polar solvent such as an alkaline aqueous solution, alcohol, ketone, or ether in an uncured state. Since it is hardly soluble in these solvents, a pattern substrate for transfer can be produced by photolithography. For example, it is used as follows. That is, it is applied to a predetermined substrate using a coating device such as a spinner, and when the composition contains a solvent, the solvent is removed by heating, air drying, etc., preferably 50 μm or less (thickness after solvent drying), More preferably, after forming a composition film of 10 μm or less, 0.1 μm or more, particularly 0.5 μm or more, using a mask aligner or the like, the composition film surface is shielded directly or with a photomask, Irradiate light. Examples of the light to be irradiated include ultraviolet rays such as far ultraviolet rays (wavelengths: examples 193 nm and 253 nm), i rays (wavelength: 365 nm), g rays (wavelength: 436 nm), h rays (wavelength: 405 nm), and the like. After the exposure, the exposed portion of the composition film is cured by heat treatment. The heat treatment is preferably performed at 50 to 100 ° C. for several minutes to several tens of minutes.

  The composition film of the uncured portion (non-exposed portion) shielded by the photomask is, for example, inorganic alkalis such as potassium hydroxide, sodium carbonate, aqueous ammonia, primary amines such as ethylamine, diethylamine, etc. Consists of aqueous solutions of secondary amines, tertiary amines such as triethylamine, quaternary ammonium salts such as tetramethylammonium hydroxide, unsubstituted or hydroxy-substituted tetraalkylammonium hydroxide such as trimethylhydroxyethylammonium hydroxide A pattern corresponding to the photomask, that is, a fine pattern can be obtained by dissolving and removing an alkali developer or the like alone or in combination. Preferably, the alkaline aqueous solution is 0.1 to 5% by mass, preferably 1 to 3% by mass of an alkaline aqueous solution such as unsubstituted or hydroxy-substituted tetraalkylammonium hydroxide such as tetramethylammonium hydroxide. Alternatively, the same resolution can be achieved by using a polar organic solvent such as methanol or THF. After curing, heat treatment, preferably 100 ° C. or higher, particularly preferably by heating at a temperature of 120 to 150 ° C. for 1 to 2 hours, volatile components such as the solvent remaining in the cured film are completely scattered, Further, the curing reaction proceeds, and a film excellent in solvent resistance, heat resistance, moisture resistance, adhesion, releasability, and mechanical properties can be obtained.

  The material for forming a fine pattern transfer original plate of the present invention can form a pattern with good resolution in a thin film having a thickness of 0.5 μm or a thick film having a thickness of 50 μm in patterning using photolithography.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited to the following Example. In addition, in this example, an average molecular weight is a polystyrene conversion value by GPC (gel permeation chromatograph), the symbol Mw means a weight average molecular weight, and Me is a methyl group.

[Synthesis Example 1]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane (i) 0.15 mol and phenyltrimethoxysilane (ii) 0.15 mol were charged in a methanol solvent, and pure water and concentrated hydrochloric acid as an acid catalyst were added thereto. Was added dropwise with stirring, and a hydrolysis reaction was carried out at 25 ° C. Next, the reaction mixture is heated and refluxed in a 100 ° C. oil bath for 1 hour or longer to conduct a condensation polymerization reaction, and then the condensation polymerization reaction is further carried out while distilling off the solvent and by-produced alcohols. For 2 hours. Next, the obtained hydrolysis condensate was washed with water and then dissolved in tetrahydrofuran. The solution was filtered through a filter having a hole diameter of 0.8 μm. The solvent in the filtrate was distilled off under reduced pressure at 80 ° C./2 mmHg, and further vacuum-dried at room temperature for 24 hours to obtain an alkali-soluble organopolysiloxane (A) as a powdery solid. As a result of GPC measurement, the obtained polysiloxane (A) was Mw2,800.

[Synthesis Example 2]
In the same manner as in Synthesis Example 1, instead of 0.15 mol of 2- (3,4-epoxycyclohexylethyl) trimethoxysilane (i) and 0.15 mol of phenyltrimethoxysilane (ii), 2- (3, Alkali-soluble organopolysiloxane (B) was obtained using 0.06 mol of 4-epoxycyclohexylethyl) trimethoxysilane (i) and 0.24 mol of phenyltrimethoxysilane (ii). As a result of GPC measurement, the obtained polysiloxane (B) was Mw 3,200.

[Synthesis Example 3]
In the same manner as in Synthesis Example 1, instead of 0.15 mol of 2- (3,4-epoxycyclohexylethyl) trimethoxysilane (i) and 0.15 mol of phenyltrimethoxysilane (ii), 2- (3, Alkali-soluble organopolysiloxane (C) was obtained using 0.24 mol of 4-epoxycyclohexylethyl) trimethoxysilane (i) and 0.06 mol of methyltrimethoxysilane (iii). As a result of GPC measurement, the obtained polysiloxane (C) was Mw 3,500.

[Synthesis Example 4]
In the same manner as in Synthesis Example 1, instead of 0.15 mol of 2- (3,4-epoxycyclohexylethyl) trimethoxysilane (i) and 0.15 mol of phenyltrimethoxysilane (ii), 2- (3, 4-epoxycyclohexylethyl) trimethoxysilane (i) 0.06 mol, phenyltrimethoxysilane (ii) 0.18 mol, and dimethyldimethoxysilane (iv) 0.06 mol were used to convert the alkali-soluble organopolysiloxane (D). Obtained. As a result of GPC measurement, the obtained polysiloxane (D) was Mw 4,000.

[Synthesis Example 5]
In the same manner as in Synthesis Example 1, instead of 0.15 mol of 2- (3,4-epoxycyclohexylethyl) trimethoxysilane (i) and 0.15 mol of phenyltrimethoxysilane (ii), 2- (3, 4-epoxycyclohexylethyl) trimethoxysilane (i) 0.12 mol, methyltrimethoxysilane (iii) 0.12 mol and tetraethoxysilane (v) 0.06 mol were used to convert the alkali-soluble organopolysiloxane (E). Obtained. As a result of GPC measurement, the obtained polysiloxane (E) was Mw2,300.

[Examples 1 to 5]
10 parts by mass of each of the synthesized alkali-soluble organopolysiloxanes (A) to (E) as a material for forming a pattern portion constituting a fine pattern transfer master, and 4-methoxytriphenylsulfonium triflate as a photoacid generator (Midori Kagaku, MDS-105) 20 parts by mass of diglyme in which 0.5 parts by mass were dissolved were mixed uniformly to obtain the original materials (a) to (e) for pattern transfer of the present invention.

The obtained pattern transfer master forming materials (a) to (e) were applied to a mirror-finished SUS substrate by spin coating so as to adjust the number of revolutions so that the film thickness was about 5 μm. It was made to dry for 10 minutes with a ° C dryer. These coatings were not tacky in an uncured state. These coatings were exposed with a mask aligner through a quartz glass mask (50 mJ / cm ² ) and then heated with an 80 ° C. dryer for 15 minutes to cure the exposed portions. 2. Dissolve the unexposed film in 38% Me ₄ NOH aqueous solution by dipping method and clean it with pure water, so that the surface of SUS (conductive substrate) is reversed to the desired pattern by silicone resin (for transfer) ) An electrodeposited metal pattern coated with a pattern (L / S = 10 μm / 10 μm resolution pattern) was obtained. These pattern transfer master forming materials (a) to (e) were able to draw fine patterns of L / S = 1 μm / 1 μm by the same method. An SUS substrate patterned with these silicone resins was heated with a 150 ° C. dryer for 60 minutes to produce a fine pattern transfer master.

  Using these, a heat resistance and moisture resistance test, a solvent resistance test, a peelability test of the resin to be transferred, an adhesion test, and a transfer durability test were performed by the following methods.

Heat and humidity resistance tests Using the pattern transfer masters produced in Examples 1 to 5, a thermal cycle test (-20 ° C / 120 ° C) was performed 100 times. It was not seen. Moreover, although it processed at 85 degreeC / 85% RH for 100 hours, swelling of resin, peeling from a board | substrate, and generation | occurrence | production of a crack were not seen.

Solvent Resistance Test Using the pattern transfer original plate prepared in Examples 1 to 5, the solvent resistance of the resin was tested. After standing in a solvent for 24 hours, pattern deformation, peeling, swelling, dissolution, surface roughness and the like were confirmed. Table 1 shows the measurement results. In addition, the solvent resistance is one in which all of deformation, peeling, swelling, dissolution and surface roughness of the pattern are not recognized, and one in which any of deformation, peeling, swelling, dissolution and surface roughness of the pattern is recognized. X.

Removability test of transferred resin Several types of resins were applied on the pattern transfer masters prepared in Examples 1 to 5, and the resin was tested for releasability after pattern transfer. For the resin to be transferred, silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KJR-9022), epoxy resin (manufactured by Shin-Etsu Chemical Co., Ltd., Semicoat 115), PI (polyimide resin, manufactured by Shin-Etsu Chemical Co., Ltd.), X-45-300) was used. After curing, an adhesive tape was applied on each resin and peeled off from the original plate to test the peelability of each resin from the original plate. Table 3 shows the measurement results. The peelability was evaluated as “◯” when the same pattern as the original plate was transferred to the pressure-sensitive adhesive tape side, and “X” when all or part of the film was not transferred due to insufficient peeling. All of these polymers were completely peeled off and the pattern could be transferred.

Adhesion test The cured film (L / S = 1 mm / 1 mm, film thickness of about 10 μm) of the original plate forming materials (a) to (e) for pattern transfer on various substrates of SUS, silicon wafer, glass plate, BT, nickel In the same manner as described above, adhesion to various substrates was tested. The test method was performed by aligning a stainless steel plate having a thickness of 0.5 mm horizontally with respect to the interface between the various substrates and the cured coating, applying a peeling force laterally, and peeling the cured coating from the substrate. Table 3 shows the measurement results. In addition, the adhesiveness was evaluated as “◯” for completely cohesive failure, “Δ” for mixed peeling, and “×” for interfacial peeling. As a result, the peeling mode was cohesive failure for any substrate.

Transfer Durability Test In the pattern transfer masters produced in Examples 1 to 5, the exposed portion of the SUS surface not covered with the silicone resin pattern portion was subjected to an electrodeposition rate of 1.0 μm / mm using a copper plating bath. Copper plating was performed to a thickness of 5 μm at min (5 A / dm ² ). The electrodeposited metal pattern transfer original plate subjected to copper plating and a base material coated with an epoxy resin adhesive for printed circuit on one side of a prepreg are bonded together using a vacuum press machine at a pressure of 3 atm. Heating was performed for 120 minutes (120 ° C.) to cure the epoxy resin adhesive. After cooling, the copper plating pattern was completely transferred to the prepreg, and no damage was observed on the electrodeposition metal pattern transfer master. The same operation was repeated 100 times, but no pattern collapse, cracks, peeling, surface roughness, etc. of the original plate were observed. In addition, there was no difference in the pattern accuracy of the transferred resin between the first time and the 100th time.

[Comparative Example 1]
UV curable polysiloxane rubber (methyl phenyl polysiloxane having acryloxy groups at both ends of molecular chain (viscosity 3,000 cs at 25 ° C.) 10 parts by mass, photoinitiator (Darocur-1173C) 0.3 parts by mass uniformly The silicone resin composition mixed with was applied onto a silicon wafer by a spin coat method so as to have a thickness of about 5 μm, and exposed with a mask aligner (200 mJ / cm ² ) through a quartz glass mask. Since the resin did not become tack-free, the contact exposure could not be performed, and the silicone resin composition did not show alkali-solubility, and after exposure, developed with toluene, L / S = 1 mm / 1 mm, film thickness 5 μm A cured coating was obtained.
When the solvent resistance test with respect to the copper sulfate plating liquid of the obtained hardened film was conducted, it was found that the resin film was attacked by the plating liquid and was not resistant.

  As is clear from the above test results, according to the present invention, a master for fine pattern transfer excellent in heat and moisture resistance, solvent resistance, releasability from a transfer target, adhesion to a substrate, and durability. Can be obtained.

Claims (6)

(A) (i) The following general formula (1):
R ¹ _X R ² _Y Si (OR ³ ) _4-XY (1)
(In the formula, R ¹ represents a monovalent organic group having 2 to 30 carbon atoms having at least one hydrolyzable epoxide, and R ² represents an unsubstituted or substituted monovalent carbon group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 1 to 3, and Y is an integer of 0 to 2. Yes, 1 ≦ X + Y ≦ 3 is satisfied.)
And (ii) the following general formula (2):
R ² _Z Si (OR ³ ) _4-Z (2)
(In the formula, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon having 1 to 10 carbon atoms. Z represents an integer of 0 to 3.)
1 type or 2 types or more of silane compounds represented by the formula ( ¹⁾ with a proportion of 10 mol% or more based on the total organic groups excluding the organoxy group in which the organic group represented by R ¹ is bonded to a silicon atom, The weight average molecular weight obtained by mixing and co-hydrolyzing and condensing the organotriorganoxysilane compound and the tetraorganoxysilane compound in a proportion of 40 mol% or more of the total silane compounds is 500 to 50,000. A material for forming an original for fine pattern transfer comprising an alkali-soluble silicone resin (polystyrene equivalent value by GPC) and (B) a photocurable organopolysiloxane composition containing a photoacid generator.   Furthermore, the photocurable organopolysiloxane composition contains a condensation catalyst, The material for forming a fine pattern transfer original plate according to claim 1.   Furthermore, the photocurable organopolysiloxane composition contains a solvent and / or a reactive diluent. The material for forming a fine pattern transfer original plate according to claim 1 or 2, wherein:   Further, the photocurable organopolysiloxane composition is selected from an epoxy curing agent, a photosensitizer, a light absorber, a dehydrating agent, inorganic oxide fine particles, a polymerization inhibitor, an antioxidant, an antifoaming agent and a leveling agent. The material for forming a fine pattern transfer original plate according to any one of claims 1 to 3, wherein the material comprises one or more of the following.   A master for fine pattern transfer, on which a photocured film pattern of the forming material of the master for fine pattern transfer according to any one of claims 1 to 4 is formed. After forming the film | membrane of the forming material of any one of Claims 1 thru | or 4 on a base | substrate and exposing the required part of this film | membrane, the non-exposed part of this film | membrane is melt | dissolved and removed with alkaline aqueous solution or polar organic solvent And forming a photocured film pattern of the forming material having a shape corresponding to the exposed portion.