JP2009013317A - Energy beam-sensitive polymeric composition for release sheet, release sheet, and manufacturing method for release sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide cation polymeric ultraviolet ray-hardening type silicone release agent having excellent stability in storage, high hardening rate, and excellent transparency and to provide a release sheet having stable release performance for achieving excellent transparency and preventing change of release strength irrespective of elapse of time owing to the use of this release agent. <P>SOLUTION: This energy beam-sensitive polymeric composition for release sheet contains energy beam-sensitive acid generating agent (A), an amine compound (B), and a cation hardening silicone resin (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an energy-sensitive ray polymerizable composition for a release sheet, a release sheet, and a method for producing the release sheet. However, the present invention relates to a release sheet having a stable release performance with little change in release force and a method for producing the same.

  The silicone release sheet consists of a silicone release agent that has release properties for adhesive materials such as polyorganosiloxane on the surface of a support substrate such as coated paper, laminate paper, synthetic paper, nonwoven fabric, plastic film, and metal foil. Manufactured by forming a silicone release layer and used as a release sheet for adhesive processed products such as adhesive tapes and labels, synthetic leather, prepregs, flooring materials, marking films, various molded products, etc. ing.

  Moreover, the silicone release agent is generally known as a thermosetting type or an energy-sensitive ray curable type depending on the curing means, and the energy-sensitive ray curable type can be classified into an ultraviolet ray curable type and an electron beam curable type. . In particular, energy-sensitive radiation-curing silicone release agents are excellent in energy-saving curing conditions, and UV-curing silicone release agents are plastic base materials with poor heat resistance in addition to low cost and compact curing equipment. Is used because it has the advantage of being applicable (Patent Documents 1 to 3).

  The ultraviolet curable silicone release agent can be classified according to its curing mechanism, and is mainly classified into four types: cationic polymerization type, radical addition reaction type, hydrosilylation reaction type, and radical polymerization type (Patent Document 4). Among them, cationic polymerization type ultraviolet curable silicone is not subject to curing inhibition by oxygen in the atmosphere, so it is not necessary to cure in an inert gas atmosphere such as nitrogen gas, and the volume shrinkage after curing is small. There are many advantages, such as being excellent in adhesiveness with a support base material, and being able to easily control the peeling load on the adhesive substance from heavy peeling to light peeling (Patent Document 5).

  A cationic polymerization type ultraviolet curable silicone release agent (hereinafter referred to as “cationic polymerizable ultraviolet curable silicone release agent”) is prepared by blending an energy-sensitive linear acid generator and a cationic curable silicone resin. The improvement of the curing rate and the improvement of storage stability for the cationic polymerizable UV curable silicone release agent is a permanent requirement, and in particular, the development of a cationic polymerizable UV curable silicone release agent with excellent curing rate This is particularly desirable because it is possible to improve workability by shortening the irradiation time of the active energy ray and to reduce the deterioration of the supporting base material due to the energy ray irradiation.

JP-A-5-169595 JP-A-8-144198 JP 2000-265153 A JP 2005-343073 A Japanese Patent No. 3735857

  The problem to be solved by the present invention is to provide a cationically polymerizable ultraviolet curable silicone release agent that is excellent in storage stability and curing speed, and by using this release agent, the change in the release force is maintained even with time. An object of the present invention is to provide a release sheet having a small and stable release performance.

  As a result of intensive studies to solve the above problems, the present inventors have found the following method.

  That is, the present invention relates to an energy-sensitive linear acid generator (A) represented by the following general formula (1), an amine compound (B) represented by the following general formula (2), and a cation curable silicone resin (C). The present invention relates to an energy-sensitive polymerizable composition for a release sheet.

General formula (1)

(However, L ⁺ represents an arbitrary cation.
X ⁻ represents an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ . )

General formula (2)

^{(Wherein, Ar 1, Ar 2, Ar} 3 each independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group.
Ar ¹ and Ar ² , Ar ¹ and Ar ³ , or Ar ² and Ar ³ may be bonded to each other to form a ring structure. )

  Furthermore, the present invention provides the above-mentioned release sheet-sensitive sheet, wherein the energy-sensitive linear acid generator (A) is a sulfonium salt represented by the following general formula (3) or an iodonium salt represented by the following general formula (4). The present invention relates to an energy beam polymerizable composition.

General formula (3)

(However, R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted complex, Cyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted It represents a group selected from a substituted oxycarbonyl group or a halogen atom.
R ¹ And R ² , R ¹ And R ³ or R ² And R ³ may be bonded to each other to form a ring structure.
X ⁻ represents an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ . )

General formula (4)

(However, Ar ⁴ and Ar ^{5 each} represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
X ⁻ represents an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ . )

Furthermore, the present invention relates to the energy-sensitive polymerizable composition for a release sheet as described above, wherein X ⁻ is selected from PF ₆ ⁻ and SbF ₆ ⁻ .

  Furthermore, the present invention relates to the energy-sensitive polymerizable composition for a release sheet as described above, wherein the cationic curable silicone resin (C) is a polyorganosiloxane having an epoxy group in the molecule.

  Furthermore, this invention relates to the peeling sheet which consists of a support base material (D) and the silicone peeling layer formed by superposing | polymerizing the energy-sensitive-polymerizable composition for release sheets of the said description.

  Furthermore, the present invention provides a release comprising irradiating an active energy ray after forming a silicone release layer on the at least one surface of the support substrate (D) with the above-described energy-sensitive polymerizable composition for release sheet. The present invention relates to a method for manufacturing a sheet for use.

  The energy sensitive ray polymerizable composition for release sheet of the present invention could be cured with a small amount of active energy ray irradiation. In addition, the energy-sensitive polymerizable composition for release sheet of the present invention uses an energy-sensitive acid generator (A) and an amine compound (B), so that even when irradiated with a small amount of energy rays. Since extremely strong acid is generated, it is possible to improve workability by shortening the irradiation time of active energy rays and to reduce deterioration of the support base material due to energy ray irradiation. Further, by using the energy-sensitive polymerizable composition for release sheet of the present invention, a release sheet having a stable release performance with little change in release force over time can be provided.

  Hereinafter, embodiments of the present invention will be described in detail.

  The energy sensitive ray polymerizable composition for release sheet of the present invention comprises an energy sensitive acid generator (A) comprising an onium cation and a counter anion, and an amine compound (B) having a specific structure as a photosensitizer. In combination with the conventional energy-sensitive ray-polymerizable composition for release sheet, high acid generation efficiency is exhibited even in irradiation with near ultraviolet rays of 300 nm or more by a high-pressure mercury lamp or the like, and active energy rays. An energy-sensitive polymerizable composition for a release sheet that can shorten the irradiation time is realized.

First, the energy sensitive acid generator (A) of the present invention will be described. General formula (1) is mentioned as an energy-sensitive linear acid generator (A) of this invention. Here, the onium cation L ⁺ constituting the general formula (1) includes iodonium, sulfonium, sulfoxonium, selenonium, phosphonium, ammonium, metal arene cation, pyridinium, quinolinium, isoquinolinium, benzoxazolium, benzo Heterocyclic cations such as thiazolium can be mentioned.

Preferable examples of the onium cation structure as the onium cation L ⁺ constituting the general formula (1) include onium cations selected from the general formula (5) to the general formula (13).

General formula (5)

General formula (6)

General formula (7)

General formula (8)

General formula (9)

General formula (10)

Formula (11)

Formula (12)

Formula (13)

(Wherein, R ^1, R ² and R ³ have the same meaning as R ^1, R ² and R ³ as described in the general formula (3).
R ⁴ represents a group similar to the groups described for R ¹ , R ² and R ³ .
R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylthio group.
R ⁶ and R ⁷ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxyl group.
R is a halogen atom, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl Group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted Or an arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbonyloxy group, or a substituted or unsubstituted oxycarbonyl group.
Ar ^4, Ar ⁵ has the same meaning as Ar ^4, Ar ⁵ described in the general formula (4).
X represents an oxygen or sulfur atom.
i represents an integer of 0 to 5; j represents an integer of 0 to 4. k represents an integer of 0 to 3.
Also, adjacent Rs, Ar ⁴ and Ar ⁵ , R ² and R ³ , R ² and R ⁴ , R ³ and R ⁴ , R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R, or R ¹ and R ⁵ may be a cyclic structure bonded to each other. )

  Among these, a more preferable onium cation structure is selected from General Formula (5), General Formula (6), General Formula (8), General Formula (10), General Formula (12), and General Formula (13). Particularly preferred onium cation structures are onium cations selected from general formula (5), general formula (6), general formula (12), and general formula (13). The structure is an onium cation selected from general formula (5) and general formula (13).

  This is because the onium cation described above generally has a high reduction potential, that is, a high electron accepting property. Therefore, it decomposes by the irradiation of energy rays, especially light, and easily generates an acid. This is particularly noticeable when combined with photosensitizers.

  Furthermore, the onium cations of the general formula (5) and the general formula (13) can be cited as one of the reasons that the ease of synthesis and the availability are preferable.

  Below, the substituent in the onium cation which comprises the energy-sensitive linear acid generator (A) of this invention is demonstrated.

Examples of the substituted or unsubstituted alkyl group in the substituents R ^{1 to} R ⁷ and R include substituted or unsubstituted linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms. Is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, cyclopentyl Cyclohexyl group, 4-decylcyclohexyl group, fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, hydroxymethyl group, carboxymethyl group, mercaptomethyl group, cyanomethyl group, Nitromethyl group, azidomethyl group, etc. can be mentioned. Not intended to be constant.

Examples of the substituted or unsubstituted alkenyl group in the substituents R ^{1 to} R ⁴ and R include linear, branched, and cyclic alkenyl groups having 2 to 18 carbon atoms. Specific examples include a vinyl group, 1-propenyl group, 2-propenyl group, 1-octenyl group, 1-octadecenyl group, isopropenyl group, 1-cyclohexenyl group, trifluoroethenyl group, 1-chloroethenyl group, 2,2-dibromoethenyl group, 4 -Hydroxy-1-butenyl group, 1-carboxyethenyl group, 5-mercapto-1-hexenyl group, 1-cyanoethenyl group, 3-nitro-1-propenyl group, 4-azido-2-butenyl group, etc. However, it is not limited to these.

Examples of the substituted or unsubstituted aryl group in the substituents R ^{1 to} R ⁴ , R, Ar ⁴ and Ar ⁵ include monocyclic and condensed polycyclic aryl groups having 6 to 18 carbon atoms. Phenyl group, biphenyl group, terphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecyl Phenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m- Examples thereof include, but are not limited to, a ruoxyphenyl group, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group. ) To sulfur atom of general formula (6), phosphorus atom of general formula (7), carbon atom of general formula (8) to general formula (11), nitrogen atom of general formula (8) to general formula (11), Any substitution position capable of forming a covalent bond with the iodine atom of the general formula (13) may be bonded at any substitution position, and these are also R ^{1 to} R ⁴ , R, Ar ⁴ and Ar of the present invention. It is included in the category of the substituent represented by ⁵ .

Examples of the substituted or unsubstituted heterocyclic group in the substituents R ^{1 to} R ⁴ , R, Ar ⁴ and Ar ⁵ include an aromatic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. Or an aliphatic heterocyclic group is mentioned, 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2- Benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, Indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl Group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group Phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group Pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, Examples include ruphorinyl group, thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, and 3-coumarinyl group. In addition, the sulfur atom of the general formula (5) to the general formula (6), the phosphorus atom of the general formula (7), the carbon atom of the general formula (8) to the general formula (11), the general formula (8) to formula (11) nitrogen atom of the general formula (13) may be bonded at any substitution positions for a substitution position which is capable of forming a covalent bond with an iodine atom, R ¹ ~ thereof are also the present invention It is included in the category of substituents represented by R ⁴ , R, Ar ⁴ and Ar ⁵ .

Examples of the substituted or unsubstituted alkoxyl group in the substituents R ^{1 to} R ⁴ , R ⁶ , R ⁷ and R include linear, branched and cyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples As methoxy, ethoxy, propoxy, butoxy, octyloxy, octadecanoxy, isopropoxy, t-butoxy, cyclopentyloxy, cyclohexyloxy, fluoromethoxy, chloromethoxy, bromomethoxy Groups, trifluoromethoxy groups, trichloromethoxy groups, tribromomethoxy groups, hydroxymethoxy groups, carboxymethoxy groups, mercaptomethoxy groups, cyanomethoxy groups, nitromethoxy groups, azidomethoxy groups, and the like. Is not to be done.

Examples of the substituted or unsubstituted aryloxy group in the substituents R ^{1 to} R ⁴ and R include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, 1 -Naphtyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group 1-acenaphthyloxy group, 9-fluorenyloxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, 2,3-xylyloxy group, 2,5-xylyloxy group, mesityloxy group, p- Cumenyloxy group, p-decylphenoxy group, p-cyclohexylphenoxy group, 4-biphenoxy group, o-fluorophenoxy group Group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercaptophenoxy group, p-cyanophenoxy group, m-nitrophenoxy group, m-azidophenoxy group, etc. However, the aryl group and the oxygen atom may be bonded at positions other than those described above, and these are also represented by R ^{1 to} R ⁴ and R of the present invention. Included in the category of substituents.

Examples of the substituted or unsubstituted heterocyclic oxy group in the substituents R ^{1 to} R ⁴ and R include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and a monocyclic or condensed polycyclic group having 4 to 18 carbon atoms. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy. Group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like, but are not limited thereto, The ring group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of substituents represented by R ^{1 to} R ⁴ and R of the present invention.

As the substituted or unsubstituted acyl group in the substituents R ^{1 to} R ⁴ and R, a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded. A carbonyl group, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, a monocyclic or condensed having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom Examples include a carbonyl group to which a polycyclic heterocyclic group is bonded, and specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, Palmitoyl, stearoyl, cyclopentylcarbonyl, cyclohexylcarbonyl, acryloyl, methacryloyl, Tonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, etc. However, the present invention is not limited thereto, and the aryl group and the carbonyl group, the heterocyclic group and the carbonyl group may be bonded at positions other than those described above, and these are also R ^{1 to} R of the present invention. Included in the category of substituents represented by ⁴ and R.

Examples of the substituted or unsubstituted carbonyloxy group in the substituents R ^{1 to} R ⁴ and R include a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms. A bonded carbonyloxy group, or a carbonyloxy group bonded with a monocyclic or condensed aryl group having 6 to 18 carbon atoms, or a nitrogen atom, oxygen atom, sulfur atom, or phosphorus atom, and having 4 to 18 carbon atoms A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group is bonded, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. , Pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, Clopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyl Examples thereof include an oxy group, a cinnamoyloxy group, a 3-furoyloxy group, a 2-thenoyloxy group, a nicotinoyloxy group, an isonicotinoyloxy group, a 9-anthroyloxy group, and a 5-naphthacenoyloxy group. However, the aryl group and the carbonyloxy group, the heterocyclic group and the carbonyloxy group may be bonded at positions other than those described above, and these are also the substituents R ^{1 to} R of the present invention. Included in the category of substituents represented by ⁴ and R.

Examples of the substituted or unsubstituted oxycarbonyl group in the substituents R ^{1 to} R ⁴ and R include a carbonic acid ester group having 1 to 12 carbon atoms or a monocyclic or condensed polycyclic aryloxycarbonyl group having 7 to 19 carbon atoms. Specific examples include tert-butoxycarbonyloxy group, tert-pentyloxycarbonyloxy group, 1,1-diethylpropyloxycarbonyloxy group, 1-ethyl-2-cyclopentenyloxycarbonyloxy group, 2-tetrahydro Pyranyloxycarbonyloxy group, 1-ethylcyclopentyloxycarbonyloxy group, phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 9-anthryloxycarbonyl group, 9-phenanthryloxycarbonyl group , 1-pilet Ruoxycarbonyl group, 5-naphthacenyloxycarbonyl group, 1-indenyloxycarbonyl group, 2-azurenyloxycarbonyl group, 1-acenaphthyloxycarbonyl group, 9-fluorenyloxycarbonyl group, o-tolyl Oxycarbonyl group, m-tolyloxycarbonyl group, p-tolyloxycarbonyl group, 2,3-xylyloxycarbonyl group, 2,5-xylyloxycarbonyl group, mesityloxycarbonyl group, p-cumenyloxycarbonyl Group, p-cyclohexylphenoxycarbonyl group, 4-phenylphenoxycarbonyl group, o-fluorophenoxycarbonyl group, m-chlorophenoxycarbonyl group, p-bromophenoxycarbonyl group, p-hydroxyphenoxycarbonyl group, m-carboxyphenoxy Carbonyl group, o- mercapto phenoxycarbonyl group, p- cyanophenoxy group, m- nitrophenoxy carbonyl group, can be exemplified m- azide phenoxycarbonyl group and the like, but is not limited thereto.

Examples of the halogen atom in the substituents R ^{1 to} R ⁴ and R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the substituted or unsubstituted alkylthio group in the substituents R and R ⁵ include linear, branched, and cyclic alkylthio groups having 1 to 18 carbon atoms. Specific examples include a methylthio group, an ethylthio group, Propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, isopropylthio, isobutylthio, sec-butylthio, t-butylthio, cyclopentylthio, cyclohexylthio 4-decylcyclohexylthio group, fluoromethylthio group, chloromethylthio group, bromomethylthio group, trifluoromethylthio group, trichloromethylthio group, tribromomethylthio group, hydroxymethylthio group, carboxymethylthio group, mercaptomethylthio group Group, cyanomethyl thio group, a nitro methylthio group, there may be mentioned an azide methyl thio group, but is not limited thereto.

  Examples of the substituted or unsubstituted arylthio group in the substituent R include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group. , 9-anthrylthio group, 9-phenanthrylthio group, and the like, but are not limited thereto, and the aryl group and the sulfur atom may be bonded at positions other than those described above. It is included in the category of the substituent represented by R of the invention.

  Examples of the substituted or unsubstituted heterocyclic thio group in the substituent R include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, and 3-carbazolylthio group. , 4-carbazolylthio group and the like, but are not limited thereto, and the heterocyclic group and the sulfur atom may be bonded at positions other than the above, and they are also represented by R in the present invention. Are included in the category of substituents.

  Examples of the substituted or unsubstituted carbamoyl group in the substituent R include carbamoyl groups having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N -3-Shear Phenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like can be mentioned, but are not limited thereto.

Further adjacent Rs, Ar ⁴ and Ar ⁵ , R ² and R ³ , R ² and R ⁴ , R ³ and R ⁴ , or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R, R ¹ and R ⁵ may be a cyclic structure bonded to each other.

The above-mentioned substituents R ^{1 to} R ⁷ , R, Ar ⁴ and Ar ⁵ may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a mercapto group, and a cyano group. Nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkyl Examples include an amino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group Tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include monocyclic or condensed polycyclic heterocyclic groups having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyl group, A 2-thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like can be mentioned.

  As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic group having 6 to 18 carbon atoms, A carbonyl group to which a condensed polycyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded; They may have an unsaturated bond in the structure. Specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group. , Palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group Crotonoyl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyl. Oxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group , Sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy Group, boronyloxy group, 4- Sill cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and 9-anthryl. Oxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group Etc.

  Examples of the heterocyclic oxy group include monocyclic or condensed polycyclic heterocyclic oxy groups having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include 2-furanyloxy. Group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group Group, 4-carbazolyloxy group, 9-acridinyloxy group and the like.

  As the acyloxy group, a hydrogen atom, a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic group having 6 to 18 carbon atoms. Or a carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a carbonyloxy group to which a condensed polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is bonded. Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group Group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group , Acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3- Examples include a furoyloxy group, a 2-thenoyloxy group, a nicotinoyloxy group, an isonicotinoyloxy group, a 9-anthroyloxy group, and a 5-naphthacenoyloxy group.

  Examples of the alkylthio group include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms, and specific examples include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group. Group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

  Examples of the arylthio group include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms. Specific examples include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, and 9-phena. And enthrylthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include 2-furylthio. Group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group and the like. .

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

Furthermore, the hydrogen atoms of the substituents R ^{1 to} R ⁷ , R, Ar ⁴ and Ar ⁵ described above may be further substituted with other substituents. Examples of such substituents include a fluorine atom, Halogen groups such as chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, methoxycarbonyl group, butoxycarbonyl group and phenoxy Alkoxycarbonyl groups such as carbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. -Alkylsulfanyl groups such as butylsulfanyl groups Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, alkylamino groups such as methylamino group and cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, phenylamino group , Arylamino groups such as p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl In addition to aryl groups such as groups, heterocyclic groups such as furyl groups, thienyl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, Cyano group, trifluoromethyl group, trichloromethyl group Trimethylsilyl group, a phosphinico group, a phosphono group, trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  Below, the specific example of the structure of the onium cation represented by General formula (5)-General formula (13) of the energy-sensitive linear acid generator (A) of this invention is given.

Onium cation (sulfonium cation) corresponding to general formula (5):
Dimethylphenylsulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (m-chlorophenyl) sulfonium, dimethyl (p-bromophenyl) sulfonium, dimethyl (p-cyanophenyl) sulfonium, dimethyl (m-nitrophenyl) sulfonium, dimethyl ( 2,4,6-tribromophenyl) sulfonium, dimethyl (pentafluorophenyl) sulfonium, dimethyl (p- (trifluoromethyl) phenyl) sulfonium, dimethyl (p-hydroxyphenyl) sulfonium, dimethyl (p-mercaptophenyl) sulfonium , Dimethyl (p-methylsulfinylphenyl) sulfonium, dimethyl (p-methylsulfonylphenyl) sulfonium, dimethyl (o-acetylphenyl) sulfonium Dimethyl (o-benzoylphenyl) sulfonium, dimethyl (p-methylphenyl) sulfonium, dimethyl (p-isopropylphenyl) sulfonium, dimethyl (p-octadecylphenyl) sulfonium, dimethyl (p-cyclohexylphenyl) sulfonium, dimethyl (p-methoxy) Phenyl) sulfonium, dimethyl (o-methoxycarbonylphenyl) sulfonium, dimethyl (p-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethylsulfonium, (4-methoxynaphthalene- 1-yl) dimethylsulfonium, dimethyl (p-isopropoxycarbonylphenyl) sulfonium, dimethyl (2-naphthyl) sulfonium, dimethyl (9-anthryl) Rufonium, diethylphenylsulfonium, methylethylphenylsulfonium, methyldiphenylsulfonium, triphenylsulfonium, diisopropylphenylsulfonium, diphenyl (4-phenylsulfanyl-phenyl) -sulfonium, 4,4′-bis (diphenylsulfonium) diphenyl sulfide, 4, 4′-bis [di [(4- (2-hydroxy-ethoxy) -phenyl)] sulfonium]] diphenyl sulfide, 4,4′-bis (diphenylsulfonium) biphenylene, diphenyl (o-fluorophenyl) sulfonium, diphenyl ( m-chlorophenyl) sulfonium, diphenyl (p-bromophenyl) sulfonium, diphenyl (p-cyanophenyl) sulfonium, diphenyl (m-nitrophenyl) sulfonium, Diphenyl (2,4,6-tribromophenyl) sulfonium, diphenyl (pentafluorophenyl) sulfonium, diphenyl (p- (trifluoromethyl) phenyl) sulfonium, diphenyl (p-hydroxyphenyl) sulfonium, diphenyl (p-mercaptophenyl) ) Sulfonium, diphenyl (p-methylsulfinylphenyl) sulfonium, diphenyl (p-methylsulfonylphenyl) sulfonium, diphenyl (o-acetylphenyl) sulfonium, diphenyl (o-benzoylphenyl) sulfonium, diphenyl (p-methylphenyl) sulfonium, Diphenyl (p-isopropylphenyl) sulfonium, diphenyl (p-octadecylphenyl) sulfonium, diphenyl (p-cyclohexylphenyl) Lu) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, diphenyl (o-methoxycarbonylphenyl) sulfonium, diphenyl (p-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromen-4-yl) Diphenylsulfonium, (4-methoxynaphthalen-1-yl) diphenylsulfonium, diphenyl (p-isopropoxycarbonylphenyl) sulfonium, diphenyl (2-naphthyl) sulfonium, diphenyl (9-anthryl) sulfonium, ethyldiphenylsulfonium, methylethyl ( o-tolyl) sulfonium, methyldi (p-tolyl) sulfonium, tri (p-tolyl) sulfonium, diisopropyl (4-phenylsulfanylphenyl) sulfonium, diphen Examples thereof include, but are not limited to, nyl (2-thienyl) sulfonium, diphenyl (2-furyl) sulfonium, diphenyl (9-ethyl-9Hcarbazol-3-yl) sulfonium.

Onium cation corresponding to general formula (6) (sulfoxonium cation):
Dimethylphenylsulfoxonium, dimethyl (o-fluorophenyl) sulfoxonium, dimethyl (m-chlorophenyl) sulfoxonium, dimethyl (p-bromophenyl) sulfoxonium, dimethyl (p-cyanophenyl) sulfoxonium, dimethyl (M-nitrophenyl) sulfoxonium, dimethyl (2,4,6-tribromophenyl) sulfoxonium, dimethyl (pentafluorophenyl) sulfoxonium, dimethyl (p- (trifluoromethyl) phenyl) sulfoxonium , Dimethyl (p-hydroxyphenyl) sulfoxonium, dimethyl (p-mercaptophenyl) sulfoxonium, dimethyl (p-methylsulfinylphenyl) sulfoxonium, dimethyl (p-methylsulfonylphenyl) sulfoxo , Dimethyl (o-acetylphenyl) sulfoxonium, dimethyl (o-benzoylphenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-isopropylphenyl) sulfoxonium, dimethyl (p- Octadecylphenyl) sulfoxonium, dimethyl (p-cyclohexylphenyl) sulfoxonium, dimethyl (p-methoxyphenyl) sulfoxonium, dimethyl (o-methoxycarbonylphenyl) sulfoxonium, dimethyl (p-phenylsulfanylphenyl) sulfo Xonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethylsulfoxonium, (4-methoxynaphthalen-1-yl) dimethylsulfoxonium, dimethyl (p-isopropoxyca) Bonylphenyl) sulfoxonium, dimethyl (2-naphthyl) sulfoxonium, dimethyl (9-anthryl) sulfoxonium, diethylphenylsulfoxonium, methylethylphenylsulfoxonium, methyldiphenylsulfoxonium, triphenylsulfoxonium Ni, diisopropylphenylsulfoxonium, diphenyl (4-phenylsulfanyl-phenyl) -sulfoxonium, 4,4′-bis (diphenylsulfoxonium) diphenyl sulfide, 4,4′-bis [di [(4- ( 2-hydroxy-ethoxy) -phenyl)] sulfoxonium] diphenyl sulfide, 4,4′-bis (diphenylsulfoxonium) biphenylene, diphenyl (o-fluorophenyl) sulfoxonium, diphenyl (m-chlorophenyl) sulfur Xonium, diphenyl (p-bromophenyl) sulfoxonium, diphenyl (p-cyanophenyl) sulfoxonium, diphenyl (m-nitrophenyl) sulfoxonium, diphenyl (2,4,6-tribromophenyl) sulfoxonium , Diphenyl (pentafluorophenyl) sulfoxonium, diphenyl (p- (trifluoromethyl) phenyl) sulfoxonium, diphenyl (p-hydroxyphenyl) sulfoxonium, diphenyl (p-mercaptophenyl) sulfoxonium, diphenyl ( p-methylsulfinylphenyl) sulfoxonium, diphenyl (p-methylsulfonylphenyl) sulfoxonium, diphenyl (o-acetylphenyl) sulfoxonium, diphenyl (o-benzoylphenyl) sulfur Hoxonium, diphenyl (p-methylphenyl) sulfoxonium, diphenyl (p-isopropylphenyl) sulfoxonium, diphenyl (p-octadecylphenyl) sulfoxonium, diphenyl (p-cyclohexylphenyl) sulfoxonium, diphenyl (p- Methoxyphenyl) sulfoxonium, diphenyl (o-methoxycarbonylphenyl) sulfoxonium, diphenyl (p-phenylsulfanylphenyl) sulfoxonium, (7-methoxy-2-oxo-2H-chromen-4-yl) diphenylsulfone Xonium, (4-methoxynaphthalen-1-yl) diphenylsulfoxonium, diphenyl (p-isopropoxycarbonylphenyl) sulfoxonium, diphenyl (2-naphthyl) sulfoxonium Diphenyl (9-anthryl) sulfoxonium, ethyldiphenylsulfoxonium, methylethyl (o-tolyl) sulfoxonium, methyldi (p-tolyl) sulfoxonium, tri (p-tolyl) sulfoxonium, diisopropyl ( 4-phenylsulfanylphenyl) sulfoxonium, diphenyl (2-thienyl) sulfoxonium, diphenyl (2-furyl) sulfoxonium, diphenyl (9-ethyl-9Hcarbazol-3-yl) sulfoxonium However, it is not limited to these.

Onium cation (phosphonium cation) corresponding to the general formula (7):
Examples of phosphonium cations:
Trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluorophenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium, triphenyl (p-cyanophenyl) phosphonium , Triphenyl (m-nitrophenyl) phosphonium, triphenyl (p-phenylsulfanylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenylphosphonium, triphenyl (o-hydroxyphenyl) ) Phosphonium, triphenyl (o-acetylphenyl) phosphonium, triphenyl (m-benzoylphenyl) phosphonium, triphenyl (p-methylphenyl) phospho Phonium, triphenyl (p-isopropoxyphenyl) phosphonium, triphenyl (o-methoxycarbonylphenyl) phosphonium, triphenyl (1-naphthyl) phosphonium, triphenyl (9-anthryl) phosphonium, triphenyl (2-thienyl) phosphonium , Triphenyl (2-furyl) phosphonium, triphenyl (9-ethyl-9Hcarbazol-3-yl) phosphonium and the like, but are not limited thereto.

Onium cation corresponding to general formula (8) (pyridinium cation):
Examples of pyridinium cations:
N-phenylpyridinium, N- (o-chlorophenyl) pyridinium, N- (m-chlorophenyl) pyridinium, N- (p-cyanophenyl) pyridinium, N- (o-nitrophenyl) pyridinium, N- (p-acetylphenyl) ) Pyridinium, N- (p-isopropylphenyl) pyridinium, N- (p-octadecyloxyphenyl) pyridinium, N- (p-methoxycarbonylphenyl) pyridinium, N- (9-anthryl) pyridinium, 2-chloro-1- Phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenylpyridinium, 2-phenyl-1-phenylpyridinium, 1,2-diphenylpyridinium, 2-methoxy- 1-phenylpi Dinium, 2-phenoxy-1-phenylpyridinium, 2-acetyl-1- (p-tolyl) pyridinium, 2-methoxycarbonyl-1- (p-tolyl) pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl Examples thereof include, but are not limited to, -1- (2-furyl) pyridinium, N-methylpyridinium, N-ethylpyridinium, and the like.

Onium cation (quinolinium cation) corresponding to the general formula (9):
Examples of quinolinium cations:
N-methylquinolinium, N-ethylquinolinium, N-phenylquinolinium, N-naphthylquinolinium, N- (o-chlorophenyl) quinolinium, N- (m-chlorophenyl) quinolinium, N- (p -Cyanophenyl) quinolinium, N- (o-nitrophenyl) quinolinium, N- (p-acetylphenyl) quinolinium, N- (p-isopropylphenyl) quinolinium, N- (p-octadecyloxyphenyl) quinolinium, N- ( p-methoxycarbonylphenyl) quinolinium, N- (9-anthryl) quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-vinyl-1-phenylquinolinium, 2-phenyl-1-phenyl Norinium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy-1-phenylquinolinium, 2-acetyl-1-phenylquinolinium, 2-methoxycarbonyl-1 -Phenylquinolinium, 3-fluoro-1-phenylquinolinium, 4-methyl-1-phenylquinolinium, 2-methoxy-1- (p-tolyl) quinolinium, 2-phenoxy-1- (2- Furyl) quinolinium, 2-acetyl-1- (2-thienyl) quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-isopropylquinolinium However, it is not limited to these.

Onium cation (isoquinolinium cation) corresponding to the general formula (10):
Examples of isoquinolinium cations:
N-phenylisoquinolinium, N-methylisoquinolinium, N-ethylisoquinolinium, N- (o-chlorophenyl) isoquinolinium, N- (m-chlorophenyl) isoquinolinium, N- (p-cyanophenyl) Isoquinolinium, N- (o-nitrophenyl) isoquinolinium, N- (p-acetylphenyl) isoquinolinium, N- (p-isopropylphenyl) isoquinolinium, N- (p-octadecyloxyphenyl) isoquinolinium, N- (p-methoxycarbonyl) Phenyl) isoquinolinium, N- (9-anthryl) isoquinolinium, 1,2-diphenylisoquinolinium, N- (2-furyl) isoquinolinium, N- (2-thienyl) isoquinolinium, N-naphthylisoquinolinium, etc. I can mention However, it is not limited to these.

Onium cations corresponding to general formula (11) (benzoxazolium cation, benzothiazolium cation):
Examples of benzoxazolium cations:
N-methylbenzoxazolium, N-ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium, N- (p-fluorophenyl) benzoxazolium, N- (p- Chlorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (o-methoxycarbonylphenyl) benzoxazolium, N- (2-furyl) benzoxazolium, N- (o -Fluorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (m-nitrophenyl) benzoxazolium, N- (p-isopropoxycarbonylphenyl) benzoxazolium, N- (2-thienyl) benzoxazolium, N- (m-carboxyphenyl) benzox Sazolium, 2-mercapto-3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazolium, 2-methylthio-3- (4-phenylsulfanylphenyl) benzoxazolium, 6-hydroxy-3- (p-tolyl) benzoxazolium, 7-mercapto-3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazolium, and the like can be mentioned. Absent.

Examples of benzothiazolium cations:
N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N- (1-naphthyl) benzothiazolium, N- (p-fluorophenyl) benzothiazolium, N -(P-chlorophenyl) benzothiazolium, N- (p-cyanophenyl) benzothiazolium, N- (o-methoxycarbonylphenyl) benzothiazolium, N- (p-tolyl) benzothiazolium, N- (o-fluorophenyl) benzothiazolium, N- (m-nitrophenyl) benzothiazolium, N- (p-isopropoxycarbonylphenyl) benzothiazolium, N- (2-furyl) benzothia Zolium, N- (4-methylthiophenyl) benzothiazolium, N- (4-phenylsulfanylphenyl) benzothiazolium, N (2-naphthyl) benzothiazolium, N- (m-carboxyphenyl) benzothiazolium, 2-mercapto-3-phenylbenzothiazolium, 2-methyl-3-phenylbenzothiazolium, 2-methylthio -3-phenylbenzothiazolium, 6-hydroxy-3-phenylbenzothiazolium, 7-mercapto-3-phenylbenzothiazolium, 4,5-difluoro-3-phenylbenzothiazolium, etc. However, it is not limited to these.

Onium cation corresponding to general formula (12) (furyl or thienyl iodonium cation):
Difuryliodonium, dithienyliodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5- Nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5-carboxy-2-thienyl) iodonium, bis (5-methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl) -2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium, bis (5-ethynyl-2-thienyl) iodonium, bis ( 5-cyclohexyl-2-furyl) iodonium, bis (5-hydroxy-2-thio) Nyl) iodonium, bis (5-phenoxy-2-furyl) iodonium, bis (5-mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) Although iodonium etc. can be mentioned, it is not limited to these.

Onium cation corresponding to general formula (13) (diaryliodonium cation):
Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (P-octadecyloxyphenyl) iodonium, 4-isopropyl-4′-methyldiphenyliodonium, (4-isobutylphenyl) -p-tolyliodonium, bis (1-naphthyl) iodonium, bis (4-phenylsulfanylphenyl) iodonium, Phenyl (6-benzoyl-9-ethyl-9H-carbazol-3-yl) iodonium, (7-methoxy-2-oxo-2H-chromen-3-yl) -4'-isopropylphenyliodonium, etc. However, it is not limited to these.

Then, the counter anion of the general formula (1) in X ^- is described.

The counter anion X ⁻ in the general formula (1) is not particularly limited in principle, but a non-nucleophilic anion is preferable. Counter anion wherein X ^- For non-nucleophilic anion, for nucleophilic reaction is unlikely to occur in a variety of materials that are cationic or combination coexisting in the molecule, the energy-sensitive are denoted by the general formula (1) as a result Sensan generated It is possible to improve the temporal stability of the agent itself or a composition using the agent. The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

Among the exemplified anions described above, PF ₆ ⁻ , SbF ₆ ⁻ , and AsF ₆ ⁻ are particularly preferable as the counter anion X ⁻ in the general formula (1), and PF ₆ ⁻ , SbF ₆ ^- is mentioned.

Therefore, as a specific example of a preferable onium salt constituting the energy-sensitive linear acid generator of the present invention, a specific example of the structure of the onium cation represented by the above general formula (5) to general formula (13) and PF _An onium salt composed of an anion selected from ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ .

  Specifically, “Syracure UVI-6922”, “Syracure UVI-6974” (above, manufactured by Dow Chemical Japan Co., Ltd.), “Adekaoptomer SP150”, “Adekaoptomer SP152”, “Adekaoptomer” “SP170”, “Adekaoptomer SP172” (manufactured by ADEKA Corporation), “IRGACURE250” (manufactured by Ciba Specialty Chemicals), “CI-5102”, “CI-2855” (manufactured by Nippon Soda Co., Ltd.), “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-180L” (manufactured by Sanshin Chemical Co., Ltd.), “CPI-100P”, “CPI-100A” (manufactured by San Apro Co., Ltd.), “WPI-069”, “WPI-1” 3 ”,“ WPI-116 ”,“ WPI-041 ”,“ WPI-044 ”,“ WPI-054 ”,“ WPI-055 ”,“ WPAG-281 ”,“ WPAG-567 ”,“ WPAG-596 ” (As described above, Wako Pure Chemical Industries, Ltd.) is a preferred specific example of the energy-sensitive linear acid generator of the present invention.

  The energy-sensitive linear acid generator (A) used in the present invention is used alone or in combination of two or more. It is also possible to use an acid generator with heat. When the thermal stability of the supporting substrate (D) is high, it is possible to advance the crosslinking of the cationic curable silicone resin (C) more rapidly by using these together and heating after light irradiation. is there.

  The amount of the energy sensitive acid generator (A) used in the present invention is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the cationic curable silicone resin (C). Particularly preferred is 0.5 to 10 parts by weight. When the addition amount of the energy-sensitive linear acid generator (A) is less than 0.1 parts by weight, polymerization or crosslinking by cationic polymerization does not proceed sufficiently, and good adhesive strength may not be obtained. Moreover, when there are more addition amounts of energy-sensitive linear acid generator (A) than 20 weight part, since there are too many low molecular components in the energy-sensitive-polymerizable composition for release sheets, sufficient cohesive force and adhesive force are sufficient. It is not practical in that it may not be obtained, and it may lead to concerns and cost increase due to the large amount of ionic substance remaining in the cured product.

  Next, the amine compound (B) of the present invention will be described. In the present invention, the amine compound (B) is used as a photosensitizer, so that it can be irradiated with near ultraviolet rays of 300 nm or more by a high-pressure mercury lamp or the like as compared with a conventionally known energy-sensitive acid generation composition. High acid generation efficiency. The amine compound of the present invention has an extremely high sensitizing effect as compared with known acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. It is excellent in practicality.

Examples of the substituted or unsubstituted aryl group in the substituents Ar ¹ , Ar ² , and Ar ³ in the general formula (2) include an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, Biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl Group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group Heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenyl Renyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl Groups, pentaphenyl groups, pentacenyl groups, tetraphenylenyl groups, hexaphenyl groups, hexacenyl groups, rubicenyl groups, coronenyl groups, trinaphthylenyl groups, heptaphenyl groups, heptacenyl groups, pyrantrenyl groups, and oberenyl groups. However, it is not limited to these.

The substituted or unsubstituted heterocyclic group in the substituents Ar ¹ , Ar ² , and Ar ³ in the general formula (2) has 4 to 24 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. And aromatic heterocyclic groups such as 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, and 2-thianthrenyl group. 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl Group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H- Danazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-Carborinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl Group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group Quinuclidinyl group, morpholinyl group, thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-coumarinyl group, etc. not limited to, the general formula (2) may be bonded at any substitution positions for a substitution position which is capable of forming a covalent bond with the nitrogen atom, Ar ¹ thereof are also the present invention, It is included in the category of substituents represented by Ar ² and Ar ³ .

The above-described substituents Ar ¹ , Ar ² , and Ar ³ may be further substituted with other substituents, such as a hydroxyl group, a mercapto group, a cyano group, a nitro group, Halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, dialkyl An amino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group and the like can be mentioned, and these are directly bonded to Ar ¹ , Ar ² , and Ar ³ . Through an alkylene group, an azaalkylene group, an alkynylene group, an azaalkynylene group, an arylene group, etc. Specific examples thereof include a substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group represented by the substituents Ar ⁴ and Ar ⁵ in the general formula (13) described above. The same substituents as those exemplified as the substituents which may be substituted may be mentioned, but are not limited thereto.

  Specific structures are shown below, but the structure of the amine compound (B) of the present invention is not limited thereto.

  The amine compound (B) of the present invention preferably has a maximum absorption wavelength λmax in the wavelength region of 325 nm to 400 nm and a molar extinction coefficient ε of 420 nm or more is zero. If an amine compound other than the above range is used, it may not function sufficiently as a photosensitizer, or yellowing may be remarkable, and the transparency of the energy-sensitive polymerizable composition for release sheet in the present invention may be lost. is there.

  The ratio of the energy sensitive acid generator (A) and the amine compound (B) of the present invention is not particularly limited, but with respect to 1 part by weight of the energy sensitive acid generator (A), It is preferable to use 0.01 to 5 parts by weight of the amine compound (B). If an amount of the amine compound (B) less than this range is used, the effect may not be observed. If an amount of the amine compound (B) greater than this range is used, yellowing is remarkable, and the release sheet feeling in the present invention The transparency of the energy beam polymerizable composition may be lost.

  Although the mechanism of acid generation is currently under investigation, it is considered that the amine compound (B) is probably excited by absorbing light and then transferring energy to the energy-sensitive acid generator (A). is doing. Since the efficiency of energy transfer at this time is very good compared to other combinations, polymerization of the polymerizable substance can be achieved by combining the energy-sensitive linear acid generator (A) and the amine compound (B) of the present invention. It seems that it was possible to provide a combination of compounds having a remarkably good effect as an initiator.

  Next, the cation curable silicone resin (C) of the present invention will be described. The cationic curable silicone resin (C) of the present invention is not particularly limited as long as it is cured by a reaction with energy rays in the presence of an energy sensitive acid generator. A polyorganosiloxane having an epoxy group, oxetanyl group or vinyl ether group in the molecule is preferred, and a polyorganosiloxane having an epoxy group in the molecule is particularly preferred.

  The polyorganosiloxane having an epoxy group in the molecule has at least two epoxy groups in one molecule, and may be linear, branched, or a mixture thereof. The type of epoxy group contained in the polyorganosiloxane is not particularly limited as long as ring-opening cationic polymerization proceeds by the energy-sensitive linear acid generator (A) of the present invention. Specific examples include γ-glycidyloxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, β- (4-methyl-3,4-epoxycyclohexyl) propyl group, and the like. Such polyorganosiloxane having an epoxy group in the molecule is commercially available, and examples thereof include a product name “Silicolys POLY201” manufactured by Rhodia.

  Next, the support base material (D) of the present invention will be described. As the support substrate (D) of the present invention, various known materials can be used without particular limitation, and examples thereof include paper, plastic, and plastic film. Specific examples of the paper include polyethylene laminated paper, glassine paper, clay coated paper, high quality paper, coated paper, thermal paper, synthetic paper, and the like. Examples of plastics include molded products such as polypropylene, polyethylene polyethylene terephthalate, and polyamide. Such plastic molded products are molded into various molded products, sheets, and films formed by an extraction molding machine depending on the application. In addition, those subjected to surface processing such as corona discharge treatment, flame treatment, plasma treatment, easy adhesion coating treatment, printing, etc. may be used. As the support substrate (D) of the present invention, it is particularly preferable to use paper or a plastic film.

  The energy-sensitive acid generator (A) of the present invention has a sufficiently high sensitivity as an acid generator, but can also be used in combination with other acid generators. The acid generator that can be used in combination with the energy-sensitive linear acid generator (A) is not particularly limited, and “PAG”, “acid generator”, “photoacid generator”, “photopolymerization initiator”, “ Materials known in the industry under names such as “cationic polymerization initiator” and “polymerization catalyst” can be appropriately selected and used. Moreover, when using another acid generator, it is also possible to use individually or in combination.

  Examples of other energy sensitive acid generators that can be used in combination with the energy sensitive acid generator of the present invention include onium salt compounds. Examples of such onium salt compounds include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, diazonium salt compounds, pyridinium salt compounds, benzothiazolium salt compounds, sulfoxonium salt compounds, and ferrocene compounds. These structures are not particularly limited, and may have a polyvalent cation structure such as a dication, and known counter anions can be appropriately selected and used.

  Examples of the energy-sensitive linear acid generator other than the onium salt that can be used in combination with the energy-sensitive linear acid generator of the present invention include nitrobenzyl sulfonates, alkyl or aryl-N-sulfonyloxyimides, and halogenated compounds. Alkylsulfonic acid esters, 1,2-disulfones, oxime sulfonates, benzoin tosylates, β-ketosulfones, β-sulfonylsulfones, bis (alkylsulfonyl) diazomethanes, iminosulfonates Compounds having a trihaloalkyl group, such as imide sulfonates, trihalomethyltriazines, and the like, but are not limited thereto.

  The ratio of the other acid generator used in combination with the energy sensitive acid generator (A) used in the present invention is not particularly limited, but it is 0 to 100 parts by weight of the energy sensitive acid generator (A) of the present invention. It is preferable to use in the range of 99 parts by weight.

  Moreover, the energy sensitive ray polymerizable composition for the release sheet of the present invention is an energy ray without using any other sensitizer due to the effect of using the energy sensitive acid generator (A) and the amine compound (B), In particular, it can be cured very quickly and reliably with respect to light irradiation in the wavelength region of 350 nm to 450 nm, but other sensitizers may be used in combination as required.

  Examples of other sensitizers that can be used in combination with the present invention include condensed polycyclic aromatic derivatives such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzoates Unsaturated ketones such as thiazole derivatives, chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives , Thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine Conductor, thiazine derivative, phenothiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative , Tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, carbazole derivatives, Metal arene complexes, organoruthenium complexes, etc. Edited by Nobu Okawara, "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemicals of Functional Dye" (1981, CMC), edited by Tadasaburo Ikemori, "Special Functional Materials" (1986) Dyes and sensitizers described in “Photographic Material List Book” (1996, published by Bunshin Publishing Co., Ltd.), but not limited to these, are necessary. Depending on, two or more kinds may be used in any ratio.

  Among these sensitizers, preferred are naphthalene derivatives, condensed polycyclic aromatic derivatives of anthracene derivatives, and phenothiazine derivatives, carbazole derivatives, and benzothiazole derivatives. Among them, anthracene derivatives are particularly preferred. It is done.

  Specific examples thereof include anthracene, 1-anthracene carboxylic acid, 2-anthracene carboxylic acid, 9-anthracene carboxylic acid, 9-anthracaldehyde, 9,10-bis (chloromethyl) anthracene, 9,10-bis (phenyl). Ethynyl) anthracene, 9-bromoanthracene, 1-chloro-9,10-bis (phenylethynyl) anthracene, 9-cyanoanthracene, 9,10-dibromoanthracene, 9,10-dicyanoanthracene, 9,10-dimethylanthracene, 9,10-dibutylanthracene, 9,10-diphenylanthracene, 9,10-di-p-tolylanthracene, 9,10-bis (p-methoxyphenyl) anthracene, 2-hydroxymethylanthracene, 9-hydroxymethylanthracene, -Methylanthracene, 9-phenylanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenoxyanthracene, 9,10-dimethoxyanthracene-2-sulfone Acid sodium, 1,4,9,10-tetrahydroxyanthracene, 2,2,2-trifluoro-1- (9-anthryl) ethanol, 1,8,9-trihydroxyanthracene, 1,8-dimethoxy-9, 10-bis (phenylethynyl) anthracene, 9-vinylanthracene, 9-anthracenemethanol, trimethylsiloxy ether of 9-anthracenemethanol, N, N′-diphenyl-N, N′-di-m-tolyl-biphenyl-4, 4'-diamine, phenothiazine N- ethylcarbazole, N- phenyl carbazole, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dimethoxy naphthalene.

  Although the addition amount in the case of using said other sensitizer together is not specifically limited, 0-100 weight part is preferable with respect to 100 weight part of energy-sensitive linear acid generators (A) of this invention.

  In the energy-sensitive polymerizable composition for release sheet of the present invention, various known additives such as a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, and a leveling agent are used as necessary. A pigment or the like can also be added. In some cases, a silicon compound or the like may be added without departing from the object of the present invention.

  The energy-sensitive polymerizable composition for release sheet of the present invention can be used by dissolving it in a solvent that dissolves each of the above components and applying it to the support substrate (D). The solvent used here is not particularly limited as long as it can uniformly dissolve the energy-sensitive polymerizable composition for release sheet of the present invention. Specific examples include 1,1,2,2-tetrachloroethane, ethylene dichloride, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl methoxypropionate, ethyl ethoxypro Pionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, isoamyl acetate, methyl lactate, Ethyl lactate, ethyl ethoxypropionate, N, N monodimethylformamide, N, N monodimethylacetamide, dimethyl sulfoxide, N-methylpyrrole Are preferred, such as down, the use of these solvents alone or in combination.

  The energy rays used to generate an acid from the energy sensitive linear acid generator (A) of the energy sensitive ray polymerizable composition for the release sheet of the present invention and to polymerize or crosslink the cation curable silicone resin (C), Energy-sensitive linear acid generator (A) or amine compound (B) absorbs energy-sensitive linear acid generator (A) and decomposes to generate an acid, which damages the supporting substrate (D). If it does not give, it will not specifically limit. Examples of such energy rays include, but are not limited to, ultra-high pressure mercury lamps, high pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed xenon lamps. Absent. Also suitable are lasers having an emission wavelength in the wavelength region of 300 nm to 450 nm, such as Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, and semiconductor excitation solid laser. An energy ray source etc. are mentioned. An electron beam can also be used as a suitable energy beam source. In addition, these light sources can be appropriately irradiated through optical devices such as filters, mirrors, and lenses. Furthermore, you may use together other hardening means, such as heat hardening, for example as needed in the range which does not degrade a support base material (D). Although the heating temperature in the case of using the said heat curing together is not specifically limited, It is preferable that it is 50-200 degreeC.

  The release sheet of the present invention is formed by irradiating active energy rays after forming a silicone release layer on the at least one surface of the support substrate (D) with the energy sensitive ray polymerizable composition for the release sheet of the present invention. It is formed by curing an energy-sensitive polymerizable composition for use, and is in close contact with both the support substrate (D) and the silicone release layer between the support substrate (D) and the silicone release layer. Various well-known sealing layers are used for the purpose of preventing the bleeding of the ink and additives in the cation curable silicone resin (C) from the printed support substrate (D) in order to improve the properties. It may be provided.

  When the energy-sensitive polymerizable composition for release sheet of the present invention is applied to the supporting substrate (D) or the sealing layer, any known method can be used. For example, bar coater, applicator, roll coater, Mayer bar, wire bar, blade coater, air knife coater, calendar method, extrusion coating, comma coater, die coater, lip coater, gravure, curtain coater, micro gravure coater, slide coater, etc. And coating methods such as coating, dispensing, stamping, and screen printing.

The coating amount of the energy-sensitive polymerizable composition for release sheet of the present invention applied on the supporting substrate (D) or the sealing layer varies depending on the type of the supporting substrate (D) or the sealing layer. .1 to 20 g / m ² , more preferably 0.5 to 10 g / m ² . When the coating amount of the composition is extremely small as less than 0.1 g / m ^2, it is difficult to form a uniform silicone release layer on the supporting substrate (D) or the sealing layer, and the peelability is deteriorated. Further, even if the coating amount of the composition exceeds 20 g / m ² , the properties do not change, and only the cost increases, which is not preferable.

  As the most general production method of the release sheet of the present invention, the energy-sensitive polymerizable composition for the release sheet of the present invention is applied on the support substrate (D) or the sealing layer, and then the energy described above. A silicone release layer is formed by irradiating a line. Furthermore, you may heat in the range which does not degrade a support base material (D), a sealing layer, or a silicone peeling layer as needed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all.

  The structures of the acid generator, the amine compound, and the sensitizer used in Examples and Comparative Examples of the present invention are shown below.

Table 1

Commercially available energy sensitive acid generators used in the examples are as follows.
"Cyracure UVI-6992": Dow Chemical Japan Co., Ltd., sulfonium · PF ₆ ^- salt,
"Cyracure UVI-6974": Dow Chemical Japan Co., Ltd., sulfonium · SbF ₆ ^- salt,
"ADEKAOPTOMER SP150": ADEKA Corporation, Ltd., sulfonium · PF ₆ ^- salt,
"ADEKAOPTOMER SP152": ADEKA Corporation, Ltd., sulfonium · PF ₆ ^- salt,
"ADEKAOPTOMER SP170": ADEKA Corporation, Ltd., sulfonium · SbF ₆ ^- salt,
"ADEKAOPTOMER SP172": ADEKA Corporation, Ltd., sulfonium · SbF ₆ ^- salt,
"IRGACURE250": Ciba Specialty Chemicals Inc., iodonium · PF ₆ ^- salt,
"CI-5102": manufactured by Nippon Soda Co., Ltd., iodonium · PF ₆ ^- salt,
"CI-2855": manufactured by Nippon Soda Co., Ltd., iodonium · PF ₆ ^- salt,
"San-Aid SI-60L": Three New Chemical Co., Ltd., sulfonium · SbF ₆ ^- salt,
"San-Aid SI-80L": Three New Chemical Co., Ltd., sulfonium · SbF ₆ ^- salt,
"San-Aid SI-100L": Three New Chemical Co., Ltd., sulfonium · SbF ₆ ^- salt,
"San-Aid SI-110L": Three New Chemical Co., Ltd., sulfonium · PF ₆ ^- salt,
"San-Aid SI-180L": Three New Chemical Co., Ltd., sulfonium · PF ₆ ^- salt,
"CPI-100P": San-Apro Ltd., sulfonium · PF ₆ ^- salt,
"CPI-100A": San-Apro Ltd., sulfonium · SbF ₆ ^- salt,
"WPI-113": manufactured by Wako Pure Chemical Industries, Ltd., iodonium · PF ₆ ^- salt,
"WPI-116": manufactured by Wako Pure Chemical Industries, Ltd., iodonium · SbF ₆ ^- salt,
"WPI-041": manufactured by Wako Pure Chemical Industries, Ltd., sulfonium, iodonium · PF ₆ ^- salt,
"WPI-044": manufactured by Wako Pure Chemical Industries, Ltd., sulfonium, iodonium · PF ₆ ^- salt,
"WPI-054": manufactured by Wako Pure Chemical Industries, Ltd., sulfonium, iodonium · PF ₆ ^- salt,
"WPI-055": manufactured by Wako Pure Chemical Industries, Ltd., sulfonium, iodonium · PF ₆ ^- salt,
The energy-sensitive acid generator is partially marketed as a propylene carbonate solution. The addition amount of the energy-sensitive linear acid generator in Examples and Comparative Examples is the addition amount of only the onium salt converted from the weight concentration and the molecular weight of the onium salt, and does not include the weight of the solvent.

Example 1
As an energy-sensitive linear acid generator of the present invention, 1 part by weight of “Syracure UVI-6992”, 0.2 part by weight of compound (15) as an amine compound, a cationic curable silicone resin (trade name “Silicolys POLY201”). ”, Produced by Rhodia Co., Ltd.) and 4 parts by weight of isopropyl alcohol as a diluent solvent were mixed to prepare an energy-sensitive polymerizable composition for a release sheet. After applying this energy-sensitive polymerizable composition for release sheet to polyethylene laminated paper (75 g / m ² ) so that the film thickness after curing is 2 μm, using a 120 W / cm metal halide lamp, 50 m / min. The energy-sensitive polymerizable composition for release sheet was cured by passing it on a conveyor, and a release sheet was obtained. Each item was evaluated about the obtained peeling sheet. The results are shown in Table 2.

  The following evaluation methods were used for evaluation of Examples and Comparative Examples.

(1) Curability The surface state when the release sheet obtained in Example or Comparative Example was lightly rubbed with a finger was visually evaluated.
○: No trace of rubbing remains and curing is sufficient.
X: Rubbed traces remain and curing is insufficient.

(2) Adhesiveness The drop-off when the release sheet obtained in the example or comparative example was rubbed with a finger 5 times was evaluated.
○: No dropout and sufficient adhesion.
(Triangle | delta): There exists some omission and adhesiveness is not enough.
X: Dropping is large and adhesion is insufficient.

Examples 2-39 and Comparative Examples 1-12
1 part by weight of the energy-sensitive linear acid generator of Example 1 is 1 part by weight of each of the energy-sensitive linear acid generators shown in Table 2, and 0.2 parts by weight of the amine compound is shown in Table 2 or sensitization. Except having replaced 0.2 parts by weight of each agent, the energy-sensitive polymerizable composition for release sheet was prepared in exactly the same manner as in Example 1 to obtain a release sheet. Table 2 shows the evaluation results of the curability and adhesion of the obtained release sheet.

Table 2

  As in Examples 1 to 39, the energy-sensitive polymerizable composition for release sheet using the energy-sensitive acid generator and amine compound of the present invention creates a release sheet with a small amount of active energy ray irradiation. I was able to. Further, the obtained release sheet had particularly excellent characteristics in curability and adhesion. On the other hand, when an energy-sensitive linear acid generator other than the present invention is used (Comparative Examples 1 to 4) and when the amine compound of the present invention is not used (Comparative Examples 5 to 12), irradiation with a predetermined active energy ray is performed. When the amount was sufficient, curing did not proceed and the desired release sheet could not be obtained.

Example 40
A double-sided pressure-sensitive adhesive tape (trade name “Double-Face”, manufactured by Toyo Ink Manufacturing Co., Ltd.) was attached to the release sheet obtained in Example 1, and left at 25 ° C. under a load of 20 g / cm ² . 1 day and 7 days later, the adhesive tape attached at an angle of 180 ° at a peeling speed of 300 mm / min was peeled off, and the force required for peeling (g / 50 mm) was measured, and the load during peeling, and The change with time of the peeling load was evaluated. The results are shown in Table 3.

Examples 41-78
Except that the release sheet of Example 40 was replaced with the release sheet shown in Table 3, the load at the time of peeling and the change with time of the peeling load were evaluated in exactly the same manner as in Example 40. The results are shown in Table 3.

Table 3

  The release sheet using the energy-sensitive linear acid generator of the present invention has excellent release characteristics and exhibits a stable release load over time (Examples 40 to 78). On the other hand, when the energy-sensitive polymerizable composition for release sheet of the present invention was not used, since release sheets having sufficient curability as in Comparative Examples 1 to 12 could not be created, Examples 40 to 78 and A similar evaluation could not be made.

  The energy sensitive ray polymerizable composition for release sheet of the present invention could be cured with a small amount of active energy ray irradiation. Further, the energy-sensitive radiation polymerizable composition for release sheet of the present invention uses a small amount of energy by using the energy-sensitive linear acid generator (A) having a specific structure and the amine compound (B). Even in the irradiation of rays, very strong acid is efficiently generated, so it is possible to improve workability by shortening the irradiation time of active energy rays and to reduce the deterioration of the supporting substrate due to the irradiation of energy rays. . Further, by using the energy-sensitive polymerizable composition for release sheet of the present invention, a release sheet having a stable release performance with little change in release force over time can be provided.

Claims (6)

An energy-sensitive linear acid generator (A) represented by the following general formula (1), an amine compound (B) represented by the following general formula (2), and a cation curable silicone resin (C) An energy-sensitive polymerizable composition for a release sheet.
General formula (1)

(However, L ⁺ represents an arbitrary cation.
X ⁻ represents an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ . )
General formula (2)

^{(Wherein, Ar 1, Ar 2, Ar} 3 each independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group.
Ar ¹ and Ar ² , Ar ¹ and Ar ³ , or Ar ² and Ar ³ may be bonded to each other to form a ring structure. ) 2. The energy sensitive linear polymerization for release sheet according to claim 1, wherein the energy sensitive acid generator (A) is a sulfonium salt represented by the following general formula (3) or an iodonium salt represented by the following general formula (4). Sex composition.


General formula (3)

(However, R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted complex, Cyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted It represents a group selected from a substituted oxycarbonyl group or a halogen atom.
R ¹ And R ² , R ¹ And R ³ or R ² And R ³ may be bonded to each other to form a ring structure.
X ⁻ represents an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ . )
General formula (4)

(However, Ar ⁴ and Ar ^{5 each} represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
X ⁻ represents an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ . ) Wherein X ^-, PF ₆ ^-, SbF ₆ ^- claim 1 or 2 release sheet for sensitive energy ray polymerizable composition according selected from either.   The energy-sensitive polymerizable composition for a release sheet according to any one of claims 1 to 3, wherein the cationic curable silicone resin (C) is a polyorganosiloxane having an epoxy group in the molecule.   A release sheet comprising a support substrate (D) and a silicone release layer obtained by polymerizing the energy-sensitive polymerizable composition for release sheet according to any one of claims 1 to 4.   A silicone release layer is formed on the at least one surface of the support substrate (D) with the energy-sensitive polymerizable composition for release sheet according to any one of claims 1 to 4, and then irradiated with active energy rays. A method for producing a release sheet.