JP2008076630A - Method for stripping film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stripping a film by which the film can be stripped from a substrate, without using an acid or alkali or a special liquid, such as organic solvents, in a method for stripping from the substrate a film obtained, by applying a photosensitive composition comprising a condensate of an alkoxysilane on the substrate, and curing the photosensitive composition. <P>SOLUTION: The method for stripping from a substrate 2 a film 1C obtained by applying on the substrate 2 a photosensitive composition 1 comprises a condensate (A) of an alkoxysilane and a material (B), capable of crosslinking the condensate of the alkoxysilane upon irradiation with an active energy ray, and curing the photosensitive composition 1, by irradiation with an active energy ray, wherein the film 1C is stripped from the substrate 2 by applying ultrasonic waves to the film 1C, in water at 80-100°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for peeling a film obtained by curing a photosensitive composition from a substrate, and more specifically, a photosensitive composition containing a condensate of alkoxysilane is applied on a substrate, and the photosensitive composition is exposed. The present invention relates to a method for peeling a film obtained by curing a functional composition.

  In manufacturing electronic devices such as semiconductors, a passivation film, a gate insulating film, and the like are formed by a fine pattern forming method. For forming these films, for example, a photosensitive resin composition containing an alkoxysilane condensate or the like is used.

  In Patent Document 1 below, as an example of a photosensitive resin composition used for pattern formation, (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent are mainly used. A photosensitive resin composition as a component is disclosed. In Patent Document 1, (1) an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing alkoxysilane with water and a catalyst is used as the alkali-soluble siloxane polymer. Yes.

Patent Document 1 discloses a pattern forming method in which the photosensitive resin composition is applied onto a substrate, dried, exposed through a mask, and subsequently developed. In the pattern forming method described in Patent Document 1, specifically, a photosensitive resin composition layer made of a photosensitive resin composition is formed, and the photosensitive resin composition layer is exposed through a mask. In the exposed area, the crosslinking reaction of the alkoxysilane condensate was advanced to cure the photosensitive resin composition layer. Furthermore, by developing using a developing solution, the uncured photosensitive resin composition layer that was not cured was removed, and a pattern film was obtained.
Japanese Patent Laid-Open No. 06-148895

  However, when the pattern film is configured by the method described in Patent Document 1, a pattern film having a desired shape may not be obtained. In recent years, the miniaturization of the pattern film has progressed. However, in particular, when a fine pattern film is formed, a desired shape may not be obtained.

  When a pattern film having a desired shape cannot be obtained, it is necessary to discard the pattern film together with the substrate or peel the pattern film from the substrate. Conventionally, when peeling a pattern film from a substrate, a special liquid such as an acid, an alkali, or an organic solvent has been used. When such a special liquid is used, there is a problem that the environmental load is large and the cost is high.

  An object of the present invention is to peel off a film obtained by applying a photosensitive composition containing an alkoxysilane condensate on a substrate and curing the photosensitive composition in view of the above-described state of the art. An object of the present invention is to provide a film peeling method that can peel a film from a substrate without using a special liquid such as an acid, an alkali, or an organic solvent.

  In the present invention, an active energy ray is applied after a photosensitive composition containing an alkoxysilane condensate (A) and a substance (B) that crosslinks an alkoxysilane condensate by irradiation with active energy rays is applied on a substrate. Is a method of peeling a film obtained by curing a photosensitive composition by irradiating the film from the substrate, and peeling the film from the substrate by applying ultrasonic waves to the film in water at 80 to 100 ° C. It is characterized by.

  In a specific aspect of the film peeling method according to the present invention, ultrasonic waves are applied to the film for 5 to 30 minutes under the conditions of 0.8 to 3 MHz and 0.5 to 2 kW.

  In the film peeling method according to the present invention, the film is peeled off from the substrate by applying ultrasonic waves in water at 80 to 100 ° C. to the film obtained by curing the photosensitive composition on the substrate. The film can be peeled from the substrate without using a special liquid such as alkali, organic solvent, or the like. In the present invention, since it is not necessary to use a special liquid such as an acid, an alkali, or an organic solvent, the film can be peeled at a low cost, and the environmental load due to the waste liquid can be reduced.

  When ultrasonic waves are applied to the film for 5 to 30 minutes under the conditions of 0.8 to 3 MHz and 0.5 to 2 kW, the film can be more easily peeled from the substrate.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the inventors of the present invention have made extensive studies on a method of peeling a film obtained by curing a photosensitive composition from a substrate. As a result, ultrasonic waves are applied to the film in water at 80 to 100 ° C. By hitting, it has been found that the film can be sufficiently peeled from the substrate, and the present invention has been made.

  In the film peeling method of the present invention, the film is peeled from the substrate by applying ultrasonic waves to the film in water at 80 to 100 ° C. When the temperature of the water to which the ultrasonic waves are applied is less than 80 ° C., the film does not peel sufficiently from the substrate.

  In the present invention, ultrasonic waves are applied to the film in water at 80 to 100 ° C., and water is used to peel the film from the substrate. That is, the film is peeled from the substrate without using a special liquid such as an acid, an alkali, or an organic solvent. Since a special liquid such as an acid, an alkali, or an organic solvent is not used, the film can be peeled at a low cost, and the environmental load due to the waste liquid can be reduced. If a special liquid such as an acid, an alkali, or an organic solvent is used, the cost increases and the environmental load due to the waste liquid increases.

  Since the film can be more easily peeled from the substrate, it is preferable to apply ultrasonic waves to the film for 5 to 30 minutes under the conditions of 0.8 to 3 MHz and 0.5 to 2 kW.

  Next, the photosensitive composition used for constituting the film on the substrate and the method for forming the film will be described below.

  In the present invention, a photosensitive composition comprising an alkoxysilane condensate (A) and a substance (B) that crosslinks an alkoxysilane condensate by irradiation with active energy rays is used to form a film on a substrate. Used. After this photosensitive composition is coated on a substrate, the photosensitive composition can be cured by irradiating active energy rays to obtain a film.

  The alkoxysilane condensate (A) comprises a condensate obtained by condensing alkoxysilane. At least one kind of alkoxysilane condensate (A) is contained, and therefore, a condensate (A) of two or more kinds of alkoxysilanes may be contained.

  As the alkoxysilane condensate (A), an alkoxysilane condensate obtained by condensing an alkoxysilane represented by the following formula (1) is preferably used.

Si (R1) _p (R2) _q (R3) _4-pq Formula (1)
In the above formula (1), R1 represents hydrogen or a non-hydrolyzable organic group having 1 to 30 carbon atoms, R2 represents an alkoxy group, R3 represents a hydrolyzable group other than an alkoxy group, p represents an integer of 0 to 3, q represents an integer of 1 to 4, and p + q ≦ 4. When p is 2 or 3, the plurality of R1 may be the same or different. When q is 2-4, several R2 may be the same and may differ. When p + q ≦ 2, the plurality of R3 may be the same or different.

  The alkoxy group R2 and the hydrolyzable group R3 other than the alkoxy group are usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. without catalyst in the presence of excess water. A group capable of forming a silanol group, or a group capable of further condensation to form a siloxane bond.

  Although it does not specifically limit as said alkoxy group R2, Specifically, C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

  Although it does not specifically limit as hydrolysable group R3 other than the said alkoxy group, Specifically, halogeno groups, such as chlorine and a bromine, an amino group, a hydroxyl group, or a carboxyl group, etc. are mentioned.

  Although it does not specifically limit as said non-hydrolyzable organic group R1, It is hard to raise | generate hydrolysis and a C1-C30 organic group which is a stable hydrophobic group is mentioned. As the organic group having 1 to 30 carbon atoms which is a stable hydrophobic group, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, Alkyl groups having 1 to 30 carbon atoms such as hexadecyl group, octadecyl group and eicosyl group, and alkyl halide groups such as fluorinated, chlorinated and brominated alkyl groups (for example, 3-chloropropyl group, 6-chloropropyl group) , 6-chlorohexyl group, 6,6,6-trifluorohexyl group, etc.), aromatic substituted alkyl groups such as halogen-substituted benzyl groups (for example, benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, etc.) ), Aryl groups (eg phenyl group, tolyl group, mesityl group, naphthyl group, etc.), vinyl groups and epoxy groups Group, an organic group containing an amino group, and the like organic group containing a thiol group.

  Specific examples of the alkoxysilane include, for example, triphenylethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, ethyldimethylmethoxysilane, methyldiethylmethoxysilane, ethyldimethylethoxysilane, methyldiethyl. Ethoxysilane, phenyldimethylmethoxysilane, phenyldiethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylethoxysilane, methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, methyldiphenylethoxysilane, ethyldiphenylethoxysilane, tert-butoxytrimethylsilane, butoxy Trimethylsilane, dimethylethoxysilane, methoxydimethylvinylsilane , Ethoxydimethylvinylsilane, diphenyldiethoxysilane, phenyldiethoxysilane, dimethyldimethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane, diethoxydimethylsilane, Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-n Propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Tripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, tetra Decyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripropoxysilane, hex Sadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, eicosyldecyltrimethoxysilane, eicosyltriethoxysilane, eicosyltripropoxy Silane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane, benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltri Methoxysilane, triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraiso Examples include propoxysilane and tetraacetoxysilane. An alkoxysilane condensate obtained by condensing these alkoxysilanes is more preferably used. In constituting the alkoxysilane condensate, it is sufficient that at least one alkoxysilane is used, and therefore two or more alkoxysilanes may be used.

  In addition to the alkoxysilane condensate (A), the photosensitive composition further contains a substance (B) that crosslinks the alkoxysilane condensate by irradiation with active energy rays. When the photosensitive composition contains the substance (B), crosslinking of the alkoxysilane condensate (A) can be promoted when the photosensitive composition is irradiated with active energy rays.

  The substance (B) is not particularly limited as long as it can crosslink the alkoxysilane condensate by irradiation with active energy rays, but a photoacid generator or a photobase generator is preferably used. By selectively irradiating the photosensitive composition containing the photoacid generator or photobase generator with active energy rays, the photosensitive composition in the exposed portion can be cured.

  The content of the substance (B) is desirably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A). When the substance (B) is less than 0.05 parts by weight, the alkoxysilane condensate (A) may not be sufficiently crosslinked, and it may be difficult to form a film. When the amount of the substance (B) exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive composition on the substrate, and a residue may be generated after development.

Although it does not specifically limit as said photo-acid generator, For example, onium salt etc. are mentioned. More specifically, diazonium, phosphonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ , and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. .

  The photoacid generator is not particularly limited, but is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, Sulfonium salt compounds such as dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, iodonium salts such as diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide Such as trifluoromethanesulfonate. It is. A photo-acid generator may be used independently and 2 or more types may be used together.

  As the photoacid generator, at least one compound selected from the group consisting of a more reactive onium salt, diazonium salt, and sulfonic acid ester is more preferably used.

  Although it does not specifically limit as said photobase generator, For example, a cobalt amine complex, o-acyl oxime, a carbamic acid derivative, a formamide derivative, a quaternary ammonium salt, a tosyl amine, a carbamate, an amine imide compound etc. can be mentioned. Specific examples include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate, and the like. . A photobase generator may be used independently and 2 or more types may be used together.

  As the photobase generator, an amine imide compound that generates a base by irradiation with active energy rays is preferably used. Such an amine imide compound is not particularly limited as long as it generates a base when irradiated with active energy rays. Examples of such amine imide compounds include compounds represented by the following general formula (2) or (3).

In the above formulas (2) and (3), R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylidene having 1 to 8 carbon atoms. Group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group And a benzyl group substituted with a group, a benzyl group, an electron donating group and / or an electron withdrawing group. As a C1-C8 alkyl group, the alkyl group which has a substituent other than a linear alkyl group, for example, an isopropyl group, an isobutyl group, t-butyl group etc. are included. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 7 to 12 carbon atoms. Is preferred. R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. Ar ¹ in the general formula (2) is an aromatic group, and such an amine imide compound is known prior to the filing of the present application as disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-35949. Are available. In the general formula (3), Ar ² is an aromatic group.

  The amine imide compound has higher base generation efficiency than a compound that generates a primary or secondary amine when irradiated with active energy rays. Therefore, it is desirable to include an amine imide compound because the exposure time can be shortened and the manufacturing process can be shortened.

  In addition to these photoacid generators and photobase generators, a sensitizer may be further added to increase sensitivity.

  The sensitizer is not particularly limited. Specifically, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, Anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2- Chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-t rt-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis ( 5,7-dimethoxycarbonylcoumarin) and coronene, and the like are preferable.

  The photosensitive composition may contain a thermal acid generator or a thermal base generator capable of crosslinking the alkoxysilane condensate (A) by heat treatment, in addition to the substance (B). When the photosensitive composition contains a thermal acid generator or a thermal base generator, a condensate of alkoxysilane that is not crosslinked in the exposed area (A, for example, by heat treatment after irradiating the photosensitive composition with active energy rays (A ) Or the crosslinking of the alkoxysilane condensate (A) can be suppressed in the exposed area.

  When the photosensitive composition contains a thermal acid generator or a thermal base generator, the thermal acid generator or thermal base generator is added in an amount of 0.001 to 30 with respect to 100 parts by weight of the alkoxysilane condensate (A). It is preferably contained in the range of parts by weight. It is preferable to contain in the ratio of 0.001-30 weight part. When the thermal acid generator or the thermal base generator is less than 0.001 part by weight, the alkoxysilane condensate (A) is crosslinked or the crosslinking of the alkoxysilane condensate (A) is suppressed when heat-treated. The effect may not be sufficiently obtained, and if it exceeds 30 parts by weight, a residue resulting from an excessive thermal acid generator or thermal base generator tends to be generated in the obtained film.

  The thermal acid generator is not particularly limited, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and sulfonic acid esters. It is done.

Examples of the thermal acid generator include diazonium salts (SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Bal et al, Polymer, 21, 423 (1980). Clarified), ammonium salts (specified in the specifications of U.S. Pat. Nos. 4,0690,05, 4,690,056, Reissued 27992, and JP-A-4-365049), phosphonium salts (DC Necker et al, Macromolecules) 17, 2468 (1984), C. S. Wen et al, Teh, Proc. Conf. Rad, Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent Nos. 4069055 and 4069056. ), Iodonium salts (J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104143, US Pat. No. 3,39049, No. 410201 Specification, JP-A-2-150848 and JP-A-2-296514), sulfonium salts (JV Crivello et al, Polymer J. 17, 73 (1985), JV Crivello et al. J. Org.Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivello et al, Polymer Bull., 1 , 279 (1985), JV Crivello et al, Macromolecules, 14 (5), 1141 (1981), JV Crivel. Lo et al, J. Polymer Sci., Polymer Chem. Ed., 17, U.S. Pat. No. 2833827, German Patent Nos. 2904626, 3604580 and 360481, and selenonium salt (JV Crivello et al, Macromolecules, 10 (6) 1307 (1977), J. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979)), and arsonium salts (specified in CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988)). Examples of the counter anion of the onium salt include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ . These thermal acid generators may be used alone or in combination of two or more.

  Since acid is efficiently generated by heat treatment, at least one compound selected from the group consisting of iodonium salts, sulfonium salts and sulfonic acid esters is more preferably used as the thermal acid generator.

  The thermal base generator is not particularly limited, and examples thereof include ammonium salts such as monoalkyltrimethylammonium chloride, monoalkylbenzyldimethylammonium chloride, dialkylethylmethylammonium ethosulphate, dialkyldimethylammonium chloride, and alkyldiammonium chloride; Amines such as alkylamines, dialkylamines, trialkylamines, aromatic amines, alkanolamines; diamino compounds having 2 nitrogen atoms in the same molecule, diamino polymers having 3 or more nitrogen atoms, Examples include amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

  Examples of these compounds or polymers include monoalkylamines such as n-decylamine, hexadecylamine, and octadecylamine; di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di- Dialkylamines such as -n-octylamine, di-n-nonylamine, di-n-decylamine; tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, Examples thereof include trialkylamines such as tri-n-octylamine, tri-n-nonylamine and tri-n-decylamine; aromatic amines such as diphenylamine, triphenylamine and 1-naphthylamine. Diamino compounds having two nitrogen atoms in the same molecule, for example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2- ( 3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxy Phenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, etc. be able to. Examples thereof include diamino polymers having 3 or more nitrogen atoms, such as polymers of polyethyleneimine, polyallylamine, and dimethylaminoethylacrylamide.

  Examples of the nitrogen-containing heterocyclic compound include imidazoles such as 4-methyl-2-phenylimidazole; pyridines such as 2-phenylpyridine, 4-phenylpyridine and N-methyl-4-phenylpyridine. be able to. These thermal base generators may be used alone or in combination of two or more.

  Since the base is efficiently generated by the heat treatment, at least one compound selected from the group consisting of dialkylamines, trialkylamines and aromatic amines is more preferably used as the thermal base generator.

  In addition to the alkoxysilane condensate (A) and the substance (B) that crosslinks the alkoxysilane condensate (A) by irradiation with active energy rays, an appropriate solvent may be added to the photosensitive composition. . By adding a solvent, a photosensitive composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the alkoxysilane condensate (A), but aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, cyclohexene, Saturated or unsaturated hydrocarbons such as dipentene, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane Compound: diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di Propyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclo Xylene, methylcyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone Ketones such as cyclohexanone and cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, stearin And esters such as butyl acid. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select suitably the mixture ratio of the said solvent so that it may apply uniformly, for example, when a photosensitive composition is applied on a board | substrate and a film | membrane is formed. Preferably, the concentration of the photosensitive composition is 0.5 to 60% by weight, more preferably about 2 to 40% by weight in terms of solid content.

  If necessary, other additives may be further added to the photosensitive composition. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors.

  In this invention, after apply | coating a photosensitive composition on a board | substrate, the film obtained by hardening a photosensitive composition by irradiating an active energy ray is peeled from a board | substrate. In FIG. 1, an example of the manufacturing flow of the film | membrane using the photosensitive composition mentioned above is shown with a schematic block diagram.

  As shown in FIG. 1, when forming a film, for example, a step of applying a photosensitive composition on a substrate, a step of curing the photosensitive composition, a step of developing the photosensitive composition to obtain a film, This is done in this order.

  Although it does not specifically limit in the process of apply | coating the photosensitive composition on the said board | substrate, As shown to Fig.2 (a), the photosensitive composition 1 is apply | coated to the predetermined thickness on the board | substrate 2, for example. As a specific method in this case, a general coating method can be used, for example, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating. Work, gravure coating, etc. can be used. As a substrate to which the photosensitive composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. Although the thickness of the photosensitive composition apply | coated on the board | substrate 2 changes with uses, 10 nm-10 micrometers become a standard.

  Next, as shown in FIG. 2B, the photosensitive composition 1 is irradiated with active energy rays according to the pattern to be formed, and the alkoxysilane condensate (A) is crosslinked by the action of the substance (B). Then, the photosensitive composition 1 is cured.

  For example, by selectively irradiating the photosensitive composition 1 with active energy rays using a photomask 3 or the like, the alkoxysilane condensate (A) is crosslinked in the exposed area, and the photosensitive composition in the exposed area. 1A becomes insoluble in the developer. On the other hand, the photosensitive composition 1B in the unexposed area that has not been irradiated with active energy rays remains soluble in the developer. As the photomask 3, a commercially available general mask may be used.

The light source for irradiating active energy rays such as ultraviolet rays, visible rays, or radiation is not particularly limited, but an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, etc. may be used. it can. These light sources are appropriately selected according to the photosensitive wavelength of the substance (B) or the sensitizer. The irradiation energy of active energy rays is generally in the range of 10 to 3000 mJ / cm ² , although it depends on the desired film thickness, substance (B), or type of sensitizer. When 10 mJ / cm ² less than, may condensate of alkoxysilane (A) is not sufficiently crosslinked, and greater than 3000 mJ / cm ^2, there is a possibility that the exposure time becomes long, production efficiency per time of the membrane May decrease.

  After irradiating the active energy ray, as shown in FIG. 2C, the photosensitive composition 1 is developed with a developing solution, and the photosensitive composition 1B in the unexposed area is removed, whereby a film that is a pattern film A step of obtaining 1C is performed.

  By developing the photosensitive composition with a developer, the unexposed area of the photosensitive composition is dissolved and removed in the developer, and the exposed area of the photosensitive composition remains on the substrate. As a result, a film that is a pattern film is obtained. This pattern is called a negative pattern because the photosensitive composition in the unexposed area is removed, and a negative photosensitive composition is used.

  In FIG. 2, the photosensitive composition in the unexposed area is removed, but the positive photosensitive composition capable of obtaining a pattern film called a positive pattern from which the photosensitive composition in the exposed area is removed. Things are also known. In the film peeling method of the present invention, not only a film obtained by curing a negative photosensitive composition but also a film obtained by curing such a positive photosensitive composition. Can be used.

  Here, the development is an operation of immersing the photosensitive composition in the exposed area or the photosensitive composition in the unexposed area in a developer such as an alkaline aqueous solution, and washing the surface of the photosensitive composition with the developer. Alternatively, various operations for treating the photosensitive composition with the developer, such as an operation of spraying the developer onto the surface of the photosensitive composition, are included.

  The developer is a solution that dissolves the photosensitive composition in the unexposed area or the exposed area after irradiating the photosensitive composition with active energy rays. In the formation of the negative pattern, since the photosensitive composition in the exposed portion is cured, it does not dissolve in the developer. The developer is not limited to an alkaline aqueous solution, and an acid aqueous solution or various solvents may be used. Examples of the solvent include the various solvents described above. Examples of the acidic aqueous solution include oxalic acid, formic acid, acetic acid and the like.

  As the developer, an explosion-proof facility is unnecessary, and the burden on the facility due to corrosion or the like is small, so an alkaline aqueous solution is preferably used. For example, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, are mentioned. The time required for development depends on the thickness of the photosensitive composition and the type of solvent, but is preferably in the range of 10 seconds to 5 minutes because development can be efficiently performed and production efficiency is increased. It is preferable to wash the film with distilled water after development to remove the developer such as an aqueous alkali solution remaining on the film.

  As shown in FIG. 1, when a film obtained by developing the photosensitive composition after developing the photosensitive composition and then developing the photosensitive composition has a good shape, the film is left as a pattern film. Can be used. On the other hand, as shown in FIG. 2D, the film is peeled off when it is desired to peel the film from the substrate, for example, because the film has a non-uniform shape. The substrate can be reused by peeling the film from the substrate as described above.

  The photosensitive composition is used to form a pattern film in various apparatuses. For example, a film obtained by curing the photosensitive composition is used as an insulating protective film of an electronic device. Examples of such an insulating protective film for an electronic device include a TFT protective film for protecting a thin film transistor (TFT) in a liquid crystal display element, and a protective film for protecting a filter in a color filter. Moreover, the film | membrane obtained by hardening the said photosensitive composition is used also as an interlayer insulation film of a semiconductor element, or a passivation film. Furthermore, the film obtained by curing the photosensitive composition can be used as an insulating protective film for various electronic devices such as a TFT protective film for organic EL elements, an interlayer protective film for IC chips, and an insulating layer for sensors. Widely used.

  Hereinafter, the present invention will be clarified by giving examples of the present invention. In addition, this invention is not limited to a following example.

(Examples and Comparative Examples)
First, films L1 to L3 were respectively formed on the substrate.

(1) Membrane L1
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate (A1).

  100 parts by weight of the above-mentioned alkoxysilane condensate (A1) and naphthalimide camphor sulfonate (sulfonium salt photoacid generator, CAS No. 83697-56-7, manufactured by Midori Chemical Co., Ltd. as a product (B1) Name: NAI-106) 5 parts by weight was mixed and then dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a negative photosensitive composition.

  As the substrate, a glass substrate having aluminum deposited on the surface layer was used, and the photosensitive composition was spin-coated on the glass substrate at a rotation speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, the coating film is irradiated with ultraviolet light having a wavelength of 365 nm through a photomask having a predetermined pattern, using an ultraviolet irradiation device (USHIO ELECTRIC CO., LTD., Spot Cure SP-5). The condensate (A1) was crosslinked to cure the photosensitive composition. Irradiation was performed for 5 seconds at an ultraviolet illuminance of 100 mW / cm ² so that the irradiation energy of the ultraviolet light was 500 mJ / cm ² .

  Next, the coating film was heat-treated in a hot air oven at 150 ° C. for 5 minutes. Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a film L1 on the substrate.

(2) Membrane L2
To a 100 ml flask equipped with a condenser, 12.8 g of phenyltriethoxysilane, 2.2 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate (A2).

  100 parts by weight of the above-mentioned alkoxysilane condensate (A2) and sulfonate (photoacid generator, CAS No. 34684-40-7, Midori Chemical, trade name: SI-105) as a substance (B2) 5 weight After mixing with 500 parts by weight of tetrahydrofuran as a solvent, a negative photosensitive composition was prepared.

  A film L2 was formed on the substrate in the same manner as the formation of the film L1 except that this photosensitive composition was used.

(3) Membrane L3
100 parts by weight of the above alkoxysilane condensate (A1) and a carbamate compound as the substance (B3) (photobase generator, CAS No. 119137-03-0, manufactured by Midori Chemical Co., Ltd., trade name: NBC-101) 5 parts by weight and 3 parts by weight of cyclohexyl-p-toluenesulfonate (thermal acid generator) were mixed and then dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a positive photosensitive composition.

  In addition, when this positive photosensitive composition is exposed and heat-treated, in the exposed portion, a neutralization reaction between a base generated from the photobase generator by exposure and an acid generated from the thermal acid generator by heat treatment. And the crosslinking of the alkoxysilane condensate is prevented, while in the unexposed area, the crosslinking of the alkoxysilane condensate proceeds by the action of the acid generated from the thermal acid generator.

  A film is formed on the substrate in the same manner as in the formation of the film L1 except that this photosensitive composition is used to crosslink the alkoxysilane condensate (A1) in the unexposed area to cure the photosensitive composition. L3 was formed.

[Membrane peeling]
For the films L1 to L3 obtained as described above, an attempt was made to peel off the films L1 to L3 by ultrasonic waves. Under the conditions shown in Table 1 below, the peeled state of the films L1 to L3 was evaluated according to the following evaluation criteria by applying ultrasonic waves to the film in water.

Evaluation criteria for peeling state of film ○: The film was peeled from the substrate Δ: The film was slightly left on the substrate ×: The film was not peeled from the substrate The results are shown in Table 1 below.

  As apparent from Table 1, when ultrasonic waves were applied to the films L1 to L3 in water at 80 to 100 ° C., the films L1 to L3 were peeled off from the substrate. On the other hand, the films L1 to L3 were not peeled from the substrate even when immersed for 1 hour only by immersing the films L1 to L3 in 80 ° C. water or 100 ° C. water without applying ultrasonic waves. Further, even when ultrasonic waves were applied to the films L1 to L3 for 10 minutes in water at 70 ° C., the films L1 to L3 did not peel from the substrate.

The schematic block diagram which shows the manufacture flow which forms a film | membrane using the photosensitive composition. (A)-(d) is sectional drawing for demonstrating each process which peels a film | membrane after forming a film | membrane using the photosensitive composition.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition 1A ... Photosensitive composition of exposed part 1B ... Photosensitive composition of unexposed part 1C ... Film | membrane 2 ... Board | substrate 3 ... Photomask

Claims (2)

After the photosensitive composition containing the alkoxysilane condensate (A) and the substance (B) that crosslinks the alkoxysilane condensate by irradiation with active energy rays is applied on the substrate, the active energy rays are irradiated. A method of peeling the film obtained by curing the photosensitive composition from the substrate,
A method for peeling a film, comprising peeling the film from the substrate by applying ultrasonic waves to the film in water at 80 to 100 ° C.   The film peeling method according to claim 1, wherein ultrasonic waves are applied to the film for 5 to 30 minutes under conditions of 0.8 to 3 MHz and 0.5 to 2 kW.

Images