CN107229185B - Energy-sensitive composition, cured product, and method for producing the cured product - Google Patents

Abstract

The present invention relates to an energy-sensitive composition, a cured product, and a method for producing a cured product. The present invention addresses the problem of providing an energy-sensitive composition having excellent thermal weight stability, a cured product obtained by curing the composition, and a method for producing the cured product. The invention provides an energy-sensitive composition comprising at least 1 compound component (P) selected from the group consisting of (P1) a cationic and/or acid-catalytic polymerizable and/or crosslinkable compound, (P2) a compound having increased solubility in a developer under the action of an acid, and (Px) a radically polymerizable or crosslinkable compound, and (Q) a sulfonium salt represented by formula (a 1).

Description

Energy-sensitive composition, cured product, and method for producing the cured product

technical field

The present invention relates to an energy-sensitive composition containing a sulfonium salt, a cured product obtained by curing the composition, and a method for producing the cured product.

Background technique

Conventionally, it has been proposed to contain an epoxy compound in a sealant for an organic EL display element or an energy-sensitive composition for a wafer-level lens (Wafer-Level lens). For example, Patent Document 1 proposes an energy-sensitive resin having an epoxy group or an oxetanyl group and having an epoxy group or an oxetanyl group in addition to an The energy-sensitive resin composition which does not contain an ether bond and an ester bond other than an oxy group or an oxetanyl group. In addition, Patent Document 2 proposes an alicyclic epoxy compound having a specific structure and having 2 An energy-sensitive resin composition comprising a silicone compound having at least one glycidyl group, and a curing agent.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2015/064410

Patent Document 2: International Publication No. 2015/129503

SUMMARY OF THE INVENTION

The problem to be solved by the invention

However, for the previous energy-sensitive compositions, weight stability in a high temperature environment is required.

An object of the present invention is to provide an energy-sensitive composition excellent in thermogravimetric stability, a cured product obtained by curing the composition, and a method for producing the cured product.

means of solving problems

The inventors of the present application discovered that the thermogravimetric stability can be improved by using a sulfonium salt having a specific structure, and completed the present invention.

A first aspect of the present invention is an energy-sensitive composition comprising at least one compound component (P) and (Q) a sulfonium salt represented by the following formula (a1) selected from the group consisting of: The group consists of (P1) a polymerizable and/or crosslinkable compound based on a cationic and/or acid-catalyzed manner, (P2) a compound whose solubility in a developer under the action of an acid increases, and (Px) It consists of a radically polymerizable or crosslinkable compound.

(in the formula, R ¹ and R ² independently represent an alkyl group which may be substituted by a halogen atom or a group represented by the following formula (a2), and R ¹ and R ² may be bonded to each other and form a ring together with the sulfur atom in the formula , R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, X ^- represents a monovalent anion, wherein R ¹ and R ² cannot also be an alkyl group which can be substituted by a halogen atom.)

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, R ⁴ represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a thiophene which may be substituted by a halogen atom base, thienylcarbonyl, furanyl, furanylcarbonyl, selenophenyl, selenophenylcarbonyl, heterocyclic aliphatic hydrocarbon, alkylsulfinyl, alkylsulfonyl, hydroxy(poly)alkylene An oxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more.)

(in the formula, R ⁵ represents an alkylene group or a group represented by the following formula (a5), and the alkylene group may be represented by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryl group Oxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl Acyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, which may be substituted by substituted amino group, cyano group, nitro group or halogen atom, R ⁶ represents an alkyl group or the following formula (a6) Represents a group, the alkyl can be hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio , alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy , may be substituted by a substituted amino, cyano, nitro or halogen atom, A ² represents a single bond, S, O, sulfinyl, or carbonyl, and n1 represents 0 or 1.)

(in the formula, R ⁷ and R ⁸ independently represent an alkylene group or a group represented by the following formula (a5), and the alkylene group may be represented by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxy group ylcarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, aryl Sulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, may be substituted by a substituted amino, cyano, nitro or halogen atom, R ⁹ and R ¹⁰ independently represent a Halogen atom-substituted alkyl group or group represented by the above formula (a2), R ⁹ and R ¹⁰ can bond with each other and form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, sulfinyl, or carbonyl, X ^- as described above, n2 represents 0 or 1, wherein, R ⁹ and R ¹⁰ are not simultaneously an alkyl group which may be substituted by a halogen atom.)

(in the formula, ring Z ² represents an aromatic hydrocarbon ring, R ¹¹ represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, which may be substituted by a halogen atom, Arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, Arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m2 represents an integer of 0 or more.)

(in the formula, ring Z ³ represents an aromatic hydrocarbon ring, R ¹² represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, which may be substituted by a halogen atom, Arylthiocarbonyl, acyloxy, arylthio, alkylthio, thienylcarbonyl, furylcarbonyl, selenophenylcarbonyl, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl Acyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m3 represents an integer of 0 or more .)

A second aspect of the present invention is a cured product obtained by curing the energy-sensitive composition of the first aspect of the present invention.

A third aspect of the present invention is a method for producing a cured product including a step of polymerizing and/or crosslinking the energy-sensitive composition of the first aspect of the present invention.

effect of invention

According to this invention, the energy-sensitive composition excellent in thermogravimetric stability, the hardened|cured material obtained by hardening this composition, and the manufacturing method of this hardened|cured material can be provided.

Description of drawings

FIG. 1 is a TG/DSC curve showing the thermogravimetric change of Example 3. FIG.

FIG. 2 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 7. FIG.

FIG. 3 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 8. FIG.

FIG. 4 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 9. FIG.

[ Fig. 5] Fig. 5 is a TG/DSC curve showing the thermogravimetric change of the reference example.

Detailed ways

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the object of the present invention.

In this specification, descriptions such as "cationic and/or acid-catalyzed", etc., "A and/or B", "A and/or B", "A and/or B", etc. mean "selected from A and at least one of the group consisting of B". Here, A and B are arbitrary terms.

<Energy sensitive composition>

The energy-sensitive composition according to the present invention contains at least one compound component (P) selected from the group consisting of (P1) based on cationic properties, and (Q) a sulfonium salt represented by the above formula (a1). and/or acid-catalyzed polymerizable and/or cross-linkable compounds, (P2) compounds with increased solubility in developing solutions under the action of acids, and (Px) radically polymerizable or cross-linkable compounds composition of compounds.

By making the energy-sensitive composition according to the present invention contain the sulfonium salt (hereinafter, also referred to as "sulfonium salt (Q)") represented by the above formula (a1), the compound component (P) and the sulfonium salt (Q) are contained in the composition. ), the concentration of protons increases as the temperature rises, so it is presumed that the stepwise polymerization of the compound component (P) continues, the polymerization is accelerated, and the amount of monomers decomposed by heat is small. From this, it is presumed that the energy-sensitive composition according to the present invention has improved weight stability with respect to heat. In addition, the system of generating a proton by the sulfonium salt (Q) includes a system of generating a proton by decomposition of the sulfonium salt (Q) itself, and a system of generating a proton by removing hydrogen from the components in the system.

[(P1) Polymerizable and/or crosslinkable compound based on cationic and/or acid-catalyzed form]

The polymerizable and/or crosslinkable compound based on a cationic and/or acid-catalyzed system (hereinafter, also referred to as "compound (P1)") includes, for example, a cation containing an alkyl group or an aryl group or a proton capable of A compound that undergoes cationic polymerization. Examples of these include cyclic ethers, especially epoxy compounds, oxetane compounds, vinyl ether compounds, and hydroxyl-containing compounds. In addition, lactone compounds, cyclic sulfide compounds, and vinyl sulfide compounds can also be used. However, in this specification, the compound containing an ethylenically unsaturated group (vinyl group) is a compound (containing an epoxy group and an oxetanyl group) further having an epoxy group and/or an oxetanyl group (oxetanyl group). /vinyl-containing compound), it belongs to compound (P1); when it is a compound other than that (does not contain epoxy/oxetanyl/vinyl-containing compound), it belongs to compound (Px). In the present specification, unless otherwise specified, the "epoxy group" usually includes not only oxiranyl but also oxetanyl and alicyclic epoxy groups.

Further examples include aminoplasts and phenol-based Resol resins. They are especially melamine resins, urea resins, epoxy resins, phenolic resins, acrylic resins, polyester resins and alkyd resins, especially acrylic resins, polyester resins or mixtures of alkyd resins and melamine resins. Moreover, these modified surface coating resins (for example, acrylic-modified polyester resin, acrylic-modified alkyd resin, etc.) are mentioned. The term surface coating resin preferably includes amino resins. Examples of these include etherified and non-etherified melamine resins, urea resins, guanidine resins, and biuret resins. Contains etherified amino resins (eg, methylated melamine resins or butylated melamine resins (N-methoxymethyl-melamine or N-butoxymethyl-melamine), methylated/butylated glycolurils ) surface coating resin curing acid catalyst is particularly important.

When the compound (P1) is an epoxy compound, it is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, but it is preferably a compound having at least two epoxy groups in the molecule. The epoxy compound can be selected from various compounds having an epoxy group conventionally incorporated in curable compositions. The epoxy compound may be a low-molecular compound having an epoxy group as a non-polymer, or a polymer having an epoxy group, but preferably a non-polymer. As the non-polymer having an epoxy group, an aliphatic epoxy compound not containing an aromatic group is preferable from the viewpoint of excellent thermogravimetric stability of a cured product formed using the energy-sensitive composition. Among the aliphatic epoxy compounds, an aliphatic epoxy compound having an alicyclic epoxy group is preferable because stepwise polymerization is performed by ring-opening polymerization and polymerization can be accelerated.

Specific examples of the aliphatic epoxy compound having an alicyclic epoxy group include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane- m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3 ,4-Epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl Alkyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate , β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexanecarboxylate) cyclohexane), bis(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalate Dioctyl dicarboxylate (epoxycyclohexahydrophthalic acid dioctyl), epoxycyclohexahydrophthalic acid di-2-ethylhexyl, epoxy resin having tricyclodecenyl oxide, following formula (P1-1) A compound represented by ~(P1-5). Among the specific examples of these aliphatic epoxy compounds, the alicyclic epoxy compounds represented by the following formulae (P1-1) to (P1-4) are preferable, and more preferable from the viewpoint that the stepwise polymerization is performed and the polymerization can be accelerated. Alicyclic epoxy compounds represented by the following formulae (P1-1) to (P1-2). These alicyclic epoxy compounds may be used alone or in combination of two or more. The compound component (P) or the compound (P1) preferably contains an alicyclic epoxy compound represented by the formula (P1-1) and an alicyclic epoxy compound represented by the formula (P1-2), especially when reduction in outgassing is desired. The ratio of at least one of the group consisting of the formula epoxy compound and the alicyclic epoxy compound represented by the formula (P1-8) in the compound component (P) or the entire compound (P1) may be 1 to 99 mass % is 10-90 mass %, 20-80 mass %, 30-70 mass %, 40-60 mass %, etc. Moreover, it is preferable to use together the alicyclic epoxy compound represented by formula (P1-1) and the alicyclic epoxy compound represented by formula (P1-2) from the viewpoint of exhaust gas reduction and the viscosity of an energy-sensitive composition. When the alicyclic epoxy compound represented by the formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) are used in combination, as the alicyclic epoxy compound represented by the formula (P1-1) The content of the alicyclic epoxy compound represented by the formula (P1-1) relative to the total amount of the alicyclic epoxy compound represented by the formula (P1-2) is not particularly limited, and may be, for example, 1 to 99 mass %, 10-90 mass %, 20-80 mass %, 30-70 mass %, 40-60 mass %, etc. may be sufficient.

(In formula (P1-1), Z represents a single bond or a linking group (divalent group having one or more atoms). R ^a1 to R ^a18 are each independently selected from a hydrogen atom, a halogen atom, and an organic group The groups in the group consisting of, for example, a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an oxygen atom or a halogen atom, may be the same or different from each other.)

As the linking group Z, for example, a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, -C(CF ₃ ) ₂ -, and a divalent group in the group consisting of -R ^a19 -O-CO-, a group formed by bonding a plurality of them, etc., among which, preferred are -R ^a19 -O-CO-.

As a divalent hydrocarbon group which is a linking group Z, a C1-C18 linear or branched alkylene group, a divalent alicyclic hydrocarbon group, etc. are mentioned, for example. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, and 1,2-ethylene. , 1,3-propylene, etc. Examples of the above-mentioned divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,2-cyclopentylene, Cycloalkylene (including cycloalkylidene) such as 3-cyclohexylene, 1,4-cyclohexylene, cyclohexylidene and the like.

R ^a19 is an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and among them, a methylene group or an alkylene group is preferred ethyl.

As the compound represented by the formula (P1-1), it is preferable that a conjugated structure (particularly a π-electron conjugated structure) is not easily formed by dehydrogenation from the viewpoint of obtaining a cured product excellent not only in thermogravimetric stability but also in transparency. (conjugated structure), particularly preferably an alicyclic epoxy compound, specifically a compound in which two alicyclic epoxy groups in one molecule are bonded via a linking group containing a quaternary carbon and/or a heteroatom .

Moreover, as a compound (P1), the alicyclic epoxy compound represented by following formula (P1-2) - (P1-5) is mentioned.

(In formula (P1-2), R ^a1 to R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, for example, a hydrogen atom, a halogen atom, or may contain oxygen The hydrocarbon groups of atoms or halogen atoms may be the same or different. R ^a2 and R ^a10 may be bonded to each other.)

(In formula (P1-3), R ^a1 to R ^a10 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, for example, a hydrogen atom, a halogen atom, or may contain oxygen The hydrocarbon groups of atoms or halogen atoms may be the same or different. R ^a2 and R ^a8 may be bonded to each other.)

(In formula (P1-4), R ^a1 to R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, for example, a hydrogen atom, a halogen atom, or may contain oxygen The hydrocarbon groups of atoms or halogen atoms may be the same or different. R ^a2 and R ^a10 may be bonded to each other.)

(In formula (P1-5), R ^a1 to R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, for example, a hydrogen atom, a halogen atom, or may contain oxygen The hydrocarbon groups of atoms or halogen atoms may be the same or different from each other.)

In formula (P1-1), when R ^a1 to R ^a12 are organic groups, the organic groups are not particularly limited as long as the object of the present invention is not hindered, and may be hydrocarbon groups or may be formed of carbon atoms and halogen atoms. A group containing not only a carbon atom and a hydrogen atom but also a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a hetero atom such as a silicon atom may be used. As an example of a halogen atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, etc. are mentioned.

As the organic group, the following groups are preferable: a hydrocarbon group; a group formed of a carbon atom, a hydrogen atom, and an oxygen atom; a halogenated hydrocarbon group; a group formed of a carbon atom, an oxygen atom, and a halogen atom; A group formed by carbon atoms, hydrogen atoms, oxygen atoms, and halogen atoms. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1-20 are preferable, as for the carbon number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-decyl Chain alkyl groups such as heptaalkyl, n-octadecyl, n-nonadecyl, and n-eicosyl; vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-propenyl Chain alkenyl such as butenyl, 2-n-butenyl, and 3-n-butenyl; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; phenyl , o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthracenyl, and phenanthryl Aralkyl groups such as benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl, and β-naphthylethyl.

Specific examples of the halogenated hydrocarbon group are chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2 ,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, and perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl and other halogenated chain alkyl groups; 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl Hexyl, and halocycloalkyl such as 4-bromocyclohexyl; 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl , 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4 -Bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl and other halogenated aryl; 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl base, 2-bromophenylmethyl, 3-bromophenylmethyl, 4-bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl, 4-fluorophenylmethyl, etc. Halogenated aralkyl.

Specific examples of groups consisting of carbon atoms, hydrogen atoms, and oxygen atoms are hydroxy chain alkyl groups such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl; 2 -Halocycloalkyl such as hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-dihydroxyphenyl , 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl, and 3,5-dihydroxyphenyl and other hydroxyaryl groups ; hydroxyaralkyl groups such as 2-hydroxyphenylmethyl, 3-hydroxyphenylmethyl, and 4-hydroxyphenylmethyl; methoxy, ethoxy, n-propoxy, isopropoxy, n- Butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethyl Hexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-decyloxy Chain alkoxy groups such as hexaalkyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, and n-eicosyloxy; vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, 3-n-butenyloxy, etc. Alkenyloxy; phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, alpha-naphthyloxy, beta-naphthyloxy, biphenyl-4-yloxy aryloxy, biphenyl-3-yloxy, biphenyl-2-yloxy, anthracenyloxy, and phenanthrenyloxy; benzyloxy, phenethyloxy, α-naphthalene Aralkyloxy groups such as phenylmethyloxy, β-naphthylmethyloxy, α-naphthylethyloxy, and β-naphthylethyloxy; methoxymethyl, ethoxymethyl base, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl alkoxyalkyl groups such as 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; methoxy Methoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methyl Oxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy-n-propoxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, and alkoxyalkoxy groups such as 4-n-propoxy-n-butyloxy; alkoxyaryl groups such as 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl ; 2-methoxyphenoxy, 3-methoxyphenoxy, and 4-methoxyphenoxy and other alkoxyaryloxy groups; formyl, acetyl, propionyl, butyryl, pentyl Aliphatic acyl groups such as acyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, and decanoyl; aromatic acyl groups such as benzoyl, α-naphthoyl, and β-naphthoyl; methoxycarbonyl, ethoxy ylcarbonyl, n-propoxycarbonyl, n-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n- Chain alkyloxycarbonyl such as octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl; oxycarbonyl; formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and aliphatic acyloxy groups such as decanoyloxy; aromatic acyloxy groups such as benzoyloxy, α-naphthoyloxy, and β-naphthoyloxy.

R ^a1 to R ^a18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, especially, More preferably, all of R ^a1 to R ^a18 are hydrogen atoms from the viewpoint of excellent mechanical properties of the cured product obtained by using the energy-sensitive composition.

In formulae (P1-2) to (P1-5), R ^a1 to R ^a12 are the same as R ^a1 to R ^a12 in formula (P1-1). In the formula (P1-2) and the formula (P1-4), examples of the divalent group formed when R ^a2 and R ^a10 are bonded to each other include -CH ₂ - and -C(CH ₃ ) ₂ - . In the formula (P1-3), examples of the divalent group formed when R ^a2 and R ^a8 are bonded to each other include -CH ₂ - and -C(CH ₃ ) ₂ -.

Among the alicyclic epoxy compounds represented by formula (P1-1), specific examples of preferable compounds include lipids represented by the following formulae (P1-1a), (P1-1b) and (P1-1c) Cyclic epoxy compounds, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane [=2,2-bis(3,4-epoxycyclohexyl)propane], and the like.

Among the alicyclic epoxy compounds represented by the formula (P1-2), specific examples of preferred compounds include bicyclononadiene diepoxides represented by the following formula (P1-2a), or bicyclononane Diene diepoxide, etc.

Among the alicyclic epoxy compounds represented by formula (P1-3), specific examples of preferred compounds include S-spiro[3-oxatricyclo[3.2.1.0 ^2,4 ]octane-6, 2'-oxirane] and so on.

Among the alicyclic epoxy compounds represented by the formula (P1-4), specific examples of preferred compounds include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, and 1-methylmethane. yl-4-(3-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane, etc.

Among the alicyclic epoxy compounds represented by formula (P1-5), specific examples of preferred compounds include 1,2,5,6-diepoxycyclooctane (1,2,5,6- diepoxycyclooctane) and so on.

As an example of a non-polymer having an epoxy group that can be used as the compound (P1) other than the aliphatic epoxy compound having an alicyclic epoxy group described above, (meth)acrylic acid shrinkage can be mentioned (Meth)acrylic acid ring such as glycerol ester, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. Oxyalkyl esters; 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxyn-propyl (meth)acrylate, 4-glycidyloxyn-butyl (meth)acrylate Esters, 5-glycidyloxy-n-hexyl (meth)acrylate, 6-glycidyloxy-n-hexyl (meth)acrylate and other epoxyalkyloxyalkyl (meth)acrylates; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin and other bifunctional epoxy resins; phenol Novolac type epoxy resin, brominated phenol Novolac type epoxy resin, o-cresol Novolac type epoxy resin, bisphenol A Novolac type epoxy resin, and bisphenol AD Novolac type epoxy resin and other Novolac type epoxy resin; two Cycloaliphatic epoxy resins such as epoxides of cyclopentadiene-type phenolic resins; aromatic epoxy resins such as epoxies of naphthalene-type phenolic resins; 9,9-bis[4-(glycidyloxy) Phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9-bis[4-[2-( Glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9,9-bis [4-(Glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, and 9,9-bis(6-glycidyloxynaphthalen-2-yl)-9H-fluorene , 9,9-bis(6-glycidyloxynaphthalene-1-yl)-9H-fluorene, 9,9-bis(5-glycidyloxynaphthalene-1-yl)-9H-fluorene, etc. 9 ,9-bis(glycidyloxynaphthyl)fluorenes; 9,9-bis[6-(2-glycidyloxyethoxy)naphthalene-2-yl]-9H-fluorene, 9,9 -Bis[6-(2-glycidyloxypropoxy)naphthalen-2-yl]fluorene, 9,9-bis[5-(2-glycidyloxyethoxy)naphthalene-1-yl ] Fluorene ; 9,9-bis{6-[2-(2-glycidyloxyethoxy)ethoxy]naphthalen-2-yl}-9H-fluorene, 9,9-bis{6-[2- (2-Glycidyloxypropoxy)propoxy]naphthalen-2-yl}-9H-fluorene, 9,9-bis{5-[2-(2-glycidyloxyethoxy) Ethoxy]naphthalene-1-yl}-9H-fluorene, 9,9-bis{5-[2-(2-glycidol Fluorene compounds containing epoxy groups such as 9,9-bis(glycidyloxydialkoxynaphthyl)fluorenes ; Glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl aminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl isophthalic acid Glycidyl amine epoxy resins such as methylamine and tetraglycidyl bisaminomethyl cyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-glycidoxy)phenyl]- 2-[4-[1,1-bis[4-(2,3-glycidoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4 -(2,3-glycidoxy)phenyl]-1-[4-[1-[4-(2,3-glycidoxy)phenyl]-1-methylethyl]benzene Tri-functional epoxy resins such as ethyl]ethyl]phenoxy]-2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bis-resorcinol tetraglycidyl Glyceryl ether, tetrafunctional epoxy resin such as tetraglycidoxybiphenyl, and 1,2-epoxy-4-(2-butanol of 2,2-bis(hydroxymethyl)-1-butanol oxopropyl)cyclohexane adduct. The 1,2-epoxy-4-(2-oxacyclopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol has been used as EHPE-3150 (manufactured by Daicel) sold in the market.

In addition, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3-hydroxymethyloxetane methacrylate can also be suitably used. Cyclobutyl ester, bis-1-ethyl-3-oxetanyl methyl ether, 1,4-bis-3-ethyloxetan-3-ylmethoxymethylbenzene, 3-ethyl Compounds having oxetanyl groups (oxetan alkane compound), and a monofunctional or a bifunctional or more oxetane compound in which the oxetanyl group in 1 molecule is 1 or more is mentioned suitably.

Among the non-polymers having an epoxy group that can be used as the compound (P1) other than the aliphatic epoxy compound having an alicyclic epoxy group, an epoxy group-containing fluorene is preferable from the viewpoint of increasing the refractive index The compound is more preferably the following formula (P1-8) containing 9,9-bis(glycidyloxynaphthyl)fluorenes.

(In formula (P1-8), ring Z ⁴ represents a condensed polycyclic aromatic hydrocarbon ring, R ^P35 and R ^P36 represent a substituent, R ^P37 represents a hydrogen atom or a methyl group, k1 is an integer of 0 to 4, and k2 is an integer of 0 or more, and k3 is an integer of 1 or more.)

In the above formula (P1-8), examples of the condensed polycyclic aromatic hydrocarbon ring represented by ring Z ⁴ include condensed bicyclic hydrocarbon rings (for example, C8-C20 condensed bicyclic hydrocarbon rings such as indene rings and naphthalene rings) The cyclic hydrocarbon ring is preferably a C10-C16 condensed bicyclic hydrocarbon ring), a condensed tricyclic hydrocarbon ring (for example, an anthracene ring, a phenanthrene ring, etc.), a condensed bi-tetracyclic hydrocarbon ring, or the like. As a preferable condensed polycyclic aromatic hydrocarbon ring, a naphthalene ring, an anthracene ring, etc. are mentioned, Especially a naphthalene ring is preferable. It should be noted that the two rings Z ⁴ substituted at the 9-position of fluorene may be the same or different rings, and usually may be the same ring.

It should be noted that the substitution position of the ring Z ⁴ substituted at the 9-position of fluorene is not particularly limited. For example, the naphthyl group substituted at the 9-position of fluorene may be 1-naphthyl, 2-naphthyl, etc., particularly preferred For 2-naphthyl.

In addition, in the above formula (P1-8), the substituent represented by R ^P35 includes, for example, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, an aryl group ( A non-reactive substituent such as a phenyl group (C6-C10 aryl group such as a phenyl group), etc.], in particular, is often a halogen atom, a cyano group, or an alkyl group (especially an alkyl group). The alkyl group may, for example, be a C1-C6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a tert-butyl group (for example, a C1-C4 alkyl group, especially a methyl group). In addition, when k1 is plural (two or more), R ^P35 may be different or the same. In addition, R ^P35 substituted on the two benzene rings constituting fluorene (or fluorene skeleton) may be the same or different. In addition, the bonding position (substitution position) of R ^P35 on the benzene ring constituting the fluorene is not particularly limited. k1 is preferably 0 to 1, particularly preferably 0. In addition, among the two benzene rings which comprise fluorene, k1 may be the same or different from each other.

Examples of R ^P36 substituted on ring Z ⁴ include alkyl groups (for example, C1-C12 alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, preferably C1-C8 alkyl groups). , more preferably C1-C6 alkyl, etc.), cycloalkyl (for example, C5-C8 cycloalkyl such as cyclohexyl, preferably C5-C6 cycloalkyl, etc.), aryl (for example, phenyl, tolyl, C6-C14 aryl groups such as xylyl, preferably C6-C10 aryl groups, more preferably C6-C8 aryl groups, etc.), aralkyl groups (such as benzyl, phenethyl and other C6-C10 aryl groups and C1- A hydrocarbon group such as an aralkyl group formed by bonding a C4 alkyl group, etc.); an alkoxy group (for example, a C1-C8 alkoxy group such as a methoxy group, preferably a C1-C6 alkoxy group, etc.), a cycloalkoxy group (C5 -OR ^P38 group [wherein, R ^P38 represents a hydrocarbon group (the hydrocarbon group exemplified above, etc.). ]; -SR ^P38 group (in the formula, R ^P38 is the same as above.) ; Acyl groups (for example, C1-C6 acyl groups such as acetyl groups, etc.); alkoxycarbonyl groups (for example, alkoxycarbonyl groups formed by bonding C1-C4 alkoxy groups such as methoxycarbonyl groups to carbonyl groups, etc.); halogen atoms ( A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); a hydroxyl group; a nitro group; a cyano group;

Among these, R ^P36 is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like, and R ^P36 is particularly preferably a hydrocarbon group [For example, an alkyl group (for example, a C1-C6 alkyl group)], an alkoxy group (C1-C4 alkoxy group, etc.), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), and the like.

In addition, in the same ring ^Z4 , when k2 is multiple (two or more), R ^P36 may be mutually different or the same. In addition, in the two rings ^Z4 , R ^P36 may be the same or different. Moreover, preferable k2 is 0-8, Preferably it is 0-6 (for example, 1-5), More preferably, it is 0-4, Especially, it may be 0-2 (for example, 0-1). It should be noted that, in the two rings Z ⁴ , k2 may be the same or different from each other.

In addition, in said formula (P1-8), R ^P37 is a hydrogen atom or a methyl group, R ^P37 is preferably a hydrogen atom.

In the above formula (P1-8), k3 may be 1 or more, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, especially 1. It should be noted that k3 may be the same or different in each ring Z, and generally, the same is often the case. It should be noted that the substitution position of the epoxy group-containing group is not particularly limited, as long as it is substituted at an appropriate substitution position of ring Z ⁴ . In particular, the epoxy group-containing group is at least in a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of the fluorene in the condensed polycyclic hydrocarbon ring (for example, the 5-position, the 6-position of the naphthalene ring, etc.) There are many cases where substitutions have been made.

As a specific compound represented by the above formula (P1-8), for example, 9,9-bis(glycidyloxynaphthyl)fluorene [for example, 9,9-bis(6-glycidyloxy) -2-naphthyl) fluorene, 9,9-bis(5-glycidyloxy-1-naphthyl) fluorene, etc.] and the like compound in which k3 is 1 in the above formula (P1-8).

(polymer having epoxy group)

The polymer having an epoxy group may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group, or may be a polymer having an epoxy group such as epichlorohydrin. A compound containing a hydroxyl group, a carboxyl group, an amino group, or the like, and a polymer obtained by introducing an epoxy group into a polymer having a reactive functional group such as an amino group. Moreover, the partial oxide of the polymer which has an unsaturated aliphatic hydrocarbon group in a side chain like 1, 2- polybutadiene can also be used suitably as a polymer which has an epoxy group. The partial oxide includes an epoxy group generated by oxidation of an unsaturated bond included in a side chain.

From the viewpoints of ease of availability, ease of production, ease of adjustment of the amount of epoxy groups in the polymer, etc., as the polymer having an epoxy group, it is preferable to use a monomer having an epoxy group or to include a monomer having an epoxy group. A polymer obtained by polymerizing a monomer mixture of the same monomer, and a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain.

(polymer of a monomer having an epoxy group or a monomer mixture comprising a monomer having an epoxy group)

Among the polymers having an epoxy group, from the viewpoints of ease of preparation, coatability of the energy-sensitive composition on a substrate, etc., a homopolymer of (meth)acrylate having an epoxy group, or a homopolymer having a ring Copolymers of oxy (meth)acrylates with other monomers.

The (meth)acrylate having an epoxy group may be a (meth)acrylate having a chain aliphatic epoxy group, or may be a (meth)acrylate having an alicyclic epoxy group as described later. . In addition, the (meth)acrylate having an epoxy group may contain an aromatic group. From the viewpoint of transparency of the cured product formed using the energy-sensitive composition, among (meth)acrylates having an epoxy group, an aliphatic (meth)acrylate having a chain-like aliphatic epoxy group, The aliphatic (meth)acrylate having an alicyclic epoxy group is more preferably an aliphatic (meth)acrylate having an alicyclic epoxy group.

Examples of (meth)acrylates containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate and 3-glycidyl (meth)acrylate. Oxyphenyl ester, 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxybenzene (meth)acrylate methyl ester, 2-glycidyloxyphenyl methyl (meth)acrylate, and the like.

Examples of aliphatic (meth)acrylates having a chain-like aliphatic epoxy group include epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. (meth)acrylate in which a chain-like aliphatic epoxy group is bonded to an oxy group (-O-) in an ester group (-O-CO-), such as. The chain-like aliphatic epoxy group which such a (meth)acrylate has may contain one or more oxy groups (-O-) in a chain. The number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the aliphatic (meth)acrylate having a chain-like aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and (methyl) glycidyl (meth)acrylate. ) Epoxyalkyl acrylates such as 3,4-epoxybutyl acrylate and 6,7-epoxyheptyl (meth)acrylate; 2-glycidyloxyethyl (meth)acrylate , 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, (meth)acrylate (meth)acrylic acid epoxyalkyloxyalkyl esters such as 6-glycidyloxyn-hexyl acrylate.

As a specific example of the aliphatic (meth)acrylate which has an alicyclic epoxy group, the compound represented by following formula (a2-1) - (a2-15) is mentioned, for example. Among these, compounds represented by the following formulae (a2-1) to (a2-5) are preferable, and compounds represented by the following formulae (a2-1) to (a2-3) are more preferable.

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a22 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents 0 to 10 carbon atoms. Integer. As R ^a21 , a linear or branched alkylene group is preferable, for example, a methylene group, an ethylene group, a propylene group, a 1,4-butylene group, an ethylethylene group, and a 1,5-ethylene group are preferable. -Pentylene, 1,6-hexylene. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a 1,4-butylene group, an ethylethylene group, a 1,5-pentylene group, a 1,6-hexylene group, and a phenylene group are preferable. base, cyclohexylene.

As the polymer having an epoxy group, a homopolymer of (meth)acrylate having an epoxy group, and a copolymer of a (meth)acrylate having an epoxy group and other monomers can be used. 70 mass % or more is preferable, 80 mass % or more is more preferable, 90 mass % or more is especially preferable, and 100 mass % or more is the most preferable content of the unit derived from the (meth)acrylate which has an epoxy group in the polymer of an oxy group. quality%.

When the polymer having an epoxy group is a copolymer of a (meth)acrylate having an epoxy group and other monomers, examples of the other monomers include unsaturated carboxylic acids and (methyl) having no epoxy group. ) acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of two or more. Copolymerization of epoxy group-containing (meth)acrylates and other monomers from the viewpoints of storage stability of the energy-sensitive composition and chemical resistance of the cured product formed using the energy-sensitive composition to alkalis, etc. The compounds preferably do not contain units derived from unsaturated carboxylic acids.

Examples of unsaturated carboxylic acids include (meth)acrylic acid; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and these dicarboxylic acids. acid anhydride.

Examples of (meth)acrylates not having an epoxy group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and amyl (meth)acrylate. , (meth) tert-octyl acrylate and other linear or branched alkyl (meth) acrylates; (meth) ethyl chloroacrylate, (meth) acrylate 2,2-dimethylhydroxypropyl ester, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; containing alicyclic skeleton (meth)acrylate of the group. Among the (meth)acrylates not having an epoxy group, the (meth)acrylates containing a group having an alicyclic skeleton are preferred from the viewpoint of transparency of the cured product formed using the energy-sensitive composition.

In the (meth)acrylate containing a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned.

As (meth)acrylate containing the group which has an alicyclic skeleton, the compound represented by following formula (a3-1) - (a3-8) is mentioned, for example. Among these, compounds represented by the following formulae (a3-3) to (a3-8) are preferable, and compounds represented by the following formula (a3-3) or (a3-4) are more preferable.

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R ^a24 , a single bond, a linear or branched alkylene group such as methylene, ethylene, propylene, 1,4-butylene, ethylethylene, 1,5 is preferred -Pentylene, 1,6-hexylene. As R ^a25 , a methyl group and an ethyl group are preferable.

Examples of (meth)acrylamides include (meth)acrylamides, N-alkyl(meth)acrylamides, N-aryl(meth)acrylamides, and N,N-dialkyl groups. (Meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide acrylamide, etc.

Examples of allyl compounds include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, and allyl benzoate. esters, allyl acetoacetate, allyl lactate and other allyl esters; allyloxyethanol; and the like.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl Ethyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol ethylene alkyl vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. Ethers; vinyl phenyl ether, vinyl cresyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthracenyl ether and other vinyl aryl ethers ether; etc.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, and vinyl chloroacetate. , Vinyl Dichloroacetate, Vinyl Methoxyacetate, Vinyl Butoxy Vinyl Acetate, Vinyl Phenyl Acetate, Vinyl Acetoacetate, Vinyl Lactate, Vinyl β-Phenyl Butyrate, Vinyl Benzoate, Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylbenzene Ethylene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc. Alkoxystyrenes; methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and other alkoxystyrenes; chlorostyrene, dichlorostyrene, trichlorostyrene , tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro- Halogenated styrenes such as 3-trifluoromethylstyrene; etc.

(Partial oxide of polymer having unsaturated aliphatic hydrocarbon group in side chain)

The polymer having an unsaturated aliphatic hydrocarbon in a side chain is not particularly limited, but 1,2-polybutadiene having a vinyl group in a side chain is preferable from the viewpoints of easy availability and easy synthesis. By partially oxidizing 1,2-polybutadiene, an epoxidized polybutadiene having an oxetanyl group and a vinyl group in the side chain can be obtained. The ratio of the oxanyl group in such an epoxidized polybutadiene is preferably 10 to 70 mol %, more preferably 10 to 50 mol%, more preferably 10 to 40 mol%. As the epoxidized polybutadiene, JP-100 and JP-200 sold by Nippon Soda Co., Ltd. can be suitably used.

The molecular weight of the epoxy group-containing polymer described above is not particularly limited as long as the object of the present invention is not inhibited, but the weight average molecular weight in terms of polystyrene is preferably 3,000 to 30,000, and more preferably 5,000 to 15,000.

Moreover, as a compound (P1), the compound represented by following formula (P1-6) is mentioned.

(In formula (P1-6), R ^P31 to R ^P33 are linear, branched or cyclic alkylene, arylene, -O-, -C(=O)-, -NH- and The groups formed by their combination may be the same or different. E ¹ to E ³ are selected from epoxy groups, oxetanyl groups, ethylenically unsaturated groups, alkoxysilyl groups, and isocyanates At least one substituent or hydrogen atom selected from the group consisting of an ethylene group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group and a succinic anhydride group, wherein at least one of E ¹ to E ³ is selected from epoxy groups and at least one of the group consisting of oxetanyl.)

In formula (P1-6), among groups represented by R ^P31 and E ¹ , R ^P32 and E ² , and R ^P33 and E ³ , for example, at least one of the groups is preferably the following formula (P1-6a) The groups represented are more preferably at least two groups each represented by the following formula (P1-6a), and more preferably all three groups are each represented by the following formula (P1-6a). The group represented by the formula (P1-6a) bonded to one compound is preferably the same group.

-L-C(P1-6a)

(In formula (P1-6a), L is a linear, branched or cyclic alkylene group, arylene group, -O-, -C(=O)-, -NH- and combinations thereof In the formed group, C is at least one selected from the group consisting of an epoxy group and an oxetanyl group. In the formula (P1-6a), L and C may be bonded to form a cyclic structure.)

In the formula (P1-6a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is, Preferably, it is an arylene group having 5 to 10 carbon atoms. In the formula (P1-6a), L is preferably a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH-, and a combination thereof The group formed is preferably at least one of linear alkylene groups having 1 to 3 carbon atoms, such as methylene, and phenylene groups, or a combination of these with -O-, -C(=O)- A group formed by a combination of at least one of NH-.

In the formula (P1-6a), when L and C are bonded to form a cyclic structure, for example, a branched alkylene group is bonded to an epoxy group to form a cyclic structure (those having an alicyclic structure). In the case of epoxy group structure), the organic group represented by following formula (P1-6b) or (P1-6c) is mentioned.

(In formula (P1-6b), R ^P34 is a hydrogen atom or a methyl group.)

Hereinafter, as an example of the compound represented by the formula (P1-6), a compound having at least one group selected from the group consisting of oxetanyl group, oxetanyl group, and alicyclic epoxy group is shown. Examples of epoxy compounds, but the present invention is not limited to these.

Moreover, as a compound (P1), the siloxane compound (henceforth "siloxane compound (B)") which has two or more glycidyl groups in a molecule|numerator is mentioned, for example.

The siloxane compound (B) can impart anti-yellowing (= heat-resistant transparency) to the obtained cured product to prevent yellowing when exposed to a high temperature environment for a long time, and has two or more glycidyl groups in the molecule, A compound further having a siloxane skeleton composed of a siloxane bond (Si-O-Si). Examples of the siloxane skeleton in the siloxane compound (B) include a cyclic siloxane skeleton, a polysiloxane skeleton (for example, a linear or branched polysiloxane (linear chain). (like or branched polysiloxane), cage-type, ladder-type polysilsesquioxane, etc.).

Among them, as the siloxane compound (B), a compound having a cyclic siloxane skeleton represented by the following formula (B-1) is preferable in terms of excellent curability and particularly excellent heat-resistant transparency of the cured product obtained (Hereinafter, it may be referred to as "cyclic siloxane").

In formula (B-1), R ^B1 and R ^B2 represent a glycidyl group-containing monovalent group or an alkyl group. Among these, at least two of n R ^B1 and n R ^B2 in the compound represented by the formula (B-1) are monovalent groups containing a glycidyl group. In addition, n in formula (B-1) represents an integer of 3 or more. In addition, R ^B1 and R ^B2 in the compound represented by formula (B-1) may be the same or different. In addition, a plurality of R ^B1 may be the same or different. The plurality of R ^B2s may also be the same or different.

As the above-mentioned glycidyl group-containing monovalent group, a glycidyl ether group represented by -DOR ^B3 is preferable [D represents an alkylene group, and R ^B3 represents a glycidyl group]. As said D (alkylene group), carbon atoms, such as methylene group, methylmethylene group, dimethylmethylene group, 1, 2- ethylene group, 1, 3- propylene group, etc. are mentioned, for example It is a linear or branched alkylene group of 1 to 18, and the like.

Examples of the alkyl group include those having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as methyl, ethyl, propyl, and isopropyl. Linear or branched alkyl.

In formula (B-1), n represents an integer of 3 or more, and is preferably an integer of 3 to 6 from the viewpoint of excellent curability of the energy-sensitive composition and excellent heat resistance and mechanical strength of the cured product.

The number of glycidyl groups which the silicone compound (B) has in the molecule is two or more, and from the viewpoints of curability of the energy-sensitive composition, heat resistance and mechanical strength of the cured product, preferably 2 to 6 pieces, particularly preferably 2 to 4 pieces.

The epoxy equivalent of the siloxane compound (B) (according to JIS K7236) is preferably 100 to 350 from the viewpoint of excellent curability of the energy-sensitive composition and excellent heat-resistant transparency of the cured product, particularly preferably It is 150-300, and it is most preferable that it is 200-270.

In addition to the siloxane compound (B), the energy-sensitive composition of the present embodiment may contain other siloxane compounds (for example, alicyclic epoxy group-containing cyclic siloxane, Japanese Patent Laid-Open No. 2008). - The alicyclic epoxy group-containing polysiloxane resin described in No. 248169, and the organic polysiloxane having at least two epoxy functional groups in one molecule described in JP-A No. 2008-19422 sesquisiloxane resin, etc.).

As a siloxane compound (B), the cyclic siloxane etc. which have two or more glycidyl groups in a molecule|numerator represented by the following formula are mentioned more specifically. In addition, as the siloxane compound (B), for example, trade names "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" ( The above are commercial products such as Shin-Etsu Chemical Co., Ltd.).

[(P2) Compounds with increased solubility in developer under the action of acid]

As an example of a compound (hereinafter, also referred to as "compound (P2)") whose solubility in a developing solution is increased by the action of an acid, for example, it can be obtained by copolymerization of the monomers listed below. oligomers, polymers and copolymers.

Acyclic or cyclic secondary and tertiary alkyl (meth)acrylates [for example, tert-butyl acrylate, tert-butyl methacrylate, 3-oxocyclohexyl (meth)acrylate, (methyl) ) tetrahydropyranyl acrylate, 2-methyl-2-adamantyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl methacrylate base ester, 5-norbornene-2-tert-butyl ester, 8-ethyl-8-tricyclodecyl (meth)acrylate, (2-tetrahydropyranyl)oxynorbornyl acrylate, methyl methacrylate (2-tetrahydropyranyl) oxymethyl tricyclododecyl methyl acrylate, trimethylsilyl methyl (meth)acrylate, (2-tetrahydropyranyl) acrylate Bornyl alcohol ester, (2-tetrahydropyranyl)oxymethyltricyclododecanemethanol methacrylate, trimethylsilylmethyl (meth)acrylate], o/m/para(3 -Oxocyclohexyloxy)styrene, o/m/p(1-methyl-1-phenylethoxy)styrene, o/m/p-tetrahydropyranyloxystyrene, o/ m/p-adamantyloxystyrene, o/m/p-cyclohexyloxystyrene, o/m/p-norbornyloxystyrene, acyclic or cyclic alkoxycarbonylstyrene [e.g. o/m/p-tert-butoxycarbonylstyrene, o/m/p-(3-oxocyclohexyloxycarbonyl)styrene, o/m/p-(1-methyl-1-phenylethoxy) carbonyl)styrene, o/m/p-tetrahydropyranyloxycarbonylstyrene, o/m/p-adamantyloxycarbonylstyrene, o/m/p-cyclohexyloxycarbonylstyrene, o/m m/p-norbornyloxycarbonylstyrene], acyclic or cyclic alkoxycarbonyloxystyrene [e.g. o/m/p-tert-butoxycarbonyloxystyrene, o/m/p( 3-Oxocyclohexyloxycarbonyloxy)styrene, o/m/p-(1-methyl-1-phenylethoxycarbonyloxy)-styrene, o/m/p-tetrahydropyran Oxycarbonyloxystyrene, o/m/p-adamantyloxycarbonyloxystyrene, o/m/p-cyclohexyloxycarbonyloxystyrene, o/m/p-norbornyloxy carbonyloxystyrene], acyclic or cyclic alkoxycarbonylalkoxystyrene [e.g. o/m/p-butoxycarbonylmethoxystyrene, p-tert-butoxycarbonylmethoxystyrene , o/m/p(3-oxocyclohexyloxycarbonylmethoxy)styrene, o/m/p(1-methyl-1-phenylethoxycarbonylmethoxy)styrene, o /m/p-tetrahydropyranyloxycarbonylmethoxystyrene, o/m/p-adamantyloxycarbonylmethoxystyrene, o/m/p-cyclohexyloxycarbonylmethoxystyrene , o/m/p-norbornyloxycarbonylmethoxystyrene, trimethylsiloxystyrene, dimethyl(butyl)siloxystyrene], unsaturated alkyl acetate ( For example, isopropenyl acetate, its derivatives), 5-norbornenyl-2-tert-butyl ester

Monomers with acid-labile groups with low activation energy [eg, p- or m-(1-methoxy-1-methylethoxy)styrene, p- or m-(1-methoxy-1 -Methylethoxy)-methylstyrene, p- or m-(1-methoxy-1-methylpropoxy)styrene, p- or m-(1-methoxy-1-methylpropoxy) yl)methylstyrene, p- or m-(1-methoxyethoxy)styrene, p- or m-(1-methoxyethoxy)-methylstyrene, p- or m-(1-ethoxy) yl-1-methylethoxy)styrene, p- or m-(1-ethoxy-1-methyl-ethoxy)methylstyrene, p- or m-(1-ethoxy-1-methyl) propoxy)styrene, p- or m-(1-ethoxy-1-methylpropoxy)methylstyrene, p- or m-(1-ethoxyethoxy)styrene, p- or m- (1-Ethoxyethoxy)-methylstyrene, p-(1-ethoxyphenylethoxy)styrene, p- or m-(1-n-propoxy-1-methylethoxy) )-styrene, p- or m-(1-n-propoxy-1-methylethoxy)methylstyrene, p- or m-(1-n-propoxyethoxy)-styrene, p- or m- (1-n-Propoxyethoxy)methylstyrene, p- or m-(1-isopropoxy-1-methylethoxy)-styrene, p- or m-(1-isopropoxy- 1-Methylethoxy)methylstyrene, p- or m-(1-isopropoxyethoxy)-styrene, p- or m-(1-isopropoxyethoxy)methylstyrene, p- or m-(1-isopropoxy-1-methylpropoxy)styrene, p- or m-(1-isopropoxy-1-methylpropoxy)-methylstyrene, p- or m- (1-Isopropoxypropoxy)styrene, p- or m-(1-isopropoxypropoxy)-methylstyrene, p- or m-(1-n-butoxy-1-methylethyl) oxy)styrene, p- or m-(1-n-butoxyethoxy)styrene, p- or m-(1-isobutoxy-1-methyl-ethoxy)-styrene, p- or m- (1-tert-Butoxy-1-methylethoxy)styrene, p- or m-(1-n-pentyloxy-1-methylethoxy)styrene, p- or m-(1-isoamyl) oxy-1-methylethoxy)styrene, p- or m-(1-n-hexyloxy-1-methyl-ethoxy)styrene, p- or m-(1-cyclohexyloxy-1 -Methylethoxy)styrene, p- or m-(1-trimethylsilyloxy-1-methylethoxy)styrene, p- or m-(1-trimethylsilyloxy) -1-Methylethoxy)-methylstyrene, p- or m-(1-benzyloxy-1-methylethoxy)styrene, p- or m-(1-benzyloxy-1- Methylethoxy)methylstyrene, p- or m-(1-methoxy-1-methylethoxy)styrene, p- or m-(1-methoxy-1-methylethoxy) - methylstyrene, p- or m-(1-trimethylsilyloxy-1-methylethoxy)-styrene, p- or m-(1-trimethylsilyloxy-1- Methyl ethoxy) methyl styrene]

As the compound (P2), a polymer having an alkoxyalkyl ester acid-labile group may be used. Examples of polymers having acid-labile groups of alkoxyalkyl esters are explicitly disclosed in US5225316 and EP829766. Examples of polymers with acetal protecting groups are described, for example, in US5670299, EP780732, US5627006, US5558976, US5558971, US5468589, EP704762, EP762206, EP342498, EP553737, and ACS Symp.Ser.614, Microelectronics Technology, pp.35-55 (1995), J.Photopolymer Sci.Technol.Vol.10, No.4(1997), pp.571-578, J.Photopolymer Sci.Technol.Vol.12, no.4(1999) pp.591-599 and "Proceedings of SPIE", Advances in Resist Technology and Processing XVII, Vol. 3999, Part One, pp. 579-590, 28. Feb.-1. March 2000. However, polymers suitable for the composition of the present embodiment are not limited to these.

In addition, for monomers having an acid-labile group, other free-radical polymerizable monomers that do not have an acid-labile group may be used in order to achieve specific solubility and adhesion in appropriate cases. [For example, styrene, acrylonitrile, methyl (meth)acrylate, (meth)acrylic acid, 4-hydroxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-vinyl ring Hexanol, norbornene, ethyl norbornene, maleic anhydride] for copolymerization. Alternatively, acid-labile groups can be introduced continuously only in polymer-like reactions. It is also known to those skilled in the art that prepolymers can be modified in a targeted manner, eg, by partial hydrogenation, partial alkylation, partial acetylation, prior to analogous reactions of the polymers. That is, polymers having acid-labile groups are not necessarily synthesized from monomers by copolymerization in all cases.

For example, also as H.-T. Schacht, P. Falcigno, N. Muenzel, R. Schulz and A. Medina, ACS Symp. Ser. 706 (Micro-and Nanopatterning Polymers), pp. 78-94, 1997; As described in H.-T. Schacht, N. Muenzel, P. Falcigno, H. Holzwarth and J. Schneider, J. Photopolymer Science and Technology, Vol. 9, (1996), 573-586, the introduction of acid labile link structure. From the viewpoint of thermal stability, the acid cross-linked structure is preferable. In addition, the acid-labile cross-linked structure can be obtained by the reaction of difunctional and polyfunctional vinyl ethers with phenolic group-containing polymers such as 4-hydroxystyrene copolymers.

Other examples of the compound (P2) are monomeric compounds in which a carboxylic acid group or a phenolic OH group is blocked with an acid-labile protecting group, respectively (for example, a carboxylic acid and a phenolic group-containing compound). The acid labile capping can be accomplished, for example, by converting the carboxyl group to tert-butyl ester, 2-methyl-2-adamantyl ester, 8-ethyl-8-tricyclodecyl ester, tetrahydropyridine alkyl ester group or some other acid-cleavable ester group. Phenolic OH groups can be terminated, for example, according to known methods based on conversion into acid-cleavable tert-butyl carbonate groups, silyl ethers, acetal groups and ketal groups.

In addition, the compound (P2) in the energy-sensitive composition is selected from the group consisting of alicyclic copolymers, 4-hydroxyphenyl group-containing copolymers, maleic anhydride-containing copolymers, acrylic acid-containing copolymers, acrylic acid ester-containing copolymers At least one compound selected from the group consisting of a copolymer and a methacrylate-containing copolymer having a functional group that increases the solubility of the polymer in an alkaline developer after reacting with an acid.

[(Px) Radical polymerizable or crosslinkable compound]

The radically polymerizable or crosslinkable compound (in this specification, it is also called "compound (Px)".), for example, the acrylate which has a reactive functional group is mentioned. The reactive functional group may, for example, be selected from the group consisting of a hydroxyl group, a thiol group, an isocyanate group, an anhydride group, a carboxyl group, an amino group, and a blocked amino group. Examples of the OH group-containing unsaturated acrylate include hydroxyethyl acrylate, hydroxybutyl acrylate, and the like. In addition, the compound (Px) may be of any desired structure (eg, it may contain units of polyester, polyacrylate, polyether, etc.) containing ethylenically unsaturated double bonds and free OH groups, COOH groups, NH ₂ group or NCO group.

In addition, the compound (Px) can also be obtained, for example, by reacting acrylic acid or methacrylic acid with an epoxy-functional oligomer. Typical examples of OH-functional oligomers with vinylic double bonds are:

It can be combined with CH 2 =CHCOOH via CH ₂ =CHCOOH

response is obtained.

Another possible method for obtaining compound (Px) is, for example, the reaction of an oligomer containing only one epoxy group and having free OH groups at other positions in the molecule.

Moreover, as a compound (Px), the compound represented by following formula (Px-1) is mentioned.

(In formula (Px-1), R ^P31 to R ^P33 are linear, branched or cyclic alkylene, arylene, -O-, -C(=O)-, -NH- and The groups formed by their combination may be the same or different. E ⁴ to E ⁶ may be between the compound (P1) and the compound represented by the formula (Px-1), or may be represented by the formula (Px-1). A functional group or hydrogen atom in which compounds undergo radical polymerization or crosslinking. Among them, at least one of E ⁴ to E ⁶ is the functional group.)

In the formula (Px-1), among the groups represented by R ^P31 and E ⁴ , R ^P32 and E ⁵ , and R ^P33 and E ⁶ , for example, at least one is preferably represented by the following formula (Px-1a) More preferably, at least two groups are each represented by the following formula (Px-1a), and more preferably, each of them is a group represented by the following formula (Px-1a). The group represented by the formula (Px-1a) bonded to one compound is preferably the same group.

-L'-C'(Px-1a)

(In formula (Px-1a), L' is a linear, branched or cyclic alkylene group, arylene group, -O-, -C(=O)-, -NH- and a The group formed by combination, C' is selected from ethylenically unsaturated group, isocyanate group, blocked isocyanate group, alkoxysilyl group, thiol group, carboxyl group, hydroxyl group, pyrazolyl group, alkoxy group, At least one substituent in the group consisting of a ketone group, a lactone ring, and a succinic anhydride group. In addition, in formula (Px-1a), L' and C' may bond to form a cyclic structure.)

In the formula (P1-6a), the linear, branched or cyclic alkylene group as L' is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L , preferably an arylene group having 5 to 10 carbon atoms. In the formula (Px-1a), L' is preferably a linear alkylene group having 1 to 6 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH-, or any of these. The group formed in combination is preferably at least one of linear alkylene groups having 1 to 6 carbon atoms, such as methylene, and phenylene groups, or these and -O-, -C(=O) A group formed by a combination of at least one of - and NH-. When a branched alkylene group is bonded to a succinic anhydride group to form a cyclic structure, specific examples thereof include cyclohexane-1,2-dicarboxylic acid anhydride.

In addition, the content of the compound component (P) in the energy-sensitive composition of the present embodiment is preferably 80 to 99.999 mass % with respect to the entire composition (excluding the solvent.), and more preferably It is 90-99.99 mass %, More preferably, it is 92-99.9 mass %. Thermogravimetric stability tends to become favorable as content of a compound component (P) exists in the said range.

As the compound component (P), one compound selected from the group consisting of the compound (P1), the compound (P2), and the compound (Px) may be used alone, or two or more may be used in combination. When two or more types are used in combination, it is preferable to contain the compound (P1). In this case, the content of the compound (P1) in the compound component (P) is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more. By making content of a compound (P1) into the said range, especially the improvement effect of thermogravimetric stability is large. In addition, when using the energy-sensitive composition for 3D printing, the compound (P1) and the compound (Px) may be combined. In this case, a photopolymerization initiator such as a radical photopolymerization initiator is preferably used in combination.

[(Q) Sulfonium salt represented by the above formula (a1)]

The sulfonium salt (hereinafter, also referred to as "sulfonium salt (Q)") represented by the above formula (a1) is characterized in that in the benzene ring in the above formula (a1), a carbon bonded to A ¹ A methyl group is bonded to the carbon atom whose atom is in the vicinal position. Since the sulfonium salt (Q) has a methyl group at the above-mentioned position, protons are more likely to be generated than conventional sulfonium salts, and the sensitivity to active energy rays such as ultraviolet rays is high.

In the above formula (a1), preferably, both R ¹ and R ² are groups represented by the above formula (a2). R ¹ and R ² may be the same or different from each other.

In the above formula (a1), when R ¹ and R ² are bonded to each other and form a ring together with the sulfur atom in the formula, the formed ring is preferably a 3- to 10-membered ring including the sulfur atom, more preferably a 5- to 7-membered ring . The formed ring may be a polycyclic ring, but preferably a ring formed by condensing 5- to 7-membered rings.

In the above formula (a1), R ³ is preferably a group represented by the above formula (a3).

In the above formula (a1), A ¹ is preferably S or O, more preferably S.

In the above formula (a2), R ⁴ is preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furylcarbonyl group, a selenophenylcarbonyl group, a substituted amino group, or a nitro group that can be substituted by a halogen atom, or a nitro group, more Preferred is an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted by a halogen atom.

In the above formula (a2), m1 may be selected according to the type of ring Z ¹ , and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

In the above formula (a3), R ⁵ represents an alkylene group or a group represented by the above formula (a5), and the alkylene group may be substituted with a substituent. Examples of the substituent which may substitute the alkylene group include a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, and an acyloxy group. , arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxyl (poly) Alkyleneoxy, optionally substituted amino, cyano, nitro or halogen atom. R ⁵ is preferably an alkylene group; an alkylene group substituted with a hydroxy group, an amino group which may be substituted, or a nitro group; or a group represented by the above formula (a5).

In the above formula (a3), R ⁶ represents an alkyl group or a group represented by the above formula (a6), and the alkyl group may be substituted with a substituent. The substituent which may be substituted for the alkyl group is the same as the substituent which may be substituted with the alkylene group described with respect to R ⁵ in the above formula (a3). R ⁶ is preferably an alkyl group; an alkyl group substituted with a hydroxy group, an amino group which may be substituted, or a nitro group; or a group represented by the above formula (a6).

In the above formula (a3), A ² is preferably S or O, more preferably S.

In the above formula (a3), n1 is preferably 0.

In the above formula (a4), R ⁷ and R ⁸ independently represent an alkylene group or a group represented by the above formula (a5), and the alkylene group may be substituted with a substituent. The substituent which may be substituted with the alkylene group is the same as the substituent which may be substituted with the alkylene group described with respect to R ⁵ in the above formula (a3). R ⁷ and R ⁸ are independently preferably an alkylene group; an alkylene group substituted with a hydroxyl group, an amino group which may be substituted, or a nitro group; or a group represented by the above formula (a5), more preferably the above formula (a5) represented group. R ⁷ and R ⁸ may be the same or different from each other.

In the above formula (a4), preferably, both R ⁹ and R ¹⁰ are groups represented by the above formula (a2). R ⁹ and R ¹⁰ may be the same or different from each other.

In the above formula (a4), when R ⁹ and R ¹⁰ are bonded to each other and form a ring together with the sulfur atom in the formula, the formed ring is preferably a 3- to 10-membered ring including the sulfur atom, more preferably a 5- to 7-membered ring . The formed ring may be a polycyclic ring, but preferably a ring formed by condensing 5- to 7-membered rings.

In the above formula (a4), A ³ is preferably S or O, more preferably S.

In the above formula (a4), n2 is preferably 0.

In the above formula (a5), R ¹¹ is preferably an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an amino group which may be substituted, or a nitro group, and more preferably an alkyl group which may be substituted by a halogen atom.

In the above formula (a5), m2 may be selected according to the type of ring Z ² , and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

In the above formula (a6), R ¹² is preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, a substituted amino group, or a nitro group that can be substituted by a halogen atom, or more Preferred is an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted by a halogen atom.

In the above formula (a6), m3 may be selected according to the type of ring Z ³ , and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

In the above formula (a1), X ^- is a monovalent anion corresponding to an acid (HX) generated by irradiating the sulfonium salt (Q) with active energy (heat, visible light, ultraviolet light, electron beam, X-ray, etc.). When a sulfonium salt (Q) is used as an acid generator, X ^- is preferably a monovalent polyatomic anion, more preferably MY _a ^- , (Rf) _b PF _6-b ^- , and R ^x1 _c BY An anion represented by 4 _-c ^- , R ^x1 _c GaY _4-c ^- , R ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ₃ C ^- , or (R ^x2 SO ₂ ) ₂ N ^- . In addition, X ^- may be a halogen anion, for example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc. are mentioned.

M represents a phosphorus atom, a boron atom, or an antimony atom.

Y represents a halogen atom (preferably a fluorine atom.).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group that forms Rf by substitution with fluorine include straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched-chain alkyl groups (isopropyl, isobutyl, etc.) base, sec-butyl and tert-butyl, etc.) and cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc.) and the like. The ratio of substitution of hydrogen atoms of these alkyl groups by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol% based on the number of moles of hydrogen atoms contained in the original alkyl group. %. When the substitution ratio based on the fluorine atom is within the above-mentioned preferable range, the photosensitivity of the sulfonium salt (Q) becomes more favorable. Particularly preferable examples of Rf include CF ₃ -, CF ₃ CF ₂ ^- , (CF ₃ ) ₂ CF ^- , CF ₃ CF ₂ CF ₂ ^- , CF ₃ CF ₂ CF ₂ CF ₂ ^- , and (CF ₃ ) ₂ CFCF ₂ ^- , CF ₃ CF ₂ (CF ₃ )CF ^- and (CF ₃ ) ₃ C ^- . The b Rfs are independent of each other, and therefore may be the same or different from each other.

P represents a phosphorus atom, and F represents a fluorine atom.

R ^x1 represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or an electron withdrawing group. As an example of such an element, a halogen atom is included, and a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. As an electron withdrawing group, a trifluoromethyl group, a nitro group, a cyano group, etc. are mentioned. Among these, a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. The c R ^x1s are independent of each other, and therefore may be the same or different from each other.

B represents a boron atom, and Ga represents a gallium atom.

R ^x2 represents an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, and the alkyl group and the fluoroalkyl group may be linear, branched or Any of the cyclic, alkyl, fluoroalkyl, or aryl groups may be unsubstituted or substituted. Examples of the substituent include a hydroxyl group, an amino group which may be substituted (for example, an amino group exemplified in the description below with respect to the above formulae (a2) to (a6)), a nitro group, and the like are mentioned. .

In addition, the carbon chain in the alkyl group, fluoroalkyl group, or aryl group represented by R ^x2 may have a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom. In particular, the carbon chain in the alkyl group or fluoroalkyl group represented by R ^x2 may have a divalent functional group (eg, ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonyl bond, etc.). amide bond, sulfonimide bond, urethane bond, etc.).

When the alkyl group, fluoroalkyl group, or aryl group represented by R ^x2 has the above-mentioned substituent, heteroatom, or functional group, the number of the above-mentioned substituent, heteroatom, or functional group may be one or two or more.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.

a represents an integer of 4-6.

b is preferably an integer of 1 to 5, more preferably an integer of 2 to 4, and particularly preferably 2 or 3.

c is preferably an integer of 1 to 4, more preferably 4.

As an anion represented by MY _a ^- , the anion represented by SbF ₆ ^- , PF ₆ ^- , or BF ₄ ^- , etc. are mentioned.

Examples of the anion represented by (Rf) _b PF _6-b ^- include (CF ₃ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , and ((CF ₃ ) ₂ CF) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^- represented by anions, etc. Among these, (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , and ((CF ₃ ) ₂ CF) An anion represented by ₂ PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- .

The anion represented by R ^x1 _c BY _4-c ^- is preferably:

R ^x1 _c BY _4-c ^-

(In the formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4.),

For example, (C ₆ F ₅ ) ₄ B ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ BF Anion represented by ₂ ^- , C ₆ F ₅ BF ₃ ^- or (C ₆ H ₃ F ₂ ) ₄ B ^- , and the like. Among these, an anion represented by (C ₆ F ₅ ) ₄ B ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- is preferable.

Examples of anions represented by R ^x1 _c GaY _4-c ^- include (C ₆ F ₅ ) ₄ Ga ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- , and (CF ₃ C ₆ H ₄ ) ₄ An anion represented by Ga ^- , (C ₆ F ₅ ) ₂ GaF ₂ ^- , C ₆ F ₅ GaF ₃ ^- or (C ₆ H ₃ F ₂ ) ₄ Ga ^- and the like. Among these, an anion represented by (C ₆ F ₅ ) ₄ Ga ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- is preferable.

Examples of anions represented by R ^x2 SO ₃ ^- include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, p-toluene Sulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion and butanesulfonic acid anion, etc. Among these, a trifluoromethanesulfonic acid anion, a nonafluorobutanesulfonic acid anion, a methanesulfonic acid anion, a butanesulfonic acid anion, a camphorsulfonic acid anion, a benzenesulfonic acid anion, or a p-toluenesulfonic acid anion is preferable.

As anions represented by (R ^x2 SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- and (C ₃ F ₇ SO ₂ ) ₃ C ^- can be mentioned or an anion represented by (C ₄ F ₉ SO ₂ ) ₃ C ^- and the like.

Examples of anions represented by (R ^x2 SO ₂ ) ₂ N ^- include (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , and (C ₃ F ₇ SO ₂ ) ₂ N ^- or an anion represented by (C ₄ F ₉ SO ₂ ) ₂ N ^- , etc.

As a monovalent polyatomic anion, except MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x1 _c GaY _4-c ^- , R ^x2 SO ₃ ^- , (R ^x2 In addition to the anions represented by SO ₂ ) ₃ C ^- or (R ^x2 SO ₂ ) ₂ N ^- , perhalogen acid ions (ClO ₄ ^- , BrO ₄ ^- etc.), halogenated sulfonic acid ions (FSO ₃ ^- , ClSO ₃ , etc.) can also be used ^- etc.), sulfate ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^- etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^- etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^- etc.), hexafluorobismuthate ion (BiF ₆ ^- ), carboxylate ion (CH ₃ COO ^- , CF ₃ COO ^- , C ₆ H ₅ COO ^- , CH ₃ C ₆ H ₄ COO ^- , C ₆ F ₅ COO ^- , CF ₃ C ₆ H ₄ COO ^- etc.), aryl borate ions (B(C ₆ H ₅ ) ₄ ^- , CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ^- etc.), thiocyanate Acid ions (SCN ^- ) and nitrate ions (NO ₃ ^- ), etc.

Among these X ^- , MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x1 _c GaY _4-c ^- and (R ^x2 SO ) are preferable from the viewpoint of cationic polymerization performance ₂ ) An anion represented by ₃ C ^- , more preferably SbF ₆ ^- , PF ₆ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (C ₆ F ₅ ) ₄ B ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- , (C ₆ F ₅ ) ₄ Ga ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- and (CF ₃ SO ₂ ) ₃ C ^- , more preferably R ^x1 _c BY _{4- c} ^- .

In the above formulas (a2), (a5), and (a6), examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C _8-20 fused bicyclic hydrocarbon ring such as naphthalene ring, preferably C _10-16 fused bicyclic hydrocarbon ring), fused tricyclic aromatic hydrocarbon ring (for example, anthracene ring, phenanthrene ring, etc.), etc. Condensed 2- to 4-ring aromatic hydrocarbon rings] etc. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.

In the above formulae (a1) to (a6), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

In the above formulae (a1) to (a6), examples of the alkyl group include straight-chain alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl) having 1 to 18 carbon atoms. base, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups with 3 to 18 carbon atoms (isopropyl, isopropyl, isopropyl, etc.) butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-amyl, isohexyl, and isooctadecyl, etc.), and cycloalkyl (cyclopropyl) having 3 to 18 carbon atoms , cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl, etc.) and the like. In particular, in the above formulae (a1), (a2), and (a4) to (a6), the alkyl group which may be substituted with a halogen atom represents an alkyl group and an alkyl group substituted with a halogen atom. Examples of the alkyl group substituted with a halogen atom include groups obtained by substituting at least one hydrogen atom in the above-mentioned straight-chain alkyl group, branched-chain alkyl group, or cycloalkyl group with a halogen atom (monofluoromethyl, monofluoromethyl, etc.). difluoromethyl, trifluoromethyl, etc.) and the like. Among the alkyl groups which may be substituted by a halogen atom, for R ¹ , R ² , R ⁹ , or R ¹⁰ , trifluoromethyl is particularly preferable, and for R ⁴ , R ⁶ , R ¹¹ , or R ¹² , A methyl group is particularly preferred.

In the above formulae (a2) to (a6), examples of the alkoxy group include linear or branched alkoxy groups (methoxy, ethoxy, propoxy, isopropoxy) having 1 to 18 carbon atoms. group, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy, etc.) and the like.

In the above formulae (a2) to (a6), examples of the alkyl group in the alkylcarbonyl group include the above-mentioned straight-chain alkyl groups having 1 to 18 carbon atoms, branched alkyl groups having 3 to 18 carbon atoms, or carbon atoms. Cycloalkyl group having 3 to 18 atoms, and examples of the alkylcarbonyl group include linear, branched or cyclic alkylcarbonyl groups (acetyl, propionyl, butyryl, 2-18 carbon atoms) - methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl, and cyclohexanoyl, etc.), etc. .

In the above formulae (a3) to (a6), examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (benzoyl, naphthoyl, etc.) and the like.

In the above formulae (a2) to (a6), examples of the alkoxycarbonyl group include linear or branched alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, propoxy) having 2 to 19 carbon atoms. Carbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxy carbonyl, etc.), etc.

In the above formulae (a3) to (a6), examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (phenoxycarbonyl group, naphthoxycarbonyl group, etc.) and the like.

In the above formulae (a3) to (a6), examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (phenylthiocarbonyl, naphthoxythiocarbonyl, etc.) and the like.

In the above formulae (a2) to (a6), the acyloxy group includes a linear or branched acyloxy group (acetoxy group, ethylcarbonyloxy group, propylcarbonyloxy group) having 2 to 19 carbon atoms. , isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy, etc.), etc.

In the above formulae (a3) to (a6), examples of the arylthio group include arylthio groups having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylthio) Phenylsulfanyl, 4-methylphenylsulfanyl, 2-chlorophenylsulfanyl, 3-chlorophenylsulfanyl, 4-chlorophenylsulfanyl, 2-bromophenylsulfanyl, 3-bromobenzene sulfanyl, 4-bromophenylsulfanyl, 2-fluorophenylsulfanyl, 3-fluorophenylsulfanyl, 4-fluorophenylsulfanyl, 2-hydroxyphenylsulfanyl, 4-hydroxyphenylsulfanyl base, 2-methoxyphenylsulfanyl, 4-methoxyphenylsulfanyl, 1-naphthylsulfanyl, 2-naphthylsulfanyl, 4-[4-(phenylsulfanyl)benzoyl ] phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenyl Sulfanyl) phenylsulfanyl, 4-benzoylphenylsulfanyl, 4-benzoyl-2-chlorophenylsulfanyl, 4-benzoyl-3-chlorophenylsulfanyl, 4-benzyl Acyl-3-methylsulfanylphenylsulfanyl, 4-benzoyl-2-methylsulfanylphenylsulfanyl, 4-(4-methylsulfanylbenzoyl)phenylsulfanyl, 4- (2-Methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylsulfanyl, 4-(p-ethylbenzoyl)phenylsulfanyl, 4-(p-ethylbenzoyl)phenylsulfanyl isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio, etc.) and the like.

In the above formulae (a2) to (a6), examples of the alkylthio group include linear or branched alkylthio groups (methylthio, ethylthio, propylthio) having 1 to 18 carbon atoms. sulfanyl, isopropylsulfanyl, butylsulfanyl, isobutylsulfanyl, sec-butylsulfanyl, tert-butylsulfanyl, pentylsulfanyl, isopentylsulfanyl, neopentylsulfanyl, tert-amyl thio, octyl thio, decyl thio, dodecyl thio, and isooctadecyl thio, etc.) and the like.

In the above formulae (a3) to (a6), examples of the aryl group include aryl groups having 6 to 10 carbon atoms (phenyl, tolyl, dimethylphenyl, naphthyl, etc.) and the like.

In the above formula (a2), examples of the heterocyclic aliphatic hydrocarbon group include heterocyclic hydrocarbon groups (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidine) having 2 to 20 (preferably 4 to 20) carbon atoms. pyridyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.) and the like.

In the above formulae (a3) to (a6), examples of the heterocyclic hydrocarbon group include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (thienyl, furyl, selenophene, pyranyl, pyrrolyl, oxa azolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carboxy azolyl, acridinyl, phenothiazinyl, phenazinyl, xanthyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl , isochromanyl, dibenzothienyl, xanthonyl (xanthonyl), thioxanthonyl (thioxanthonyl, and dibenzofuranyl, etc.) and the like.

In the above formulae (a3) to (a6), examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (phenoxy group, naphthyloxy group, etc.) and the like.

In the above formulae (a2) to (a6), examples of the alkylsulfinyl group include straight-chain or branched-chain sulfinyl groups (methylsulfinyl, ethylsulfinyl, propane, etc.) having 1 to 18 carbon atoms. sulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl acyl, neopentylsulfinyl, tert-amylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl, etc.) and the like.

In the above formulae (a3) to (a6), examples of the arylsulfinyl group include arylsulfinyl groups (phenylsulfinyl, tolysulfinyl, and naphthylidene) having 6 to 10 carbon atoms. sulfonyl, etc.) etc.

In the above formulae (a2) to (a6), examples of the alkylsulfonyl group include straight-chain or branched-chain alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, propylsulfonyl) having 1 to 18 carbon atoms. Acyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl sulfonyl, octylsulfonyl, and octadecylsulfonyl, etc.) and the like.

In the above formulae (a3) to (a6), examples of the arylsulfonyl group include arylsulfonyl (phenylsulfonyl, tosyl (toluenesulfonyl), and naphthyl) having 6 to 10 carbon atoms. sulfonyl, etc.) etc.

In the above formulae (a2) to (a6), examples of the hydroxy (poly)alkyleneoxy group include HO(AO) _q- (wherein, AO independently represents an ethyleneoxy group and/or a propylene group oxy, q represents an integer of 1 to 5. ) represents a hydroxy (poly)alkyleneoxy group, and the like.

In the above formulae (a2) to (a6), examples of the amino group which may be substituted include amino groups (—NH ₂ ) and substituted amino groups (methylamino, dimethylamino, ethylamino) having 1 to 15 carbon atoms. , methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropyl ylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.) and the like.

In the above formulae (a3) and (a4), as the alkylene group, a linear or branched alkylene group having 1 to 18 carbon atoms (methylene, 1,2-ethylene, 1,1 - Ethylene, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl , butane-1,3-diyl, butane-1,2-diyl, butane-1,1-diyl, butane-2,2-diyl, butane-2,3-diyl , pentane-1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl , 2-ethylhexane-1,6-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane- 1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, and hexadecane-1,16-diyl base, etc.) etc.

The sulfonium salt (Q) can be synthesized, for example, according to the following synthetic route. Specifically, a compound represented by the following formula (b2) is reacted with 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) in the presence of a base such as potassium hydroxide to obtain Next, the nitro compound represented by the following formula (b3) is reduced in the presence of reduced iron to obtain an amine compound represented by the following formula (b4). This amine compound is reacted with a nitrite (for example, sodium nitrite) represented by MaNO ₂ (wherein Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom) to obtain a diazo compound, and then the The diazo compound, cuprous halide represented by CuX' (wherein X' represents a halogen atom such as a bromine atom. The same applies hereinafter), and hydrogen halide represented by HX' are mixed and reacted to obtain the following formula The halide represented by (b5). A Grignard reagent is prepared from the halide and magnesium, and then the Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) in the presence of chlorotrimethylsilane to obtain the following formula (b7) ) represents the sulfonium salt. Further, this sulfonium salt is combined with Mb ⁺ X" ^- (wherein Mb ⁺ represents a metal cation, for example, an alkali metal cation such as potassium ion, and X" ^- represents a monovalent anion represented by X ^- (wherein, excluding The sulfonium salt represented by the following formula (b8) can be obtained by reacting with the salt represented by the halogen anion.) and performing salt exchange. In addition, in following formula (b2) ^- (b8), R< ¹ >-R< ³ > and A1 are the same as said formula (a1).

<composition path>

Specific examples of the cation moiety of the sulfonium salt (Q) represented by the above formula (a1) include the following examples. As a specific example of the anion part of the sulfonium salt (Q) represented by the said formula (a1), the conventionally known anion part, such as the example exemplified in the description of the said X- ^, is mentioned. The sulfonium salt (Q) represented by the above formula (a1) can be synthesized according to the above-mentioned synthetic route, and by further performing salt exchange if necessary, a cation part can be combined with a desired anion part, and R ^x1 _c BY is particularly preferred. A combination of anions represented by 4 ^- _c- (in the formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4).

In addition, the content of the sulfonium salt (Q) in the energy-sensitive composition of the present embodiment is preferably 0.001 to 20 mass % with respect to the entire composition (excluding the solvent), and more preferably It is 0.01-10 mass %, More preferably, it is 0.1-8 mass %. When content of a sulfonium salt (Q) exists in the said range, there exists a tendency for thermogravimetric stability to become favorable. In particular, when the viscosity of the energy-sensitive composition is adjusted to a low viscosity of, for example, 1000 mPa·s (1000 cP) to be described later, the sulfonium salt (Q) relative to the entire composition (which does not include the solvent.) The content of the powder may be within the above range, and may be 0.001 to 1 mass %, 0.005 to 0.1 mass %, or 0.008 to 0.05 mass %.

[other ingredients]

(Other sulfonium salts, etc.)

The energy-sensitive composition of the present embodiment may contain not only the sulfonium salt (Q) but also an onium salt other than the sulfonium salt (Q).

Examples of the onium salt include a monovalent anion represented by X ^- in the above formula (a1), and an onium salt formed of an onium ion different from a cation other than X ^- in the above formula (a1). etc., a sulfonium salt (in this specification, it is also called "sulfonium salt (Q')" is preferable.). The monovalent anion represented by X ^- is preferably the above-mentioned R ^x1 _c BY _4-c ^- .

As a sulfonium salt (Q') which has a monovalent anion represented by ^Rx1cBY4 _{-c- ,} ^the sulfonium salt represented by following formula (a1') is mentioned, for example.

(In the formula, R ¹ , R ² , R ³ , A ¹ , R ^x1 , Y and c are as described above.)

Specific examples of the cation moiety of the sulfonium salt (Q') represented by the above formula (a1') include the following examples.

Another example of the sulfonium salt (Q') is a sulfonium salt represented by the above formula (a1) (wherein, in the formula, R ¹ and R ² independently represent a group represented by the following formula (a2')).

(In the formula, the rings Z ¹ and m1 are as described above, and R ^4' represents an aryl group.)

Specific examples of the cation moiety of the sulfonium salt (Q') include the following examples.

Specific examples of the cation moiety of the sulfonium salt (Q') include the following examples.

(solvent)

In order to easily dissolve the sulfonium salt (Q) in the cationically polymerizable compound, the sulfonium salt (Q) may be previously dissolved in a solvent (S) that does not inhibit cationic polymerization.

Examples of the solvent include carbonates (1,2-propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.); esters (ethyl acetate) , methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl valerate, ethyl valerate, methyl hexanoate, ethyl hexanoate, methyl heptanoate, ethyl heptanoate Iso-chain alkyl esters; cyclopentyl acetate, cyclohexyl acetate, cyclooctyl acetate, methyl cyclohexyl acetate, ethyl cyclohexyl acetate, propyl cyclohexyl acetate, isopropyl cyclohexyl acetate , Cyclic alkyl esters such as butyl cyclohexyl acetate, isobutyl cyclohexyl acetate, sec-butyl cyclohexyl acetate, tert-butyl cyclohexyl acetate, pentyl cyclohexyl acetate: ethyl lactate, β-propiolactone, β-butyrolactone esters, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.); β-ketoester compounds (methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, α-acetyl-γ-butyrolactone, etc.); β-diketone compounds (acetylacetone, 2,4-hexanedione, 2,4-heptanedione, etc.); ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, Tripropylene glycol dibutyl ether, etc.); and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate etc.) etc., can be used individually or 2 or more types can be used.

In addition, conventionally known ketone-based solvents, alcohol-based solvents, amide-based solvents, and hydrocarbon-based solvents can be used. In addition, a solvent known as a protic solvent and/or an alkaline solvent can also be used.

Examples of the protic solvent include alcohols such as monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, and diethylene glycol monomethyl ether, and polyhydric alcohols such as ethylene glycol and glycerin; acetic acid, Carboxylic acids such as formic acid and (meth)acrylic acid; amines such as ethylenediamine and diethylamine; cyclic amides (lactams) such as N-methylpyrrolidone (NMP); formamide, N,N -Amides such as dimethylformamide; phenols such as phenol and p-butylphenol; active methylene compounds such as acetylacetone and diethyl malonate.

Examples of the basic solvent include pyridine, triethylamine, N,N-dimethylacetamide, and hexamethylphosphoryl tris in addition to the above-mentioned amines and the above-mentioned nitrogen-containing amides. Amine, 1,3-dimethyl-2-imidazolidinone, N,N,N',N'-tetramethylurea, N,N,2-trimethylpropionamide, etc.

When a solvent is used, the usage ratio of the solvent is, for example, preferably 1 to 99% by mass, and more preferably 10 to 95% by mass, relative to the entire energy-sensitive composition of the present embodiment.

(alkali-soluble resin)

The energy-sensitive composition according to the present embodiment may contain an alkali-soluble resin (A) as needed.

In addition, in this specification, the alkali-soluble resin refers to a resin formed on a substrate with a film thickness of 1 μm using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass. When the resin film was immersed in a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 1 minute, the resin having a film thickness of 0.01 μm or more was dissolved.

Examples of the alkali-soluble resins include (a) dicarboxylic acids or tricarboxylic acids or their acid anhydrides, and (b) tetracarboxylic acids or their acid dianhydrides with two glycidyl ether groups derived from bisphenols. Alkali-soluble resin (A1) obtained by reacting the epoxy compound of unsaturated group with the reactant of monocarboxylic acid containing unsaturated group; it has alkali-soluble groups such as carboxyl group, phenolic hydroxyl group, or sulfonic acid group (-SO ₃ H) known resins (A2) and the like. In the present specification, the alkali-soluble resin (A2) preferably represents an alkali-soluble resin other than the alkali-soluble resin (A1). These alkali-soluble resins are also preferable when heat resistance of the obtained cured product is desired.

The alkali-soluble resin (A2) preferably contains a resin selected from the group consisting of a resin having a Cardo structure, a resin having a phenolic hydroxyl group, a carboxyl group-containing resin, a polyimide resin, and an epoxy resin.

It does not specifically limit as an alkali-soluble resin (A2), A conventionally known alkali-soluble resin can be used. The alkali-soluble resin may or may not have an ethylenically unsaturated group.

As the alkali-soluble resin having an ethylenically unsaturated group, for example, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

Among them, the resin represented by the following formula (f-1) is preferable. The resin itself represented by the formula (f-1) has high photocurability, and is preferable from this point of view.

In the above general formula (f-1), X ^f represents a group represented by the following formula (f-2).

In the above general formula (f-2), R ^f1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^f2 each independently represents a hydrogen atom or a methyl group, and W ^f represents a single bond or A group represented by the following formula (f-3).

In addition, in the above general formula (f-1), Y ^f represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetramine Hydrogen phthalic anhydride, Chlorendic Anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

Moreover, in the said general formula (f-1), Z ^f represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. As an example of a tetracarboxylic dianhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, a diphenyl ether tetracarboxylic dianhydride, etc. are mentioned.

Moreover, in the said general formula (f-1), m represents the integer of 0-20.

In addition, as the alkali-soluble resin having an ethylenically unsaturated group, a resin obtained by condensing (meth)acrylic acid with a polyester prepolymer (which is obtained by condensing polyols with a monobasic acid or a polybasic acid) can also be used. obtained) polyester (meth)acrylate obtained by reacting; polyol and urethane (meth)acrylate obtained by reacting a compound having two isocyanate groups and then reacting with (meth)acrylic acid ; Make epoxy resins (bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol Novolac type epoxy resin, Resol type epoxy resin, trisphenol methane type epoxy resin Epoxy resin, polyglycidyl polycarboxylate, polyglycidyl polyol, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, etc.) and (methyl) Epoxy (meth)acrylate resin obtained by reacting acrylic acid, etc.

In addition, in this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Likewise, "(meth)acrylate" refers to both acrylate and methacrylate.

On the other hand, as the alkali-soluble resin not having an ethylenically unsaturated group, at least an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound not having an alicyclic group, and an alicyclic group-containing unsaturated compound can be used. A resin obtained by copolymerizing agglomerated unsaturated compounds.

Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; these dicarboxylic acids anhydride; etc. Among them, (meth)acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound not having an alicyclic group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3 (meth)acrylate, 4-Epoxybutyl, (meth)acrylate 6,7-epoxyheptyl, (meth)acrylate 3,4-epoxycyclohexyl, (meth)acrylate 4-oxatetracyclo-[6.2 .1.0 ^2,7 0 ^3,5 ] Undecyl ester and other epoxy alkyl esters of (meth)acrylate; α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-propyl acrylate α-Alkyl acrylates such as glycidyl butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, etc.; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl glycidyl ethers, such as p-vinylbenzyl glycidyl ether; and the like. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-(meth)acrylate are preferable from the viewpoints of the copolymerization reactivity and the strength of the cured resin. Epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an alicyclic group-containing unsaturated compound. Alicyclic groups may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Moreover, as a polycyclic alicyclic group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned. Specifically, as an alicyclic group containing unsaturated compound, the compound represented by the following formula is mentioned, for example.

In the above general formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^a4 is preferably a single bond, a linear or branched alkylene group, such as methylene, ethylene, propylene, 1,4-butylene, ethylethylene, 1,5 -Pentylene, 1,6-hexylene. As R ^a5 , for example, a methyl group and an ethyl group are preferable.

The ratio of the structural unit derived from the said unsaturated carboxylic acid in this alkali-soluble resin becomes like this. Preferably it is 3-25 mass %, More preferably, it is 5-25 mass %. Moreover, 71-95 mass % is preferable, and, as for the ratio of the structural unit derived from the said epoxy group-containing unsaturated compound, 75-90 mass % is more preferable. Moreover, the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound becomes like this. Preferably it is 1-25 mass %, More preferably, it is 3-20 mass %, More preferably, it is 5-15 mass %. By being in the said range, not only the alkali solubility of the obtained resin can be made moderate, but also the obtained hardened|cured material can be made to have sufficient heat resistance.

The weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. By being in the said range, the obtained hardened|cured material can have sufficient heat resistance.

In addition, as the carboxyl group-containing resin in the alkali-soluble resin (A2), a silicon-containing resin may be used, and, for example, a siloxane resin containing the following structural unit is mentioned.

It may be a siloxane resin containing a structural unit represented by the following formula (A2-1).

In formula (A2-1), R ^r1 is an organic group having at least one carboxyl group in its structure. The carboxyl group is preferably bonded to the Si atom via a linking group, such as a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group, or an arylene group, or a combination thereof. the divalent group.

The linking group may have an ether bond, an amino bond, an amide bond, or a vinyl bond, and preferably has an amide bond. For R ^r1 , for example, the following examples are given, but not limited to these. In addition, in the following formula, * represents the terminal of the chemical bond of R ^r1 which is bonded to Si in the formula (A2-1).

The ratio of the structural unit of formula (A2-1) in the silicone-containing resin is, for example, 1 to 90% by mass. The silicone-containing resin may have conventionally known structural units other than (A2-1).

The weight average molecular weight of the silicone-containing resin is, for example, 300 to 100,000, and more preferably 500 to 70,000.

When the alkali-soluble resin is contained, the content of the alkali-soluble resin is, for example, 60% by mass or less, preferably 30% by mass or less, more preferably 60% by mass or less with respect to the entire energy-sensitive composition (excluding the solvent.) 20 mass % or less, more preferably 15 mass % or less, and within the above range, the lower limit of the content may be more than 0 mass %, for example, 3 mass % or more and 5 mass % or more. By being in the said range, the obtained hardened|cured material can have sufficient heat resistance.

(Surfactant)

The energy-sensitive composition according to the present embodiment may contain a surfactant if necessary. As the surfactant, for example, a fluorine-based surfactant, a polysiloxane-based surfactant, and the like can be mentioned.

(metal oxide particles)

The energy-sensitive composition according to the present embodiment may contain metal oxide particles as needed. Thereby, the refractive index can be adjusted, and a cured product with low reflectivity and/or high transparency can be obtained. The metal oxide particles include at least one metal oxide selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, lanthanum, cerium, neodymium, gadolinium, holmium, lutetium, hafnium, and tantalum particles, etc. Oxides of zirconium, titanium, or cerium are preferably used, and titanium oxide or cerium oxide is particularly preferable from the viewpoint of increasing the refractive index. The shape of these metal oxide particles is not particularly limited, and particles having an average particle diameter measured by a dynamic scattering method of 1 to 200 nm, more preferably 3 to 100 nm, can be used. The content ratio of the metal oxide particles is, for example, 1 to 120% by mass, preferably 3 to 110% by mass, and more preferably 5 to 100% by mass in the components other than the solvent in the energy-sensitive composition. .

In addition, the energy-sensitive composition according to the present embodiment may contain known additives (radical photopolymerization initiator, sensitizer, pigment, dispersant, filler, antistatic agent, flame retardant, etc.) as needed , defoamer, flow regulator, light stabilizer, antioxidant, adhesion imparting agent, ion scavenger, anti-coloring agent, solvent, non-reactive resin and radical polymerizable compound, etc.).

In particular, the balance of thermal reactivity and photoreactivity of the energy-sensitive composition according to the present embodiment can be appropriately adjusted by combining a radical photopolymerization initiator or the like.

[characteristic]

In the energy-sensitive composition according to the present embodiment, in the thermogravimetric measurement (TG) in which the temperature is raised to 230° C. at 10° C./min in an air flow, the weight reduction rate of the weight loss from the peak is preferably 10% or less. .

As described above, it is presumed that by containing the sulfonium salt (Q), in the system containing the compound component (P) and the sulfonium salt (Q), the concentration of protons increases, the stepwise polymerization in the compound component (P) continues, and the polymerization Reification is promoted. Therefore, in the energy-sensitive composition according to the present embodiment, it is preferable that the weight reduction rate is as low as 10% or less even when the temperature is raised to 230°C.

The energy-sensitive composition according to the present embodiment is preferably used for a sealing material for an organic EL display element or a curable composition for a wafer-level lens. The energy-sensitive composition according to the present embodiment not only exhibits good curability (especially photocurability), but also has excellent weight stability even when exposed to high temperature, and can maintain quality for a long period of time, so it is preferably used for organic Sealing materials or wafer-level lenses for EL display elements. Moreover, the method of using the energy-sensitive composition which concerns on this Embodiment in the sealing material for organic EL display elements, the curable composition for wafer-level lenses, the composition for 3D printing, or the composition for inkjet printing is also One of the inventions.

In addition, the energy-sensitive composition according to the present embodiment can form a hard coat layer by, for example, preparing the composition as a coating liquid, and using a spin coater, a dip coater, a bar coater, or a slit coater. A coating device such as a machine is used to apply it to a to-be-coated object such as a polyimide film, and then to cure. In this coating liquid, even if the coating material is a thin film with a thickness of, for example, 10 mm or less, preferably 100 μm or less, for example, 50 μm or less, 30 μm or less, 20 μm or less, and furthermore, 15 μm or less, it is possible to suppress the effect of the coating liquid. or the degree of deformation such as curling of the coated object due to curing of the hard coat layer. The film thickness of the object to be coated may be, for example, 10 μm or more.

In addition, generally, in order to reduce the viscosity of the composition, a low molecular weight compound (P1), such as an epoxy monomer, can be used, but on the other hand, the more a low molecular weight compound is blended, the easier it is to reduce the heat resistance, and it will be easier to produce exhaust. However, it was confirmed that the energy-sensitive composition according to the present embodiment is excellent in heat resistance even if the viscosity is low by containing the sulfonium salt (Q), and the generation of exhaust gas can be reduced. In addition, surprisingly, even if the addition amount of the sulfonium salt (Q) is smaller than the addition amount of a general cationic polymerization initiator, etc., the viscosity of the energy-sensitive composition can be reduced and the heat resistance can be improved. And the effect of reducing the generation of exhaust gas has been confirmed by the experiments described later.

The energy-sensitive composition according to the present embodiment not only has a low viscosity, but also has excellent heat resistance and can reduce the generation of outgassing. Therefore, it can be preferably used also in inkjet printing in which low-viscosity ink is required. Inkjet inks can be preferably used in display devices such as touch panels when applied to a large area from the viewpoint of productivity and the like, and can also be preferably used in sealing materials for organic EL display elements, etc. use. Preferably, the inkjet printing composition containing the energy-sensitive composition according to the present embodiment has a viscosity of 1000 mPa·s (1000 cP) or less at 25° C. and a shear rate of 20 (l/s), and the sulfonium salt ( The content of Q) is 0.001 to 1 mass % with respect to the entire composition (excluding the solvent.).

<Manufacturing method of wafer-level lens>

Wafer-level lenses can be manufactured by molding (eg, casting molding, injection molding) the energy-sensitive composition described above. It should be noted that the wafer-level lens mold may be any of metal, glass, and plastic.

The casting molding method includes a simultaneous molding method and a single-piece molding method, and each has the following steps.

(simultaneous molding method)

Step 1: The above-mentioned energy-sensitive composition is poured into a wafer-level lens mold having a shape in which a plurality of lens molds are arranged in a certain direction, and is cured by heating and/or light irradiation

Step 2: Remove the wafer-level lens mold, perform annealing treatment, and obtain a cured product having a shape in which a plurality of wafer-level lenses are connected

Step 3: The cured product having a shape in which a plurality of wafer-level lenses are connected is diced into individual pieces to obtain wafer-level lenses

(Single-piece molding method)

Step 1: The above-mentioned energy-sensitive composition is poured into a wafer-level lens mold having one lens mold, and is cured by heating and/or light irradiation

Step 2: Remove the wafer-level lens mold and perform annealing treatment to obtain a wafer-level lens

(Injection molding method)

Step 1: The energy-sensitive composition described above is poured into a wafer-level lens mold for injection molding, and cured by heating and/or light irradiation

Step 2: Remove the wafer-level lens mold, perform annealing treatment, remove burrs, and obtain a wafer-level lens

The heat treatment in the above-mentioned step can be performed at a temperature of, for example, about 100 to 200° C. (preferably 120 to 160° C.) for a short time (for example, about 1 to 10 minutes, preferably 1 to 3 minutes). For light irradiation, as the light source, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam, a laser and the like can be used. Moreover, after light irradiation, you may heat-process at the temperature of about 50-180 degreeC, for example, and may further advance a hardening reaction.

Internal strain can be removed by annealing. For the annealing treatment, for example, it is preferable to perform heating at a temperature of 100 to 200° C. for about 30 minutes to 1 hour.

In the above-mentioned simultaneous molding method, the energy-sensitive composition is preferably low in viscosity and excellent in fluidity from the viewpoint of being excellent in filling properties into a mold. The viscosity of the energy-sensitive composition that can be used in the above-mentioned simultaneous molding method at 25° C. and a shear rate of 20 (1/s) is, for example, about 0.05 to 5 Pa·s, preferably 0.1 to 2 Pa·s. The energy-sensitive composition having the viscosity in the above-mentioned range is excellent in fluidity, hardly remains of air bubbles, and can be filled into a mold while suppressing an increase in injection pressure. That is, the coating properties and filling properties are excellent, and the handling properties are excellent during the entire molding operation.

The cured product of the energy-sensitive composition has excellent heat resistance even in a high temperature environment of about 100 to 250°C. Therefore, even if the annealing treatment is performed after removal from the mold, a wafer-level lens having excellent lens center position accuracy can be efficiently manufactured. Therefore, in step 3 of the above-mentioned simultaneous molding method, a plurality of cured products having a shape in which a plurality of wafer-level lenses are connected are stacked, and the position of the cutting line is determined with reference to the uppermost cured product, and the cutting is performed. As a result, the wafer-level lens can be separated without breaking the wafer-level lens, and the wafer-level lens or a laminate thereof can be manufactured at low cost and efficiently.

Even if the wafer-level lens obtained from the energy-sensitive composition of the present embodiment is exposed to a high temperature environment for a long period of time, yellowing can be prevented and high transparency can be maintained. Therefore, for example, it can be suitably used as a photographic lens, eyeglass lens, beam condensing lens, A lens for light diffusion, etc., can be used particularly suitably as a wafer-level lens for an in-vehicle camera that requires heat resistance.

In addition, since the wafer-level lens obtained from the energy-sensitive composition of the present embodiment is excellent in heat resistance, when it is mounted on a circuit board, it can be mounted by soldering by reflow. Therefore, a camera having such a wafer-level lens can be directly mounted on a PCB (Printed Circuit Board) substrate using the same solder reflow process as the surface mounting of other electronic components, and a product can be manufactured very efficiently.

<cured product>

The cured product according to the present invention contains at least one compound component (P) selected from the group consisting of the above-mentioned compound (P1), compound (P2), and compound (Px), and the energy of the sulfonium salt (Q) A cured product obtained by curing the sensitive composition. As described above, the cured product according to the present invention is excellent in weight stability with respect to heat. This is presumably because the concentration of protons in the system containing the compound component (P) and the sulfonium salt (Q) increases by including the sulfonium salt (Q) in the energy-sensitive composition, so that the compound component (P) The step-by-step polymerization continues, polymerization is promoted, and less monomers are decomposed under the action of heat. This cured product is suitable as, for example, a sealing material for an organic EL display element, a wafer-level lens, the above-mentioned hard coat layer, and the like. In addition, it is also suitable for flexible devices.

Moreover, the hardened|cured material of this embodiment can be set as a hardened|cured material with a high refractive index by selecting the component of an energy-sensitive composition. From the viewpoint of obtaining a cured product with a high refractive index, preferable components include metal oxide particles, an epoxy group-containing fluorene compound as the compound (P1), and the like, and these may be used alone or in combination of two. In the above-mentioned use, it is preferable to use metal oxide particles from the viewpoint of increasing the refractive index. The refractive index of the obtained cured product can be, for example, a high refractive index of 1.7 or more as a refractive index at a wavelength of 633 nm, and when metal oxide particles are used, it can be 1.75 or more, and further 1.8 or more. High refractive index. The upper limit of the refractive index at the wavelength of 633 nm is not particularly limited, but is, for example, 1.9 or less, 1.85 or less, and the like.

<Manufacturing method of cured product>

The method for producing a cured product according to the present invention includes causing at least one compound component (P) selected from the group consisting of the above-mentioned compound (P1), compound (P2), and compound (Px), and a sulfonium salt ( The energy-sensitive composition of Q) is subjected to the step of polymerizing and/or cross-linking. Since the energy-sensitive composition has energy sensitivity, it can be cured by polymerizing and/or cross-linking by imparting active energy. As the active energy to be imparted, any active energy can be used as long as it has energy capable of inducing decomposition of the sulfonium salt (Q), and examples thereof include heat, visible light, ultraviolet rays, electron beams, and X-rays.

<Inkjet ink>

The energy-sensitive composition according to the present embodiment is adjusted to be 5000 mPa·s (5000 cP) or less, preferably 100 mPa·s ( 100 cP) or less, it can be preferably used as an inkjet ink. When the viscosity of the energy-sensitive composition of the present embodiment used as an inkjet ink is within the above-mentioned range, it may be, for example, 1 mPa·s (1 cP) or more, or 10 mPa·s (10 cP) or more. For the energy-sensitive composition to be used as an inkjet ink, the content of the sulfonium salt (Q) is preferably an amount in which the viscosity is adjusted to the above-mentioned low viscosity.

Example

Hereinafter, although the Example of this invention is shown and this invention is demonstrated in detail, this invention is not limited to the following Example.

<<Examples 1 to 3 and Comparative Examples 1 to 9>>

In Examples 1 to 3 and Comparative Examples 1 to 9, the compound (P1) shown below, a sulfonium salt, and the like were mixed at the mixing ratio shown in Table 1 to prepare a mixed solution. In addition, in Table 1, the unit of a compounding ratio is a mass part.

<Material>

[Compound (P1)]

· A compound represented by the following formula (P1-1a)

· A compound represented by the following formula (P1-1c)

· A compound represented by the following formula (P1-2a)

[sulfonium salt]

Sulfonium salt represented by the following formula (Q1)

Sulfonium salt represented by the following formula (z1)

A sulfone compound represented by the following formula (z2)

Triphenylsulfoniumtetrakis(pentafluorophenyl)borate

[Evaluation 1]

The mixed solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 9 were subjected to a differential thermal/thermogravimetric measuring apparatus (TG/DTA-6200, manufactured by Seiko Instruments) in an air flow at a temperature increase rate of 10°C. Under the condition of /min, the temperature was raised from 20°C to 250°C, and the TG/DSC curve was obtained. In the obtained TG curve, the weight reduction rate of the weight reduction from the peak value was calculated. The results are shown in Table 1. In addition, the evaluation of the weight reduction rate was performed according to the following criteria.

〇: Weight reduction rate of 10% or less

△: The weight reduction rate is more than 10% and less than 40%

×: The weight reduction rate is 40% or more

In addition, the TG/DSC curves obtained in Example 3 and Comparative Examples 7, 8, and 9 are shown in FIGS. 1 to 4 . In addition, the TG/DSC curve when the compound (P1) represented by the formula (P1-2a) was independently heated under the same conditions is shown in FIG. 5 as a reference example.

[Table 1]

[inspection]

As shown in Table 1 and the TG curves shown in FIGS. 1 to 4 , in Examples 1 to 3 in which the compound (P1) and the sulfonium salt (Q) were used, the weight reduction rate was 10% or less, which was comparable to the comparative example. Compared with 1-9, favorable high heat resistance is shown. In addition, in the DSC curve of Example 3 shown in FIG. 1, gentle peaks were observed at 110.6 degreeC and 222.3 degreeC. This is presumed to be a peak showing that the epoxy group of compound (P1) opens and the polymerization progresses stepwise, and it is presumed that the polymerization proceeds from a low temperature around 110°C. In contrast, sharp peaks were observed in the DSC curves of the comparative examples shown in FIGS. 2 to 4 . This is presumed to be a peak showing decomposition of the sulfonium salt represented by the above formula (z1) or the sulfone compound represented by the above formula (z2), and it is presumed that the weight loss rate is increased. For example, as shown in FIG. 2 , in Comparative Example 7, the weight decreased by about 65% at around 170°C. As shown in FIG. 3 , in Comparative Example 8, the weight decreased by about 30% at around 150°C. As shown in FIG. 4 , in Comparative Example 9, the weight decreased by about 50% at around 170°C. In addition, according to the result of FIG. 5, when the compound (P1) represented by the formula (P1-2a) alone was confirmed, in the DSC curve, a sharp peak was observed at 50°C or lower, and the formula (P1- The compound (P1) represented by 2a) starts to decompose below 50°C, and the weight starts to decrease from around 100°C, and decreases by about 80% at around 165°C.

[Evaluation 2]

The mixed liquid obtained by changing the mass ratio of the mixed liquid obtained in Example 1 to the compound of formula (P1-1a):sulfonium salt of formula (Q1)=99:1 was applied on a glass substrate with a spin coater, A coating film having a thickness of 20 μm was obtained, and using HMW-532D (manufactured by ORC Corporation), the coating film was irradiated with ghi rays at an exposure amount of 1000 mJ/cm ² , and then the wavelength of the film was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). Transmission at 400nm. The transmittance is 99.6%.

[inspection]

This result shows that in Examples 6 to 9 to be described later, even when the same coating liquid containing the compound (P1) and the sulfonium salt (Q) as in Example 1 was applied on the polyimide film, the The formed hard coat layer does not adversely affect its transmittance.

<<Example 4, 5>>

As the compound (P1), the alicyclic epoxy compound represented by the above formula (P1-1a) or the oxetane compound represented by the following formula (P1-7a), that is, bis-1-ethyl-3-oxo Heterocyclobutyl methyl ether and the sulfonium salt represented by the above formula (Q1) were mixed in the mixing ratio shown in Table 2, and the obtained mixture was subjected to exposure (broadband) based on an exposure amount of 100 mJ/cm ² using an ultraviolet curing machine. (broad band)), and then, in Example 4, post-baking was performed at 150° C. for 2 minutes, and in Example 5, curing was attempted under curing conditions without post-baking. As a result, Example 4, The mixtures of 5 all cured without developing stickiness. In addition, in Table 2, the unit of a mixing|blending ratio is a mass part.

[Table 2]

[inspection]

From the results of Examples 4 and 5, it was confirmed that even when an oxetane compound was used as the compound component (P) or the compound (P1), by blending the sulfonium salt (Q), it was confirmed that good curability was exhibited . Further, from the results of Example 5, it was confirmed that even if an oxetane compound and an alicyclic epoxy compound were used in combination as the compound (P1), good curability was exhibited.

<<Examples 6 to 9 and Comparative Examples 10 to 13>>

First, the polyimide films 1 to 4 formed of polyimide were prepared as described below.

[Manufacturing method of polyimide film 1]

832 g of N,N-dimethylacetamide (DMAc) was charged while feeding nitrogen into a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature regulator, and a condenser as a reactor. Then, the temperature of the reactor was set to 25°C, and 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was dissolved in the solvent in the reaction vessel, and the solution was maintained at 25°C. Then, 31.09 g (0.07 mol) of 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 8.83 g (0.03 mol) of biphenyltetracarboxylic dianhydride (BPDA) were added, and then , stir for a certain period of time to dissolve and react. At this time, the temperature of the solution was maintained at 25°C. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content concentration of 13% by weight. 25.6 g of pyridine and 33.1 g of acetic anhydride were put into this polyamic acid solution, stirred at 25° C. for 30 minutes, then further stirred at 70° C. for 1 hour, cooled to room temperature, and precipitated in 20 L of methanol. The solid content was filtered and pulverized, and then dried in a vacuum at 100° C. for 6 hours to obtain 111 g of polyimide as a solid content powder.

0.03 g (0.03 wt %) of amorphous silica particles having OH groups bonded to the surface were put into N,N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, and subjected to ultrasonic treatment, Until the solvent became transparent, 100 g of the polyimide of the solid content powder was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13 wt % solution. The solution obtained as described above was applied to a stainless steel plate, cast to a thickness of 340 μm, dried with hot air at 130° C. for 30 minutes, and then the film was peeled off from the stainless steel plate and fixed to a frame with a needle. The frame to which the film was fixed was placed in a vacuum oven, gradually heated from 100° C. to 300° C. in 2 hours, then gradually cooled, and separated from the frame to obtain a polyimide film. Then, as a final heat treatment step, heat treatment was further performed at 300° C. for 30 minutes. The obtained polyimide film 1 had a film thickness of 50 μm, a total light transmittance of 88%, and a yellowness (YI) of 2.5.

[Manufacturing method of polyimide film 2]

On one side of the polyimide film 1, polysilazane (MOPS-1800, manufactured by Az Materials Co., Ltd.) having a weight average molecular weight of 2,000 g/mol was dissolved in dibutyl ether (DBE) at 2 wt % using wire bar coating. ), and then dried at a temperature of about 80° C. to form a polysilazane film with a thickness of 300 nm. Then, after standing at room temperature for about 5 minutes, the polysilazane film was thermally cured at a temperature of about 250° C. to form a silicon oxide layer, and a structure having a colorless transparent polyimide film/silicon oxide layer was produced. The polyimide film 2. The obtained polyimide film 2 had a film thickness of 50 μm, a total light transmittance of 92%, and a yellowness (YI) of 1.0.

[Manufacturing method of polyimide film 3]

1000 g of N-methylpyrrolidone (NMP) was added to a 3 L separable flask with an oil bath with a stirring bar while introducing nitrogen, and 232.4 g of 3,3-(diaminodiphenyl) was added with stirring. sulfone (referred to as diamine 1), followed by adding 218.12 g of pyromellitic dianhydride, followed by stirring at room temperature for 30 minutes. The temperature was raised to 50° C. and stirred for 12 hours. Then, 105.6 g of both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight: 4400)) was dissolved in 298 g of In NMP, it was dripped using a dropping funnel. The temperature was raised to 80° C., and the mixture was stirred for 1 hour. Then, the oil bath was removed, and the temperature was returned to room temperature to obtain a transparent polyamic acid NMP solution (hereinafter, also referred to as a varnish). The weight average molecular weight (Mw) of the obtained polyamic acid was 84,000.

The above-mentioned varnish was coated on an alkali-free glass substrate (thickness 0.7 mm) with a bar coater, and was leveled at room temperature for 5 to 10 minutes. ), heated at 140° C. for 60 minutes, further heated at 350° C. for 60 minutes in a nitrogen atmosphere (oxygen concentration: 100 ppm), left standing at room temperature for 24 hours, the resin film was peeled off from the glass, and a polyimide film was produced . The obtained polyimide film 3 had a thickness of 20 μm, a total light transmittance of 88%, and a yellowness (YI) of 7.0.

[Manufacturing method of polyimide film 4]

(Synthesis of imidazole compound (d))

First, 30 g of the cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to the methanol. Next, the methanol solution was stirred at 40°C. Methanol was distilled off, and the residue was suspended in 200 g of water. 200 g of tetrahydrofuran was mixed with the obtained suspension and stirred, and the aqueous phase was separated. Under ice-cooling, 4 g of hydrochloric acid was added, and after stirring, 100 g of ethyl acetate was mixed and stirred. The mixture was allowed to stand, then the oil phase was separated. The crystal of the target product was precipitated from the oil phase, and the precipitate was recovered to obtain an imidazole compound (d) having the following structure.

(Preparation of Tetracarboxylic Dianhydride)

According to the methods described in Synthesis Example 1, Example 1, and Example 2 of International Publication No. 2011/099518, tetracarboxylic dianhydride (norbornane-2-spiro-α-cyclopentanone) represented by the following formula was prepared -α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride).

(Preparation of polyamic acid)

First, a 30 ml three-necked flask was heated with a heat gun and dried sufficiently. Next, the atmospheric gas in the three-necked flask was replaced with nitrogen to make the interior of the three-necked flask a nitrogen atmosphere. 0.2045 g of 4,4'-diaminobenzoic anilide (0.90 mmol: DABAN, manufactured by Junyang Pharmaceutical Co., Ltd.) was added to the three-necked flask, and then 3.12 g of N,N,N',N'-tetramethyl was added. baseurea (TMU). The contents of the three-necked flask were stirred to obtain a slurry in which an aromatic diamine (DABAN) was dispersed in TMU.

Next, 0.3459 g (0.90 mmol) of tetracarboxylic dianhydride of the above formula was added to the three-necked flask, and the contents of the flask were stirred at room temperature (25° C.) for 12 hours under a nitrogen atmosphere to obtain a reaction solution. It operated as mentioned above, and the reaction liquid in which the polyamic acid became 15 mass % (TMU solvent: 85 mass parts) in a reaction liquid was formed.

(Addition step of imidazole compound (d))

In a nitrogen atmosphere, the synthesized imidazole compound (d) (0.206 g, 5.6 parts by mass when the reaction liquid was 100 parts by mass) was added to the reaction liquid obtained as described above. Next, the reaction liquid was stirred at 25 degreeC for 12 hours, and the liquid composition containing an imidazole compound (d) and a polyamic acid was obtained. With respect to 100 parts by mass of solid content in the composition, 1.5 parts by mass of a silane coupling agent represented by the following formula was added as an additive to obtain a polyimide precursor composition.

(Preparation of Polyimide Film)

On a glass substrate (large carrier glass, trade name "S9213" manufactured by Matsunami Glass Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm) so that the thickness of the coating film after heat curing becomes 13 μm The polyimide precursor composition obtained as described above is applied to form a coating film. Next, the glass substrate on which the coating film was formed was placed on a hot plate at 60° C. and left to stand for 2 hours, and the solvent was evaporated from the coating film to remove the solvent.

After removing the solvent, the glass substrate on which the coating film was formed was put into an inert oven in which nitrogen gas was circulated at a flow rate of 3 L/min. In an inert oven, in a nitrogen atmosphere (oxygen concentration: 100 ppm), it was left to stand at a temperature of 25°C for 0.5 hours, then heated at a temperature of 135°C for 0.5 hours, and further heated at a temperature of 300°C (finally The coating film was cured by heating at a heating temperature) for 1 hour to obtain a polyimide-coated glass in which a thin film (polyimide film) formed of polyimide was coated on the glass substrate.

The obtained polyimide-coated glass was immersed in hot water at 90° C., the polyimide film was peeled off from the glass substrate, and a polyimide film 4 (length 76 mm, width 52 mm, and thickness 13 μm) was obtained. ).

In order to identify the molecular structure of the resin which is the material of the obtained polyimide film, the IR of the sample of the polyimide film was measured using an IR measuring instrument (manufactured by JASCO Corporation, trade name: FT/IR-4100). spectrum. As a result of the measurement, in the IR spectrum of the resin which is the material of the polyimide film, the C=O stretching vibration of the imide carbonyl group was observed at 1696.2 cm ⁻¹ . From the molecular structure identified based on such results and the like, it was confirmed that the obtained polyimide film was indeed a film formed of a polyimide resin.

The total light transmittance of the obtained polyimide film 4 was 88%, and the yellowness (YI) was 3.5.

In addition, about the value (unit: %) of the total light transmittance of the film, and the yellowness (YI), the Nippon Denshoku Industries Co., Ltd. trade name "haze meter NDH-5000" was used as a measuring device , obtained by measuring according to JIS K7361-1 (issued in 1997).

[Preparation of coating liquid]

The energy-sensitive composition containing the compound (P1) represented by the above formula (P1-1a) and the sulfonium salt represented by the above formula (Q1) in a mass ratio of 99:1 was dissolved in a solvent (propylene glycol monomethyl ether acetate) (PGMEA)), the coating liquid 1 in which the ratio of the solvent was 80 mass % was prepared.

[Preparation of coating liquid for comparison]

A photosensitive composition containing an acrylic monomer (dipentaerythritol hexaacrylate) and a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) in a mass ratio of 99:1 was dissolved in a solvent (PGMEA) to prepare a solvent The ratio of 80% by mass of Coating Liquid 2 for comparison.

[Evaluation 3]

The coating liquid 1 and the comparative coating liquid 2 were respectively applied on one side of the polyimide films 1 to 4 attached to the wafer by a spin coater, and then dried at a temperature of 80°C. A coating film having a thickness of 4 μm was obtained. Then, using an ultraviolet curing machine with a wavelength of 365 nm, the coating layer was irradiated at 100 mJ/cm ² to obtain each polyimide film having a hard coat layer (cured film) formed on one surface. Each obtained polyimide film was peeled off from the wafer, and the external appearance was observed visually.

[Result · Investigation]

For the polyimide films 1 to 4 (Examples 6 to 9) in which the hard coat layer using the coating liquid 1 according to the present example was formed, the transparency of the film did not decrease, and the coating The degree of curling of the film by the curing of the liquid or the hard coat layer was small, and it was confirmed that the curing shrinkage was small.

On the other hand, the polyimide films 1 to 4 (Comparative Examples 10 to 13) on which the hard coat layers using the comparative coating liquid 2 were formed turned yellow to some extent, and the coating liquid or the Curl due to hard coat curing is large. The hard coat layer formed by the coating liquid 1 according to the present example is considered to have a smaller curing shrinkage rate than the hard coat layer formed by the coating liquid 2, and it was confirmed that the deformation of the polyimide film to be coated can be suppressed. degree.

[Evaluation 4]

Using Hiresta MCP-HT450 (manufactured by Mitsubishi Analytech Co., Ltd.), the surface resistance value of each hard coat layer formed on the polyimide films 1 to 4 in Evaluation 3 was measured with a probe UR-100 at a measurement voltage of 1,000 V . The surface resistance values are all higher than 1×10 ¹⁵ Ω.

From this result, it was confirmed that the coating liquid 1 according to this example can form a hard coat layer having a high surface resistance.

<<Examples 10 to 14 and Comparative Examples 14 to 15>>

In Examples 10 to 14 and Comparative Examples 14 to 15, compounds (P1-1a), (P1-2a), sulfonium salts (Q1), and compounds (P1- 6d), sulfonium salt, etc. (z3) were mixed in the mixing ratio shown in Table 1 to prepare a mixed solution. In addition, in Table 3, the unit of a mixing|blending ratio is a mass part.

<Material>

[Compound (p1-6d)]

[Sulfonium salt, etc. (z3)]

[Evaluation 5]

The viscosities of the mixed liquids obtained in Examples 10 to 14 and Comparative Examples 14 to 15 were measured under the conditions of 25° C. and 1 to 100 rpm using an E-type viscometer. The results are shown in Table 3. It should be noted that the viscosity of the compound (P1-1a) is about 60 mPa·s (60 cP), the viscosity of the compound (P1-2a) is about 20 mPa·s (20 cP), and the viscosity of the compound (P1-6d) is about 200 mPa·s s (200cP) or so.

0.3 g of the mixed solutions obtained in Examples 10 to 14 and Comparative Examples 14 to 15 were precisely weighed into a glass vial and sealed, and a UV irradiator (HMW-532D, manufactured by ORC Corporation) was used at a rate of 1500 mJ/cm. The exposure amount of ² was exposed, followed by post-baking at 100° C. for 15 minutes and 85° C. for 100 hours, and each sample was produced.

Each of the above samples was set in a headspace sampler (TurboMatrix ATD, manufactured by PerkinElmer), heated at 100°C for 30 minutes, and then the exhaust gas was measured using a gas chromatograph mass spectrometer (Clarus 580, manufactured by PerkinElmer). The results are shown in Table 3. In addition, in the table, the measured value (area %) of the comparative example 14 is shown as a relative value when 100 is used.

[table 3]

[inspection]

As shown in Table 3, it was confirmed that the viscosity of Example 10 using the compound (P1-1a) and the sulfonium salt (Q1) was comparable to that of Comparative Example 14 not using the sulfonium salt (Q1). The amount of gas produced is also small. Similarly, it was confirmed that Example 14 using the compound (P1-1a), the compound (P1-6d) and the sulfonium salt (Q1) had the same viscosity as that of Comparative Example 15 not using the sulfonium salt (Q1). At the same time, the amount of exhaust gas generated is small.

In addition, from the results of Examples 10 and 11, it was confirmed that even a very small amount of the sulfonium salt (Q1) has the effect of reducing the viscosity of the mixed solution (energy-sensitive composition) and reducing outgassing. Similarly, from the results of Examples 12 and 13, it was confirmed that even a very small amount of the sulfonium salt (Q1) has the effect of reducing the viscosity of the mixed solution (energy-sensitive composition) and reducing outgassing.

From the results of Examples 11 and 12, it was confirmed that when the total content of the compound component (P) or the compound (P1) is the same as that of using the compound (P1-1a) alone as the compound component (P) or the compound (P1) When compound (P1-1a) and compound (P1-2a) are used in combination as compound component (P) or compound (P1), the viscosity of the mixed solution (energy-sensitive composition) can be reduced, and the outgassing can be reduced. Effect. This shows that it may be preferable to use together the alicyclic epoxy compound represented by the above-mentioned formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) as the compound component (P) or the compound (P1).

<<Examples 15 to 24>>

[Preparation of high refractive index energy-sensitive composition]

In Examples 15 to 24, the following cationic and/or acid-catalyzed polymerizable and/or cross-linkable compounds (P1), sulfonium salts, etc. were prepared at the mixing ratios shown in Table 4. Mix to make an energy sensitive composition. In addition, in Table 4, the unit of a compounding ratio is a mass part, and the compounding ratio of a solvent is a mass ratio. In Example 23, 100 parts by mass of cerium oxide (average particle diameter: 50 nm) was further added with respect to 100 parts by mass of the total of the component (P1) and (Q1) in Example 15 to prepare. In Example 24, 100 parts by mass of titanium oxide (average particle diameter: 5 to 10 nm) was further added with respect to 100 parts by mass of the total of the component (P1) and (Q1) in Example 15 to prepare. In Examples 15 to 23, the amount of solvent was adjusted so that the concentration of components other than the solvent was 20% by mass. In Example 24, the amount of solvent was adjusted so that the concentration of components other than the solvent was 10% by mass.

[Table 4]

<Material>

[Compound (P)] (Compound (P1))

A compound represented by the following formula (P1-8a) (9,9-bis(6-glycidyloxynaphthalen-2-yl)-9H-fluorene)

·(P1-9) Bisphenol A epoxy resin (condensation reaction product of bisphenol A and epichlorohydrin)

[Alkali-soluble resin]

· Preparation of alkali-soluble resin (A1a)

First, put 0.34mol (3,4-epoxy)cyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, 0.68mol acrylic acid, 139.0g propylene glycol monomethyl ether acetate and 2.15 g of tetraethylammonium bromide (TEAB) was stirred for 20 hours under the condition of heating at 100 to 105° C. to carry out the reaction. Next, 0.12 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 0.27 mol of 1,2,3,6-tetrahydrophthalic anhydride were charged into the flask, at 120-125 The reaction was carried out by stirring for 8 hours under the condition of heating at °C. Furthermore, 0.28 mol of glycidyl methacrylate was charged, and it stirred for 8 hours under the conditions of heating at 100-105 degreeC, and obtained alkali-soluble resin (A1a). The solid content concentration of the obtained alkali-soluble resin (A1a) was 57.0 wt %, the acid value (in terms of solid content) was 82 mgKOH/g, and the Mw by GPC analysis was 3500.

· Preparation of alkali-soluble resin (A2a)

First, put 235g of bisphenol fluorene type epoxy resin (epoxy equivalent of 235), 110mg of tetramethylammonium chloride, 100mg of 2,6-di-tert-butyl-4-methylphenol into a 500ml four-necked bottle , and 72.0 g of acrylic acid, into which air was blown at a rate of 25 mL/min, and heated and dissolved at 90 to 100°C. Next, the temperature was gradually raised while the solution was kept cloudy, and it was heated to 120° C. to completely dissolve it. At this time, the solution gradually became transparent and viscous, and kept stirring in this state. During this period, the acid value was measured, and heating and stirring were continued until the acid value was lower than 1.0 mgKOH/g. It takes 12 hours until the acid value reaches the target value. Then, it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate represented by following formula (f-4) which is colorless, transparent and solid.

Next, 600 g of 3-methoxybutyl acetate was added and dissolved in 307.0 g of the above-mentioned bisphenol fluorene-type epoxy acrylate obtained by the above-mentioned operation, and then 80.5 g of benzophenone tetracarboxylic acid was mixed The temperature of the dianhydride and 1 g of tetraethylammonium bromide was gradually increased, and the reaction was carried out at 110 to 115° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain an alkali-soluble resin (A2a) having a Cardo structure. The disappearance of the acid anhydride group was confirmed by IR spectrum.

In addition, the alkali-soluble resin (A2a) which has this Cardo structure corresponds to the compound represented by the above-mentioned general formula (f-1).

[additive]

·(Add-1)

Polyether-modified polydimethylsiloxane [BYK Chemie Japan, BYK302]

·(Add-2)

Perfluoroalkyl group-containing oligomer [DIC Corporation, F-477]

[solvent]

·(S1) cyclohexyl acetate

·(S2) Diethylene glycol monobutyl ether acetate

·(S3) Propylene Glycol Monomethyl Ether Acetate

·(S4) Diethylene glycol methyl ethyl ether

·(S5)N-Methylpyrrolidone

[Evaluation 6]

Each of the energy-sensitive compositions of Examples 15 to 24 was applied to a glass substrate using a spin coater, pre-baked at 100° C. for 120 seconds, and then exposed to an exposure amount of 100 mJ/cm ² (wide width) using an ultraviolet curing machine. waveband), and then post-baking treatment was performed at 150° C. for 20 minutes (Example 24 was 230° C. for 20 minutes). The cured films of Examples 15 to 23 had a film thickness of 500 nm, and Example 24 had a thickness of 50 nm. Each cured film has heat resistance. For each cured film, the refractive index at a wavelength of 633 nm was measured. It was confirmed that all the compositions had a high refractive index of 1.7 or more. In particular, the refractive index of the cured film of Example 23 to which cerium oxide was added as the metal oxide particles was 1.75 or more, and the refractive index of the cured film of Example 24 to which titanium oxide was added was 1.8 or more, both of which were able to increase the refractive index. (transparency).

In addition, regarding heat resistance, each of the energy-sensitive compositions of Examples 15 to 24 was applied to a glass substrate using a spin coater, pre-baked at 100° C. for 120 seconds, and an ultraviolet curing machine was used. Exposure (broadband) based on an exposure amount of 100 mJ/cm ² , followed by post-baking treatment at 230° C. for 20 minutes to obtain a cured film having a cured film thickness of about 50 nm. The film thickness change rate when each cured film was further heated up to 250° C. was 10% or less, and it was confirmed that it had heat resistance.

Claims (8)

1. An energy sensitive composition comprising: At least one compound component (P) selected from the following group, and (Q) a sulfonium salt represented by the following formula (a1), The group consists of: (P1) a polymerizable and/or crosslinkable compound based on a cationic and/or acid-catalyzed form, (P2) a compound having increased solubility in a developer under the action of an acid, and (Px) Radically polymerizable or crosslinkable compound constitute,

In the formula (a1), R ¹ and R ² independently represent an alkyl group which may be substituted by a halogen atom or a group represented by the following formula (a2), and R ¹ and R ² may be bonded to each other and together with the sulfur atom in the formula A ring is formed, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, X ^- represents a monovalent anion, wherein R ¹ and R ² will not be an alkyl group that can be substituted by a halogen atom at the same time,

In formula (a2), ring Z ¹ represents a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, and R ⁴ represents an alkyl group, hydroxyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, Acyloxy, alkylthio, thienyl, thienylcarbonyl, furanyl, furylcarbonyl, selenophene, selenophenecarbonyl, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl, alkylsulfonyl, Hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m1 represents an integer of 0 or more,

In the formula (a3), R ⁵ represents an alkylene group or a group represented by the following formula (a5), and the alkylene group may be represented by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, Aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl , alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, may be substituted by substituted amino, cyano, nitro or halogen atom, R ⁶ represents an alkyl group or the following formula (a6) represents , the alkyl group can be replaced by hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, Alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, Can be substituted by substituted amino, cyano, nitro or halogen atom, A ² represents a single bond, S, O, sulfinyl, or carbonyl, n1 represents 0 or 1,

In the formula (a4), R ⁷ and R ⁸ independently represent an alkylene group or a group represented by the following formula (a5), and the alkylene group may be represented by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, Arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, which may be substituted by a substituted amino, cyano, nitro or halogen atom, R ⁹ and R ¹⁰ represent independently An alkyl group that can be substituted by a halogen atom or a group represented by the formula (a2), R ⁹ and R ¹⁰ can be bonded to each other and form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, Sulfonyl group, or carbonyl group, X ^- as described above, n2 represents 0 or 1, wherein, R ⁹ and R ¹⁰ will not be an alkyl group that can be substituted by a halogen atom at the same time,

In formula (a5), ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxy group which may be substituted by a halogen atom Carbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl acyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m2 represents an integer of 0 or more,

In formula (a6), ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxy group which may be substituted by a halogen atom carbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, thienylcarbonyl, furylcarbonyl, selenophenecarbonyl, aryl, heterocyclic hydrocarbyl, aryloxy, alkyl Sulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m3 represents 0 or more the integer. 2. An energy sensitive composition comprising: At least one compound component (P) selected from the following group, and (Q) a sulfonium salt represented by the following formula (a1), The group consists of: (P1) a polymerizable and/or crosslinkable compound based on a cationic and/or acid-catalyzed form, (P2) a compound having increased solubility in a developer under the action of an acid, and (Px) Radically polymerizable or crosslinkable compound constitute,

In the formula (a1), R ¹ and R ² independently represent an alkyl group which may be substituted by a halogen atom or a group represented by the following formula (a2), and R ¹ and R ² may be bonded to each other and together with the sulfur atom in the formula A ring is formed, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, X ^- represents a monovalent anion, wherein R ¹ and R ² will not be an alkyl group that can be substituted by a halogen atom at the same time,

In formula (a2), ring Z ¹ represents an aromatic hydrocarbon ring, R ⁴ represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group which may be substituted by a halogen atom , thienyl, thienylcarbonyl, furyl, furanylcarbonyl, selenophene, selenophenecarbonyl, heterocyclic aliphatic hydrocarbon, alkylsulfinyl, alkylsulfonyl, hydroxy (poly) alkylene oxide group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m1 represents an integer of 0 or more,

In the formula (a3), R ⁵ represents an alkylene group or a group represented by the following formula (a5), and the alkylene group may be represented by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, Aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl , alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, may be substituted by substituted amino, cyano, nitro or halogen atom, R ⁶ represents an alkyl group or the following formula (a6) represents , the alkyl group can be replaced by hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, Alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, Can be substituted by substituted amino, cyano, nitro or halogen atom, A ² represents a single bond, S, O, sulfinyl, or carbonyl, n1 represents 0 or 1,

In the formula (a4), R ⁷ and R ⁸ independently represent an alkylene group or a group represented by the following formula (a5), and the alkylene group may be represented by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, Arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, which may be substituted by a substituted amino, cyano, nitro or halogen atom, R ⁹ and R ¹⁰ represent independently An alkyl group that can be substituted by a halogen atom or a group represented by the formula (a2), R ⁹ and R ¹⁰ can be bonded to each other and form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, Sulfonyl group, or carbonyl group, X ^- as described above, n2 represents 0 or 1, wherein, R ⁹ and R ¹⁰ will not be an alkyl group that can be substituted by a halogen atom at the same time,

In formula (a5), ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxy group which may be substituted by a halogen atom Carbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic hydrocarbyl, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl acyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom, m2 represents an integer of 0 or more,

In formula (a6), ring Z ³ represents a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, and R ¹² represents an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkane group which may be substituted by a halogen atom Oxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, thienylcarbonyl, furylcarbonyl, selenophenylcarbonyl, aryl, heterocyclic hydrocarbyl , aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, substituted amino, cyano, nitro, or a halogen atom, and m3 represents an integer of 0 or more. 3. The energy-sensitive composition according to claim 1 or 2, wherein the compound component (P) is the (P1) compound, The compound (P1) is an epoxy compound having at least one group selected from the group consisting of an oxetanyl group, an oxetanyl group, and an alicyclic epoxy group. 4. The energy-sensitive composition according to claim 1 or 2, wherein, in the sulfonium salt, the monovalent anion represented by the X- is a boron ^- containing anion represented by the following general formula, R ^x1 _c BY _4-c ^- In the formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1-4. 5. The energy-sensitive composition according to claim 1 or 2, wherein in a thermogravimetric measurement (TG) in which the temperature is increased to 230° C. at a temperature increase rate of 10° C./min in an air stream, the amount of weight decreased from a peak The weight reduction rate is 10% or less. 6. Use of the energy-sensitive composition according to any one of claims 1 to 5 for a sealing material for an organic EL display element or a curable composition for a wafer-level lens. 7 . A cured product obtained by curing the energy-sensitive composition according to claim 1 . The manufacturing method of the hardened|cured material which comprises the process of polymerizing and/or crosslinking the energy-sensitive composition of any one of Claims 1-5.

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