JP2008224872A - Method for peeling film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for peeling a film by which the film comprising a cured product can easily be peeled from a substrate to allow reuse of the substrate, as a method for peeling from a substrate a film comprising a cured product obtained by applying a photosensitive composition on the substrate and curing it. <P>SOLUTION: A photosensitive composition 1 containing a condensate (A) of an alkoxysilane, a first stimulant (B) which is activated by a stimulus to crosslink the condensate (A) of the alkoxysilane, and a second stimulant (C) which is activated by a stimulus different from the stimulus activating the first stimulant (B) is applied on a substrate 2, and a film 1C comprising a cured product obtained by curing the photosensitive composition 1 by applying the stimulus activating the first stimulant (B) to the photosensitive composition 1 is peeled from the substrate 2 by applying the stimulus activating the second stimulant (C) to the film 1C. <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. It is related with the peeling method of the film | membrane which consists of hardened | cured material obtained by hardening an adhesive 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. As a material for these films, for example, a photosensitive resin composition containing an alkoxysilane condensate or the like is used.

  In the following Patent Document 1, as an example of a photosensitive resin composition used for forming a fine pattern, (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent. A photosensitive resin composition containing as a main component is disclosed. The (1) alkali-soluble siloxane polymer is obtained by removing water and a catalyst from a reaction solution obtained by hydrolysis and condensation by adding water and a catalyst to alkoxysilane.

In the pattern forming method described in Patent Document 1, first, a photosensitive resin composition layer made of a photosensitive resin composition is formed on a substrate. Next, the photosensitive resin composition layer is exposed through a mask. Thereby, the crosslinking reaction of the alkoxysilane condensate proceeds in the exposed area, and the photosensitive resin composition layer is cured. Curing does not proceed in the unexposed areas. After that, the photosensitive resin composition layer in the unexposed area is removed by developing with a developer. Thereby, the pattern which consists of a hardened | cured material film of a photosensitive composition was obtained.
Japanese Patent Laid-Open No. 06-148895

  By the way, when the pattern which consists of hardened | cured material films is comprised by the method of patent document 1, especially when the refinement | miniaturization of a pattern is calculated | required, the pattern of the desired shape may not be obtained.

  When a pattern having a desired shape could not be obtained, the pattern had to be discarded along with the substrate. Therefore, there is a problem that the cost is high. Alternatively, it is necessary to peel the pattern from the substrate. However, conventionally, in order to peel a cured product film constituting a pattern from a substrate, for example, a cured product such as a relatively weak acid or alkali solution used in forming the film is used. The film cannot be peeled from the substrate. Therefore, for example, a relatively strong acid or alkali solution or an organic solvent has been used. Since such a liquid had to be used, the working environment was deteriorated and the environmental load was inevitably increased.

  An object of the present invention is to provide a film made of a cured product 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 prior art. An object of the present invention is to provide a method for peeling a film from a substrate, in which a film made of a cured product can be easily peeled from the substrate, and the substrate can be reused.

  The present invention activates an alkoxysilane condensate (A), a first stimulant (B) that is activated by stimulation and crosslinks the alkoxysilane condensate (A), and the first stimulant (B). After the photosensitive composition containing the second stimulant (C) activated by a stimulus different from the stimuli to be converted is applied on the substrate, the photosensitive composition applied on the substrate is subjected to the first stimulus. A method of peeling a film made of a cured product obtained by curing the photosensitive composition by giving a stimulus for activating the agent (B) from the substrate. A stimulus for activating the stimulant (C) is given, and the film made of the cured product is peeled off from the substrate.

  In a specific aspect of the film peeling method according to the present invention, the first stimulant (B) is a stimulant activated by irradiation with active energy rays or heat treatment, and the first stimulant (B). The stimulus that activates is active energy rays or heat.

  In another specific aspect of the film peeling method according to the present invention, the first stimulant (B) is a stimulant activated by irradiation with active energy rays, and the first stimulant (B) The stimuli to be activated are active energy rays.

  In still another specific aspect of the film peeling method according to the present invention, the first stimulant (B) is a photoacid generator or a photobase generator.

  In another specific aspect of the film peeling method according to the present invention, the second stimulant (C) is a stimulant activated by irradiation of active energy rays or heat treatment, and the second stimulant (C ) Is an active energy ray or heat.

  In another specific aspect of the film peeling method according to the present invention, the second stimulant (C) is a stimulant that generates a strong acid when stimulated.

  In still another specific aspect of the film peeling method according to the present invention, the second stimulant (C) is a stimulant that is not activated by a stimulus that activates the first stimulant (B).

  In the film peeling method according to the present invention, a photosensitive composition containing a first stimulant (B) and a second stimulant (C) is applied on a substrate, and then the photosensitive composition is coated with a second composition. Since the film | membrane which consists of hardened | cured material obtained by hardening the photosensitive composition by giving the stimulus which activates 1 stimulant (B), it is 2nd in the film | membrane which consists of hardened | cured material. Of the stimulant (C). Therefore, the film made of the cured product can be peeled from the substrate by applying a stimulus for activating the second stimulant (C) such as active energy rays or heat to the film made of the cured product. Therefore, the substrate can be reused and the cost can be reduced.

  Further, by devising the second stimulant (C), the film made of the cured product can be peeled off from the substrate without using a relatively strong acid solution, a relatively strong alkali solution, or an organic solvent. it can. That is, for example, the film can be peeled from the substrate using a developing solution such as a relatively weak acid solution or a relatively weak alkali solution used when forming the film. Therefore, it is possible to prevent the working environment from deteriorating and further reduce the environmental load due to the waste liquid.

  When the first stimulant (B) is a stimulant activated by irradiation with active energy rays or heat treatment, and the stimulus for activating the first stimulant (B) is active energy rays or heat In this case, a film can be more easily formed on the substrate by irradiation with active energy rays or heat treatment.

  When the first stimulant (B) is a stimulant activated by irradiation with active energy rays, and the stimulus for activating the first stimulant (B) is active energy rays, a mask or the like By selectively irradiating an active energy ray to the photosensitive composition using a film, a film made of a cured product having a desired pattern shape can be easily formed.

  When the first stimulant (B) is a photoacid generator or a photobase generator, it is possible to generate an acid or a base simply by irradiating active energy rays. Therefore, the film can be easily formed.

  When the second stimulant (C) is a stimulant activated by irradiation of active energy rays or heat treatment, and the stimulus for activating the second stimulant (C) is active energy rays or heat In this case, the film can be more easily separated from the substrate by irradiating with active energy rays or applying heat treatment.

  When the second stimulant (C) is a stimulant that generates a strong acid when a stimulus is applied, the film can be more effectively peeled off from the substrate.

  When the second stimulant (C) is not activated by a stimulus that activates the first stimulant (B), the photosensitive composition is stimulated to activate the first stimulant (B). When applied, the second stimulant (C) is activated and does not inhibit the curing of the photosensitive composition. Further, since the second stimulant (C) is not consumed by the stimulus that activates the first stimulant (B), the cured film is given a stimulus that activates the second stimulant (C), The cured product film can be more reliably 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 intensively studied a method for peeling a film made of a cured product obtained by curing a photosensitive composition containing a condensate (A) of alkoxysilane from a substrate. As a result, the photosensitive composition constituting the film contains the first stimulant (B) that crosslinks the alkoxysilane condensate (A) and the second stimulant (C), thereby providing photosensitivity. After stimulating the composition for stimulating the first stimulant (B) to obtain a film made of a cured product, the film made of the cured product is stimulated to activate the second stimulant (C). Thus, the present inventors have found that a film made of a cured product can be easily peeled off from the substrate, and have made the present invention.

  In the present invention, in order to constitute a film made of a cured product on the substrate, the alkoxysilane condensate (A) and the first stimulant activated by stimulation to crosslink the alkoxysilane condensate (A) ( A photosensitive composition containing B) and a second stimulant (C) that is activated by a stimulus different from the stimulus that activates the first stimulant (B) is used.

  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 (a) is preferably used.

Si (R1) _p (R2) _q (R3) _4-pq Formula (a)
In the above formula (a), 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 first stimulant (B) that is activated by stimulation to crosslink the alkoxysilane condensate (A). When the photosensitive composition contains the first stimulant (B), when the photosensitive composition is stimulated to activate the first stimulant (B), a Si—O—Si bond is generated. The crosslinking of the alkoxysilane condensate (A) proceeds, and the photosensitive composition is cured. By curing the photosensitive composition on the substrate, a film made of a cured product can be formed on the substrate.

  The first stimulant (B) is not particularly limited and can be used as long as it is activated by stimulation to crosslink the alkoxysilane condensate (A).

  Since the alkoxysilane condensate (A) can be easily cross-linked by irradiation with active energy rays or heat treatment, the first stimulant (B) is a stimulant activated by irradiation with active energy rays or heat treatment. It is preferable that By selectively irradiating the photosensitive composition with active energy rays using a mask or the like, a film made of a cured product having a desired pattern shape can be easily formed. Therefore, the first stimulant (B ) Is more preferably a stimulant activated by irradiation with active energy rays.

  In addition, when the first stimulant (B) is a stimulant activated by irradiation with active energy rays, the stimulus for activating the first stimulant (B) is active energy rays, and heat treatment In the case of the stimulant that is activated by, the stimulus that activates the first stimulant (B) is heat.

  As the first stimulant (B), a photoacid generator or a photobase generator that is activated by irradiation with active energy rays is preferably used. By selectively irradiating the photosensitive composition containing the photoacid generator or photobase generator with active energy rays using a mask or the like, the photosensitive composition in the exposed portion can be cured. As the first stimulant (B), a thermal acid generator or a thermal base generator activated by heat treatment may be used.

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.

  Commercially available photoacid generators activated by an active energy ray (i-line) having a wavelength of 365 nm include trade name “IC819” manufactured by Ciba Specialty Chemicals, trade name “SP172” manufactured by ADEKA, etc. Is mentioned. Examples of the photoacid generator that is activated by an active energy ray (g-ray) having a wavelength of 436 nm include trade names “PAG103”, “PAG108”, “PAG121” manufactured by Ciba Specialty Chemicals.

  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.

  Although it does not specifically limit as said thermal acid generator, For example, onium salt etc. are mentioned, It uses preferably.

  The thermal acid generator is more preferably at least one compound selected from the group consisting of diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts.

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 US Pat. Nos. 4,0690,05, 4,690,056, and 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 salts (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 ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , C ₈ F ₁₇ SO ₃ ^— and CH ₃ SO ₃ ^— . These thermal acid generators may be used alone or in combination of two or more.

  Although it does not specifically limit as said thermal base generator, For example, dialkylamines, trialkylamines, aromatic amines, etc. are mentioned, It uses preferably. These thermal base generators may be used alone or in combination of two or more.

  The content ratio of the first stimulant (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 first stimulant (B) is less than 0.05 parts by weight, the alkoxysilane condensate (A) may not be sufficiently crosslinked, and it is difficult to form a film made of a cured product. There is. When the first stimulant (B) exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive composition onto the substrate, and a residue may be generated after development.

  In addition to the first stimulant (B), the photosensitive composition further includes a second stimulant (C) that is activated by a stimulus different from the stimulus that activates the first stimulant (B). contains.

  Since the photosensitive composition contains the second stimulant (C), the film made of a cured product obtained by curing the photosensitive composition contains the second stimulant. The film made of the cured product obtained by curing the photosensitive composition can be stimulated to activate the second stimulant (C), and the film made of the cured product can be peeled from the substrate.

  The second stimulant (C) is not particularly limited as long as it is activated by a stimulus different from the stimulus that activates the first stimulant (B), and the first stimulant (B) The above-mentioned photoacid generator, photobase generator, thermal acid generator, thermal base generator, and the like mentioned above can be used in appropriate combination with the first stimulant (B).

  Since the film can be easily peeled off from the substrate by irradiation with active energy rays or heat treatment, the second stimulant (C) is a stimulant activated by irradiation with active energy rays or heat treatment. preferable. When the second stimulant (C) is a stimulant that is activated by irradiation with active energy rays, the stimulus that activates the second stimulant (C) is active energy rays, and heat treatment In the case of the stimulant that is activated by, the stimulus that activates the second stimulant (C) is heat.

  The second stimulant (C) is preferably a stimulant that generates a strong acid when a stimulus is applied, and more preferably a stimulant that generates a strong acid when irradiated with active energy rays. Since a strong acid is generated by irradiation with active energy rays, the second stimulant (C) is more preferably a compound represented by the following formula (1).

During the above-mentioned formula (1), X ^- is PF- ₆ ^- or SbF ₆ ^- _represents, R 1, _{R 2} and _{R 3} are hydrogen, halogen, or oxygen, halogen, nitrogen, which may contain sulfur or fluorine carbide It represents a hydrogen group, and R ₁ , R ₂ and R ₃ may be the same or different, and the positions of R ₁ and R ₂ are not limited.

In the above formula (1), specific examples of R ₁ , R ₂ and R ₃ include, for example, hydrogen, halogen, alkyl group, hydroxyalkyl group, alkoxy group, hydroxyalkoxy group, acyl group, and substituent. And a group selected from the group consisting of an optionally substituted phenyl group, an optionally substituted phenoxy group, a polyoxyalkylene group and an ester group. The second stimulant (C) is R ₁ , R _2. And compounds in which R ₃ is composed of these groups are more preferably used. When R ₁ , R ₂ and R ₃ are composed of these groups, R ₁ , R ₂ and R ₃ may be the same or different.

  As a commercial item of the compound represented by the formula (1) described above, trade names “SP-150”, “SP-170”, “SP-152”, “SP-172” manufactured by ADEKA, and the like can be given. .

  The second stimulant (C) is preferably not activated by a stimulus that activates the first stimulant (B). When a stimulant that is not activated by a stimulus that activates the first stimulant (B) is used, when the stimulus that activates the first stimulant (B) is applied to the photosensitive composition, the second The stimulant (C) does not inhibit the curing of the photosensitive composition. Moreover, since the 2nd stimulant (C) is not consumed by the stimulus which activates the 1st stimulant (B), the peelability of hardened | cured material film is also improved.

  The photosensitive composition preferably contains 0.2 to 15 parts by weight of the second stimulant (C) with respect to 100 parts by weight of the alkoxysilane condensate (A). When the second stimulant (C) is less than 0.2 parts by weight, the peelability of the film made of the cured product may be inferior, and when it exceeds 15 parts by weight, the second stimulus is excessive in the cured product film. Residue resulting from the agent (C) is likely to occur.

  An appropriate solvent may be added to the photosensitive composition in addition to the components described above. 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 the photosensitive composition on a board | substrate, the film | membrane which consists of hardened | cured material obtained by hardening | curing this photosensitive composition 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 made of a cured product on a substrate, for example, a step of applying a photosensitive composition on a substrate, a step of curing the photosensitive composition, and developing the photosensitive composition. The process of obtaining a film made of a cured product is performed 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, a stimulus for activating the first stimulant (B) is applied, and the condensate (A) of alkoxysilane is formed by the action of the first stimulant (B). The photosensitive composition 1 is cured by crosslinking. In addition, when a 1st stimulant (B) is a stimulant activated by irradiation of an active energy ray, an active energy ray can be selectively irradiated according to the pattern to form.

  For example, a photomask 3 or the like is used to selectively irradiate the photosensitive composition 1 with an active energy ray that activates the first stimulant (B), whereby an alkoxysilane condensate (A ) Are crosslinked, and the photosensitive composition 1 is cured. When the photosensitive composition 1 in the exposed portion is cured, a film 1A made of a cured product is formed and 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 is soluble in the developer. As the photomask 3, a commercially available general mask may be used.

  Although it does not specifically limit as a light source for irradiating the active energy ray for activating the 1st stimulant (B), An ultrahigh pressure mercury lamp, Deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser Etc. can be used. These light sources are appropriately selected according to the photosensitive wavelength of the first stimulant (B) or sensitizer. Examples of the active energy ray include ultraviolet rays, visible rays, and radiation.

The irradiation energy of the active energy ray for activating the first stimulant (B) depends on the desired film thickness and the type of the first stimulant (B) or sensitizer, but generally 10 It is the range of -3000mJ / cm < ² >. If less than 10 mJ / cm ^2, may condensate of alkoxysilane (A) is not sufficiently crosslinked, and 3000 mJ / cm ² larger, there is a possibility that the exposure time becomes long, the time of film comprising a cured product There is a possibility that the manufacturing efficiency per hit is lowered.

  On the other hand, when the first stimulant (B) is a stimulant activated by heat treatment, the heat treatment depends on the desired film thickness and the type of the first stimulant (B) or sensitizer. Is generally carried out at 50 to 150 ° C. for 0.1 to 30 minutes. If the temperature is too low or the heat treatment time is too short, the alkoxysilane condensate (A) may not be sufficiently crosslinked, and if the temperature is too high or the heat treatment time is too long, the time of the film made of the cured product There is a possibility that the manufacturing efficiency per hit is lowered.

  After applying a stimulus for activating the first stimulant (B) to the photosensitive composition, the photosensitive composition 1 is developed with a developer as shown in FIG. By removing the composition 1B, a film 1C made of a cured product is obtained.

  By developing with the developer, the photosensitive composition 1B in the unexposed area is dissolved and removed in the developer, and the film 1A made of the cured product in the exposed area remains on the substrate 2. As a result, a pattern-shaped film 1C is obtained. This pattern is called a negative pattern because the photosensitive composition 1B in the unexposed area is removed, and a negative photosensitive composition is used.

  Here, the term “development” refers to an operation of immersing a film made of a cured product of an exposed part or a photosensitive composition of an unexposed part in a developer such as an alkaline aqueous solution, or an operation of washing these surfaces with a developer, or developing. Various operations of treating the photosensitive composition with a developer, such as an operation of spraying the liquid onto these surfaces, are included.

  The developer is a solution that dissolves the photosensitive composition and the like in the unexposed area after applying a stimulus to activate the first stimulant (B) to the photosensitive composition. In the formation of the negative pattern, the film made of the cured product in the exposed area is not dissolved 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, after developing and obtaining a film made of a cured product, the film can be used as it is, for example, when the film has a desired pattern shape. On the other hand, when a film made of a cured product having a desired shape cannot be obtained and the film on the substrate is desired to be peeled, the film made of the cured product is peeled off. The substrate can be reused by peeling the film from the substrate.

  As shown in FIG. 2D, the film 1 </ b> C made of a cured product is stimulated to activate the second stimulant (C), and the film 1 </ b> C made of the cured product is peeled from the substrate 2.

  In the present invention, in order to peel the film 1C made of the cured product from the substrate 2, a stimulus for activating the second stimulant (C) is given to the film 1C made of the cured product. A film made of a cured product can be obtained by applying a stimulus for activating the second stimulant (C) to the film 1C made of a cured product, and for example applying a physical force or immersing it in a liquid as necessary. 1C can be easily peeled from the substrate 2.

  By devising the second stimulant (C), the cured film 1C can be peeled from the substrate 2 without using a relatively strong acid solution, a relatively strong alkali solution, an organic solvent, or the like. For example, the cured product film 1C can be peeled from the substrate 2 using a developing solution such as a relatively weak acid solution or a relatively weak alkaline solution used when forming the cured product film 1C. Specifically, the developer used for forming the cured product film 1C can be used. Therefore, the work environment can be prevented from deteriorating, and the environmental load due to the waste liquid can be reduced.

  When peeling the film 1C made of the cured product from the substrate 2, it is preferable to use a relatively weak acid solution or a relatively weak alkali solution. Examples of such liquids include tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, oxalic acid, formic acid, acetic acid and the like, and tetramethylammonium hydroxide aqueous solution is particularly preferably used. .

  Although it does not specifically limit as a light source for irradiating the active energy ray for activating the 2nd stimulant (C), A super high pressure mercury lamp, Deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser Etc. can be used. These light sources are appropriately selected according to the photosensitive wavelength of the second stimulant (C).

The irradiation energy of the active energy ray for activating the second stimulant (C) is generally in the range of 10 to 3000 mJ / cm ^{2 although} it depends on the thickness of the film. If less than 10 mJ / cm ^2, may be inferior in releasability of the film, may 3000 mJ / cm ² greater than the exposure time is too long, the peeling efficiency of the cured product film may be lowered.

  On the other hand, when the second stimulant (C) is a stimulant activated by heat treatment, the heat treatment is generally at 50 to 250 ° C. for 0.1 to 30 minutes depending on the thickness of the film. Done. If the temperature is too low or the heat treatment time is too short, the peelability of the film may be inferior. If the temperature is too high or the heat treatment time is too long, the peel efficiency of the cured product film may be reduced.

  1 and 2, an example of peeling a film made of a cured product when a film made of a cured product having a desired shape is not obtained and it is desired to peel the film on a substrate has been described. The film peeling method according to the present invention can be applied, for example, when a circuit pattern is formed by etching a non-pattern portion of a resist pattern after a resist pattern is formed corresponding to the formation of a circuit pattern.

  For example, the photosensitive composition 11 is applied on a substrate 12 such as a silicon substrate (FIG. 3A). Next, a stimulus for activating the first stimulant (B) is applied to the photosensitive composition 11 through the photomask 13 to cure the photosensitive composition 11 in the exposed portion. When the photosensitive composition 11 in the exposed portion is cured, a film 1A made of a cured product is formed and becomes insoluble in the developer. On the other hand, the photosensitive composition 11B in the unexposed area is soluble in the developer (FIG. 3B). Thereafter, development is performed with a developer to obtain a film 11C made of a cured product, and a resist pattern is formed (FIG. 3C). Next, the circuit pattern 14 is formed by etching between the films 11C which are non-pattern portions of the resist pattern (FIG. 3D). After forming the circuit pattern 14, the film 11C is stimulated to activate the second stimulant (C), and the film 11C is peeled off from the substrate 12A (FIG. 3E).

  The photosensitive composition is used to form a film in various apparatuses. For example, a film made of a cured product obtained by curing the photosensitive composition as an insulating protective film of an electronic device is used. Used. 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. The film made of the cured product is also used as an interlayer insulating film or a passivation film of a semiconductor element. Further, the film made of the cured product obtained by curing the photosensitive composition is, for example, an insulation for various electronic devices such as a TFT protective film of an organic EL element, an interlayer protective film of an IC chip, and an insulating layer of a sensor. It is also widely used as a protective film.

  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.

(Materials used)
[Condensation product of alkoxysilane (A)]
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 (A).

[First stimulant (B) and second stimulant (C)]
PAG103 (photoacid generator, manufactured by Ciba Specialty Chemicals)
SP172 (photoacid generator, manufactured by ADEKA)
IC819 (photoacid generator, manufactured by Ciba Specialty Chemicals)
CGI PNBT (thermal acid generator, manufactured by Ciba Specialty Chemicals)
Cyclohexyl-p-toluene sulfonate (thermal acid generator, Lancaster)

(Example 1)
(1) Preparation of photosensitive composition 100 parts by weight of the alkoxysilane condensate (A), 1 part by weight of PAG103 as the first stimulant (B), and SP172 as the second stimulant (C) After mixing 3 parts by weight, it was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

(2) Formation and peeling of film A glass substrate having aluminum deposited on the surface layer was prepared, and the photosensitive composition was spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, in order to activate the first stimulant (B) through a photomask having a predetermined pattern, the coating film is irradiated with g-rays as an active energy ray and an irradiation energy of 200 mJ / cm ^2. For 2 seconds at an intensity of 100 mW / cm ² . Then, the condensate (A) of alkoxysilane was crosslinked in the exposed area by heating in a hot air oven at 100 ° C. for 3 minutes, and the photosensitive composition was cured.

  Next, the coating film was dipped in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a film L1 made of a cured product on the substrate.

Next, in order to activate the second stimulant (C), the cured film L1 is irradiated with i rays as active energy rays at an intensity of 100 mW / cm ² and an irradiation energy of 2000 mJ / cm ^2. Irradiated for 2 seconds. Thereafter, peeling of the cured film L1 was attempted using a 2.38% aqueous solution of tetramethylammonium hydroxide.

(Example 2)
(1) Preparation of photosensitive composition 100 parts by weight of the above-mentioned alkoxysilane condensate (A), 1 part by weight of PAG103 as the first stimulant (B), and IC819 as the second stimulant (C) After mixing 3 parts by weight, it was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

(2) Formation and peeling of film A glass substrate having aluminum deposited on the surface layer was prepared, and the photosensitive composition was spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, in order to activate the first stimulant (B) through a photomask having a predetermined pattern, the coating film is irradiated with g-rays as an active energy ray and an irradiation energy of 200 mJ / cm ^2. For 2 seconds at an intensity of 100 mW / cm ² . Then, the condensate (A) of alkoxysilane was crosslinked in the exposed area by heating in a hot air oven at 100 ° C. for 3 minutes, and the photosensitive composition was cured.

  Next, the coating film was dipped in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a film L2 made of a cured product on the substrate.

Next, in order to activate the second stimulant (C), the cured film L2 is irradiated with i-line as an active energy ray at an intensity of 100 mW / cm ² so that the irradiation energy is 1000 mJ / cm ^2. Irradiated for 2 seconds. Thereafter, peeling of the cured product film L2 was attempted using a 2.38% aqueous solution of tetramethylammonium hydroxide.

(Example 3)
(1) Preparation of photosensitive composition 100 parts by weight of the above alkoxysilane condensate (A), 2 parts by weight of SP172 as the first stimulant (B), and CGI as the second stimulant (C) After mixing 1 part by weight of PNBT, it was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

(2) Formation and peeling of film A glass substrate having aluminum deposited on the surface layer was prepared, and the photosensitive composition was spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, the intensity of the i-line as an active energy ray for activating the first stimulant (B) is applied to the coating film through a photomask having a predetermined pattern so that the irradiation energy is 200 mJ / cm ^2. Irradiated at 100 mW / cm ² for 2 seconds. Then, the condensate (A) of alkoxysilane was crosslinked in the exposed area by heating in a hot air oven at 100 ° C. for 3 minutes, and the photosensitive composition was cured.

  Next, the coating film was dipped in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a film L3 made of a cured product on the substrate.

  Next, in order to activate the second stimulant (C), the cured product film L3 was heat-treated at 200 ° C. for 10 minutes. Thereafter, an attempt was made to peel off the cured product film L3 using a 2.38% aqueous solution of tetramethylammonium hydroxide.

Example 4
(1) Preparation of photosensitive composition 100 parts by weight of the above-mentioned alkoxysilane condensate (A), 2 parts by weight of cyclohexyl-p-toluenesulfonate as the first stimulant (B), and the second stimulus After mixing 3 parts by weight of SP172 as the agent (C), the mixture was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

(2) Formation and peeling of film A glass substrate having aluminum deposited on the surface layer was prepared, and the photosensitive composition was spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

  Next, in order to activate the first stimulant (B), the coating film was heat treated at 100 ° C. for 3 minutes to form a film L4 made of a cured product on the substrate.

Next, in order to activate the second stimulant (C), the cured film L4 is irradiated with i rays as active energy rays at an intensity of 100 mW / cm ² and an irradiation energy of 2000 mJ / cm ^2. Irradiated for 2 seconds. Thereafter, peeling of the cured film L4 was attempted using a 2.38% aqueous solution of tetramethylammonium hydroxide.

(Example 5)
(1) Preparation of photosensitive composition 100 parts by weight of the above-mentioned alkoxysilane condensate (A), 2 parts by weight of cyclohexyl-p-toluenesulfonate as the first stimulant (B), and the second stimulus After mixing 2 parts by weight of CGI PNBT as the agent (C), the mixture was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

(2) Formation and peeling of film A glass substrate having aluminum deposited on the surface layer was prepared, and the photosensitive composition was spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

  Next, in order to activate the first stimulant (B), the coating film was heat treated at 100 ° C. for 3 minutes to form a film L5 made of a cured product on the substrate.

  Next, in order to activate the second stimulant (C), the cured product film L5 was heat-treated at 200 ° C. for 10 minutes. Thereafter, peeling of the cured film L5 was attempted using a 2.38% aqueous solution of tetramethylammonium hydroxide.

(Evaluation of Examples)
The peeled state of the film when the cured film was peeled as described above was evaluated.

  The results are shown in Table 1 below.

The schematic block diagram which shows the manufacture flow which forms the film | membrane which consists of hardened | cured material using a photosensitive composition. (A)-(d) is sectional drawing for demonstrating each process which peels a film | membrane after forming the film | membrane which consists of hardened | cured materials using a photosensitive composition. (A)-(e) is sectional drawing for demonstrating each process which peels a film | membrane after forming the film | membrane which consists of hardened | cured material using a photosensitive composition as a resist material, forming a circuit pattern.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition 1A ... Film | membrane consisting of hardened | cured material of exposed part 1B ... Photosensitive composition of unexposed part 1C ... Film | membrane consisting of hardened | cured material 2 ... Substrate 3 ... Photomask 11 ... Photosensitive composition 11A ... Exposed part Film 11B ... photosensitive composition 11C ... unexposed portion of photosensitive composition 11C ... film made of cured product 12 ... substrate 13 ... photomask 14 ... circuit pattern

Claims (7)

The alkoxysilane condensate (A), the first stimulant (B) that is activated by stimulation and crosslinks the alkoxysilane condensate (A), and the first stimulant (B) are activated. After the photosensitive composition containing the second stimulant (C) activated by a stimulus different from the stimulus is applied on the substrate, the photosensitive composition applied on the substrate is coated with the first composition. A method of peeling a film made of a cured product obtained by curing the photosensitive composition by applying a stimulus for activating the stimulant (B) from the substrate,
A film peeling method, wherein a stimulus for activating the second stimulant (C) is applied to the film made of the cured product, and the film made of the cured product is peeled from the substrate.   The first stimulant (B) is an activator that is activated by irradiation of an active energy ray or heat treatment, and the stimulus that activates the first stimulant (B) is an active energy ray or heat. The film peeling method according to claim 1, wherein the film peeling method is provided.   The first stimulant (B) is a stimulant that is activated by irradiation with active energy rays, and the stimulus that activates the first stimulant (B) is active energy rays. Or the method of peeling a film according to 2.   The film peeling method according to claim 3, wherein the first stimulant (B) is a photoacid generator or a photobase generator.   The second stimulant (C) is a stimulant that is activated by irradiation with an active energy ray or heat treatment, and the stimulus that activates the second stimulant (C) is an active energy ray or heat. The film peeling method according to claim 1, wherein the film peeling method is provided.   The method according to claim 5, wherein the second stimulant (C) is a stimulant that generates a strong acid when the stimulus is applied.   The membrane according to any one of claims 1 to 6, characterized in that the second stimulant (C) is not activated by a stimulus that activates the first stimulant (B). Peeling method.

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