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

Technical Field

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

Background

Conventionally, it has been proposed to contain an epoxy compound in an energy-sensitive composition for a sealing agent for an organic EL display element or a Wafer-Level lens (Wafer-Level lens). For example, patent document 1 proposes an energy-sensitive resin composition having an epoxy group or an oxetanyl group and containing no ether bond or ester bond other than the epoxy group or the oxetanyl group, as an energy-sensitive resin capable of suppressing the occurrence of outgassing (out gas), which is a factor causing the deterioration of an organic EL display device. Patent document 2 proposes an energy-sensitive resin composition containing an alicyclic epoxy compound having a specific structure, a siloxane compound having 2 or more glycidyl groups in the molecule, and a curing agent, as an energy-sensitive resin which is inhibited from yellowing even in a high-temperature environment and is excellent in transparency and curability.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2015/064410

Patent document 2: international publication No. 2015/129503

Disclosure of Invention

Problems to be solved by the invention

However, weight stability in high temperature environments is required for previous energy sensitive compositions.

The purpose of the present invention is to provide 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.

Means for solving the problems

The inventors of the present application have found that the use of a sulfonium salt having a specific structure improves the thermal weight stability, and have completed the present invention.

The 1 st embodiment of the present invention is an energy-sensitive composition comprising at least 1 compound component (P) selected from the group consisting of (P1) a cationically and/or acid-catalytically polymerizable and/or crosslinkable compound, (P2) a compound whose solubility in a developer increases by the action of an acid, and (Q) a sulfonium salt represented by the following formula (a 1).

(in the formula, R¹And R²Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (a2), R¹And R²May be bonded to each other and form a ring together with the sulfur atom in the formula R³Represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A¹Denotes S, O, or Se, X^-Represents a monovalent anion, wherein R¹And R²Will not be simultaneously halogen-capableAn atom-substituted alkyl group. )

(in the formula, ring Z¹Represents an aromatic hydrocarbon ring, R⁴Represents an alkyl group which may be substituted with a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a thienyl group, a thienylcarbonyl group, a furyl group, a furylcarbonyl group, a selenophenyl group, a selenophenylcarbonyl group, a heterocyclic aliphatic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more. )

(in the formula, R⁵Represents an alkylene group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom, or a group represented by the following formula (a5), R⁶Represents an alkyl group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom, or a group represented by the following formula (a6)²Represents a single bond, S, O, sulfinyl, or carbonyl group, and n1 represents 0 or 1. )

(in the formula, R⁷And R⁸Independently represents an alkylene group which may be substituted with a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom represented by the following formula (a5), R⁹And R¹⁰Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the above formula (a2), R⁹And R¹⁰May be bonded to each other and form a ring together with the sulfur atom in the formula A³Represents a single bond, S, O, sulfinyl, or carbonyl, X^-As mentioned above, n2 represents 0 or 1, wherein R⁹And R¹⁰And not both alkyl groups which may be substituted by halogen atoms. )

(in the formula, ring Z²Represents an aromatic hydrocarbon ring, R¹¹Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more. )

(in the formula, ring Z³Represents an aromatic hydrocarbon ring, R¹²Represents a halogen atom which may be substituted by a halogen atomA substituted alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more. )

The 2 nd embodiment of the present invention is a cured product obtained by curing the energy-sensitive composition according to the 1 st embodiment of the present invention.

The 3 rd aspect of the present invention is a method for producing a cured product, the method comprising the step of polymerizing and/or crosslinking the energy-sensitive composition according to the 1 st aspect of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides 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.

Drawings

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

FIG. 2 is a TG/DSC curve showing the thermogravimetric change of comparative example 7.

FIG. 3 is a TG/DSC curve showing the thermogravimetric change of comparative example 8.

FIG. 4 is a TG/DSC curve showing the thermogravimetric change of comparative example 9.

FIG. 5 is a TG/DSC curve showing the thermogravimetric change of the reference example.

Detailed Description

The present invention is not limited to the embodiments described below, and can be carried out with appropriate modifications within the scope of the object of the present invention.

In the present specification, for example, the expressions "a and/or B", and "a and/or B" mean "at least 1 selected from the group consisting of a and B" as in the "cationic and/or acid catalytic" and the like. Here, a and B are arbitrary terms.

< energy-sensitive composition >

The energy-sensitive composition according to the present invention comprises 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 (Q) a sulfonium salt represented by the formula (a 1).

Since the energy-sensitive composition according to the present invention contains the sulfonium salt represented by the above formula (a1) (hereinafter also referred to as "sulfonium salt (Q)") and the concentration of protons increases with increasing temperature in the system containing the compound component (P) and the sulfonium salt (Q), it is presumed that the stepwise polymerization of the compound component (P) continues, the polymerization is promoted, and the amount of the monomer decomposed by heat is small. From this, it is presumed that the weight stability against heat of the energy-sensitive composition according to the present invention is improved. The mode of generating protons by the sulfonium salt (Q) includes a mode of generating protons by decomposition of the sulfonium salt (Q) itself and a mode of generating protons by removing hydrogen from components in the system.

[ (P1) polymerizable and/or crosslinkable compounds based on cationic and/or acid-catalytic systems ]

The polymerizable and/or crosslinkable compound by the cationic and/or acid-catalytic system (hereinafter, also referred to as "compound (P1)") includes, for example, a compound which can be cationically polymerized by a cation containing an alkyl group or an aryl group or a proton. Examples thereof include cyclic ethers, particularly epoxy compounds, oxetane compounds, vinyl ether compounds, and hydroxyl group-containing compounds. In addition, lactone compounds, cyclic sulfide compounds, and vinyl sulfide compounds can also be used. In the present specification, the compound containing an ethylenically unsaturated group (vinyl group) is a compound (epoxy-oxetanyl/vinyl group-containing compound) having an epoxy group and/or an oxetanyl group (P1); the other compounds (epoxy-oxetanyl-containing/vinyl-containing compounds) are the compounds (Px). In the present specification, unless otherwise specified, the "epoxy group" generally includes not only an oxetanyl group but also an oxetanyl group and an alicyclic epoxy group.

Further examples include aminoplasts and phenol resin resins. They are in particular melamine resins, urea resins, epoxy resins, phenolic resins, acrylic resins, polyester resins and alkyd resins, in particular acrylic resins, polyester resins or mixtures of alkyd resins with melamine resins. Further, examples thereof include modified surface coating resins (for example, acrylic-modified polyester resins, acrylic-modified alkyd resins, and the like). The term surface coating resin preferably comprises an amino resin. Examples thereof include etherified and non-etherified melamine resins, urea resins, guanidine resins, and biuret resins. Acid catalysts for curing of surface-coated resins comprising etherified amino resins, such as methylated melamine resins or butylated melamine resins (N-methoxymethyl-melamine or N-butoxymethyl-melamine), methylated/butylated glycoluril, are of particular importance.

When the compound (P1) is an epoxy compound, it is not particularly limited as long as it has at least 1 epoxy group in the molecule, and a compound having at least 2 epoxy groups in the molecule is preferable. The epoxy compound can be selected from various compounds having an epoxy group which have been conventionally blended in the curable composition. The epoxy compound may be a low molecular weight compound having an epoxy group as a non-polymer, or may be a polymer having an epoxy group, and is preferably a non-polymer. The non-polymer having an epoxy group is preferably an aliphatic epoxy compound having no aromatic group, from the viewpoint of excellent thermal weight stability of a cured product formed using the energy-sensitive composition. Among the aliphatic epoxy compounds, aliphatic epoxy compounds having an alicyclic epoxy group are preferable in that the ring-opening polymerization allows stepwise polymerization and promotion of polymerization.

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, epsilon-caprolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexanecarboxylate, 2- (3, 4-epoxycyclohexylmethyl-5, 5-spirocyclo-3, 4-epoxycyclohexanecarboxylate, and mixtures thereof, Beta-methyl-delta-valerolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), bis (3, 4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxycyclohexanecarboxylate), dioctylphthalate oxide (epoxyhexahydrophthalic acid diester), di-2-ethylhexyl epoxyhexahydrophthalate, epoxy resins having an oxytetracyclodecenyl group, and compounds represented by the following formulae (P1-1) to (P1-5). Of these specific examples of the aliphatic epoxy compound, alicyclic epoxy compounds represented by the following formulae (P1-1) to (P1-4) are preferable, and alicyclic epoxy compounds represented by the following formulae (P1-1) to (P1-2) are more preferable, from the viewpoint that stepwise polymerization is carried out and the polymerization can be accelerated. These alicyclic epoxy compounds may be used alone or in combination of 2 or more. The compound component (P) or the compound (P1) preferably contains at least 1 selected from the group consisting of an alicyclic epoxy compound represented by the formula (P1-1), an alicyclic epoxy compound represented by the formula (P1-2) and an alicyclic epoxy compound represented by the formula (P1-8) when reduction of exhaust gas is particularly desired, and the proportion of the compound component (P) or the compound (P1) as a whole may be 1 to 99 mass%, 10 to 90 mass%, 20 to 80 mass%, 30 to 70 mass%, 40 to 60 mass%, or the like. In addition, from the viewpoint of exhaust gas reduction and viscosity of the energy-sensitive composition, it is preferable to use an alicyclic epoxy compound represented by the formula (P1-1) and an alicyclic epoxy compound represented by the formula (P1-2) in combination. 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, 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 (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) is not particularly limited, and may be, for example, 1 to 99% by mass, 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, 40 to 60% by mass, or the like.

(in the formula (P1-1), Z represents a single bond or a linking group (a divalent group having 1 or more atoms.) R^a1～R^a18Each independently is 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 a hydrocarbon group which may contain an oxygen atom or a halogen atom, each of which may be the same or different. )

Examples of the linking group Z include divalent hydrocarbon groups, -O-CO-, -S-, -SO-, -SO₂-、-CBr₂-、-C(CBr₃)₂-、-C(CF₃)₂-, and-R^a19A divalent group selected from the group consisting of-O-CO-, a group in which a plurality of the divalent groups are bonded, and the like, wherein-R is preferable^a19-O-CO-。

Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a1, 2-ethylene group, and a1, 3-propylene group. Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups (including cycloalkylidene groups) such as 1, 2-cyclopentylene group, 1, 3-cyclopentylene group, cyclopentylidene group (cyclopentylidene), 1, 2-cyclohexylene group, 1, 3-cyclohexylene group, 1, 4-cyclohexylene group, cyclohexylidene group (cyclohexylidene), and the like.

R^a19Is an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a carbon atomThe alkylene group having a sub-number of 1 to 3 is preferably a methylene group or an ethylene group.

The compound represented by the formula (P1-1) is preferably a compound which is not easily dehydrogenated to form a conjugated structure (particularly, a pi-electron conjugated structure), and more preferably an alicyclic epoxy compound, specifically a compound in which 2 alicyclic epoxy groups in one molecule are bonded to each other via a linking group containing a quaternary carbon and/or a hetero atom, in order to obtain a cured product having not only excellent thermal weight stability but also excellent transparency.

Examples of the compound (P1) include alicyclic epoxy compounds represented by the following formulae (P1-2) to (P1-5).

(in the formula (P1-2), R^a1～R^a12Each independently is 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 a hydrocarbon group which may contain an oxygen atom or a halogen atom, each of which may be the same or different. R^a2And R^a10Can be bonded to each other. )

(in the formula (P1-3), R^a1～R^a10Each independently is 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 a hydrocarbon group which may contain an oxygen atom or a halogen atom, each of which may be the same or different. R^a2And R^a8Can be bonded to each other. )

(in the formula (P1-4), R^a1～R^a12Each independently selected from hydrogen atom, halogenThe group of the element atom and the organic group is, for example, a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an oxygen atom or a halogen atom, and each may be the same or different. R^a2And R^a10Can be bonded to each other. )

(in the formula (P1-5), R^a1～R^a12Each independently is 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 a hydrocarbon group which may contain an oxygen atom or a halogen atom, each of which may be the same or different. )

In the formula (P1-1), R^a1～R^a12In the case of an organic group, the organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be a hydrocarbon group, a group composed of a carbon atom and a halogen atom, or a group containing not only a carbon atom and a hydrogen atom but also a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, or the like. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like.

As the organic group, the following groups are preferable: a hydrocarbyl 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; and a group formed of a carbon atom, a hydrogen atom, an oxygen atom, and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

Specific examples of the hydrocarbon group include linear alkyl groups such as 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-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl; chain alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, α -naphthyl, β -naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthryl, and phenanthryl; aralkyl groups such as benzyl, phenethyl, α -naphthylmethyl, β -naphthylmethyl, α -naphthylethyl, and β -naphthylethyl.

Specific examples of the halogenated hydrocarbon group include halogenated chain alkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl; halocycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl and 4-bromocyclohexyl; halogenated aryl groups such as 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, and 4-fluorophenyl; and halogenated aralkyl groups such as 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl, 2-bromophenylmethyl, 3-bromophenylmethyl, 4-bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl, and 4-fluorophenylmethyl.

Specific examples of the group composed of a carbon atom, a hydrogen atom and an oxygen atom include a hydroxy chain alkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group and a 4-hydroxy-n-butyl group; halocycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl; hydroxyaryl groups such as 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; a hydroxyaralkyl group such as a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, or a 4-hydroxyphenylmethyl group; chain alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, and n-eicosyloxy groups; chain alkenyloxy groups such as vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, and 3-n-butenyloxy; aryloxy groups such as phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, α -naphthyloxy, β -naphthyloxy, biphenyl-4-yloxy, biphenyl-3-yloxy, biphenyl-2-yloxy, anthryloxy, and phenanthryloxy; aralkyloxy groups such as benzyloxy, phenethyloxy, α -naphthylmethyloxy, β -naphthylmethyloxy, α -naphthylethyloxy, and β -naphthylethyloxy; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; alkoxyalkoxy groups such as methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, and 4-n-propoxy-n-butyloxy; alkoxyaryl groups such as 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl; alkoxyaryloxy groups such as 2-methoxyphenoxy group, 3-methoxyphenoxy group and 4-methoxyphenoxy group; aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, and decanoyl; aromatic acyl groups such as benzoyl, α -naphthoyl and β -naphthoyl; chain alkyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl; an aryloxycarbonyl group such as a phenoxycarbonyl group, an α -naphthyloxycarbonyl group, and a β -naphthyloxycarbonyl group; aliphatic acyloxy groups such as formyloxy, acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy; aromatic acyloxy groups such as benzoyloxy group, α -naphthoyloxy group, and β -naphthoyloxy group.

R^a1～R^a18Each independently preferably being 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, and more preferably R, from the viewpoint of excellent mechanical properties of a cured product obtained using the energy-sensitive composition^a1～R^a18All are hydrogen atoms.

In the formulae (P1-2) to (P1-5), R^a1～R^a12And R in the formula (P1-1)^a1～R^a12The same is true. In the formulae (P1-2) and (P1-4), R is^a2And R^a10Examples of the divalent group formed by bonding to each other include-CH₂-、-C(CH₃)₂-. In the formula (P1-3), as R^a2And R^a8Examples of the divalent group formed by bonding to each other include-CH₂-、-C(CH₃)₂-。

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

Among the alicyclic epoxy compounds represented by the formula (P1-2), preferable examples of the compound include a bicyclic nonadiene diepoxide represented by the following formula (P1-2a), a bicyclic nonadiene diepoxide, and the like.

Among the alicyclic epoxy compounds represented by the formula (P1-3), preferable examples of the compounds include S-spiro [ 3-oxatricyclo [3.2.1.0 ]^2,4]Octane-6, 2' -oxetanes]And the like.

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

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

Examples of epoxy group-containing nonpolymers that can be used as the compound (P1) in addition to the alicyclic epoxy group-containing aliphatic epoxy compounds described above include epoxy alkyl (meth) acrylates such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate; epoxyalkyloxyalkyl (meth) acrylates such as 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate; 2-functional epoxy resins such as 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; novolac type epoxy resins such as 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; cyclic aliphatic epoxy resins such as epoxides of dicyclopentadiene type phenol resins; aromatic epoxy resins such as epoxides of naphthalene-based phenol resins; 9, 9-bis [4- (glycidyloxy) phenyl ] -9H-fluorene, 9-bis [4- [2- (glycidyloxy) ethoxy ] phenyl ] -9H-fluorene, 9-bis [4- [2- (glycidyloxy) ethyl ] phenyl ] -9H-fluorene, 9-bis [4- (glycidyloxy) -3-methylphenyl ] -9H-fluorene, 9-bis [4- (glycidyloxy) -3, 5-dimethylphenyl ] -9H-fluorene, and 9, 9-bis (6-glycidyloxynaphthalen-2-yl) -9H-fluorene, 9-bis (6-glycidyloxynaphthalen-1-yl) -9H-fluorene, 9, 9-bis (glycidyloxynaphthyl) fluorenes such as 9, 9-bis (5-glycidyloxynaphthalen-1-yl) -9H-fluorene; 9, 9-bis (glycidyloxyalkoxynaphthyl) fluorenes such as 9, 9-bis [6- (2-glycidyloxyethoxy) naphthalen-2-yl ] -9H-fluorene, 9-bis [6- (2-glycidyloxypropoxy) naphthalen-2-yl ] fluorene, 9-bis [5- (2-glycidyloxyethoxy) naphthalen-1-yl ] fluorene and 9, 9-bis [5- (2-glycidyloxypropoxy) naphthalen-1-yl ] fluorene; 9, 9-bis {6- [2- (2-glycidyloxyethoxy) ethoxy ] naphthalen-2-yl } -9H-fluorene, 9-bis {6- [2- (2-glycidyloxypropoxy) propoxy ] naphthalen-2-yl } -9H-fluorene, epoxy group-containing fluorene compounds such as 9, 9-bis (glycidyloxydialkoxynaphthyl) fluorenes, for example, 9-bis {5- [2- (2-glycidyloxyethoxy) ethoxy ] naphthalen-1-yl } -9H-fluorene and 9, 9-bis {5- [2- (2-glycidyloxypropoxy) propoxy ] naphthalen-1-yl } -9H-fluorene; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, and tetraglycidyl bisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] ethyl ] phenyl ] propane, and 1, 3-bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetracyclooxyprophobiphenyl, and 1, 2-epoxy-4- (2-oxetanyl) cyclohexane adducts of 2, 2-bis (hydroxymethyl) -1-butanol. The 1, 2-epoxy-4- (2-oxetanyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel).

Further, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3-hydroxymethyloxetane methacrylate, bis-1-ethyl-3-oxetanyl ether, examples of the oxetane compound include compounds having an oxetanyl group (oxetane compounds) such as 1, 4-bis-3-ethyloxetan-3-ylmethoxymethylbenzene, 3-ethyl-3-2-ethylhexyloxymethyloxetane and 3-ethyl-3-phenoxymethyloxetane, and also include oxetane compounds in which the oxetanyl group in 1 molecule is 1 or 2 or more monofunctional or difunctional or more.

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

(in the formula (P1-8), ring Z⁴Represents a condensed polycyclic aromatic hydrocarbon ring, R^P35And R^P36Express getSubstituent group, R^P37Represents a hydrogen atom or a methyl group, k1 is an integer of 0 to 4, k2 is an integer of 0 or more, and k3 is an integer of 1 or more. )

In the above formula (P1-8), as ring Z⁴Examples of the fused polycyclic aromatic hydrocarbon ring include fused two-to four-ring hydrocarbon rings such as a fused bicyclic hydrocarbon ring (e.g., a C8-C20 fused bicyclic hydrocarbon ring such as an indene ring or a naphthalene ring, preferably a C10-C16 fused bicyclic hydrocarbon ring), a fused three-ring hydrocarbon ring (e.g., an anthracene ring or a phenanthrene ring), and the like. Preferred fused polycyclic aromatic hydrocarbon rings include naphthalene rings, anthracene rings, and the like, and naphthalene rings are particularly preferred. 2 rings Z substituted at the 9-position of fluorene⁴Which may be the same or different rings, and which may be generally the same ring.

In addition, a ring Z substituted at the 9-position of fluorene⁴The substitution position of (2) is not particularly limited, and for example, naphthyl substituted at the 9-position of fluorene may be 1-naphthyl, 2-naphthyl or the like, and 2-naphthyl is particularly preferable.

In the above formula (P1-8), R is^P35Examples of the substituent include a cyano group, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), a hydrocarbon group [ e.g., an alkyl group, an aryl group (e.g., a C6-C10 aryl group such as a phenyl group), and the like]And the like, in particular, a halogen atom, a cyano group or an alkyl group (particularly an alkyl group) is often used. Examples of the alkyl group include a C1-C6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a tert-butyl group (for example, a C1-C4 alkyl group, particularly a methyl group). When there are a plurality of (2 or more) k1, R^P35May be different from each other or the same. R substituted on 2 benzene rings constituting fluorene (or fluorene skeleton)^P35May be the same or different. In addition, R^P35The bonding position (substitution position) on the benzene ring constituting the fluorene is not particularly limited. k1 is preferably 0 to 1, and particularly preferably 0. In the 2 benzene rings constituting the fluorene, k1 may be the same or different from each other.

As at ring Z⁴R being substituted on^P36Examples thereof include alkyl groups (e.g., C1-C12 alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl groups, etc., preferablyA hydrocarbon group such as a C1 to C8 alkyl group, more preferably a C1 to C6 alkyl group, etc.), a cycloalkyl group (e.g., a C5 to C8 cycloalkyl group such as a cyclohexyl group, etc., preferably a C5 to C6 cycloalkyl group, etc.), an aryl group (e.g., a C6 to C14 aryl group such as a phenyl group, a tolyl group, a xylyl group, etc., preferably a C6 to C10 aryl group, more preferably a C6 to C8 aryl group, etc.), an aralkyl group (e.g., an aralkyl group in which a C6 to C10 aryl group such as a benzyl group, a phenethyl group, etc. is bonded to a C1 to C4 alkyl group, etc.); alkoxy (e.g., C1-C8 alkoxy such as methoxy, preferably C1-C6 alkoxy), cycloalkoxy (C5-C10 cycloalkyloxy), aryloxy (C6-C10 aryloxy), etc. -OR^P38Group [ in the formula, R^P38Represents a hydrocarbon group (the hydrocarbon group exemplified above, etc.).](ii) a an-SR such as an alkylthio group (e.g., a C1-C8 alkylthio group such as a methylthio group, preferably a C1-C6 alkylthio group)^P38Group (in the formula, R^P38As described above. ) (ii) a Acyl (e.g., C1-C6 acyl such as acetyl); an alkoxycarbonyl group (for example, an alkoxycarbonyl group in which a carbonyl group is bonded to a C1-C4 alkoxy group such as a methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); a hydroxyl group; a nitro group; a cyano group; and a substituted amino group (e.g., a dialkylamino group such as a dimethylamino group).

In these, R^P36Preferably a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, halogen atom, nitro group, cyano group, substituted amino group, etc., R^P36Particularly preferred is a hydrocarbon group [ e.g., an alkyl group (e.g., C1-C6 alkyl group) ]]Alkoxy groups (e.g., C1-C4 alkoxy groups), halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, and iodine atom), and the like.

Note that the same ring Z⁴In the case where k2 is plural (2 or more), R^P36May be different from each other or the same. In addition, 2 rings Z⁴In, R^P36May be the same or different. Further, k2 is preferably 0 to 8, more preferably 0 to 6 (e.g., 1 to 5), further preferably 0 to 4, and particularly preferably 0 to 2 (e.g., 0 to 1). Note that 2 rings Z⁴K2 may be the same or different from each other.

In the above formula (P1-8), R is^P37Is a hydrogen atom or a methyl group, R^P37Preferably a hydrogen atom.

In the formula (P1-8), k3 is 1 or more, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, and particularly 1. The k3 may be the same or different for each ring Z, and is usually the same in many cases. The substitution position of the epoxy group-containing group is not particularly limited as long as it is on the ring Z⁴May be substituted at the appropriate substitution position. In particular, in the fused polycyclic hydrocarbon ring, the epoxy group-containing group is often substituted at least at a hydrocarbon ring (for example, the 5-position or 6-position of the naphthalene ring) different from the hydrocarbon ring bonded to the 9-position of the fluorene.

Specific examples of the compound represented by the formula (P1-8) include compounds represented by the formula (P1-8) wherein k3 is 1, such as 9, 9-bis (glycidyloxynaphthyl) fluorene [ e.g., 9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9-bis (5-glycidyloxy-1-naphthyl) fluorene ], and the like.

(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 a polymer obtained by introducing an epoxy group into a polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group, by using a compound having an epoxy group such as epichlorohydrin. Further, a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in a side chain, such as 1, 2-polybutadiene, can be suitably used as the polymer having an epoxy group. The partial oxide includes: an epoxy group generated by oxidation of an unsaturated bond contained in a side chain.

The polymer having an epoxy group is preferably a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group, or a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in a side chain, in view of easy availability, easy preparation, easy adjustment of the amount of an epoxy group in the polymer, and the like.

(Polymer of monomer having epoxy group or monomer mixture containing monomer having epoxy group)

Among the polymers having an epoxy group, a homopolymer of a (meth) acrylate having an epoxy group or a copolymer of a (meth) acrylate having an epoxy group and another monomer is preferable in terms of ease of preparation, coatability of the energy-sensitive composition on a substrate, and the like.

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. In view of transparency of a cured product formed using the energy-sensitive composition, the epoxy group-containing (meth) acrylate is preferably an aliphatic (meth) acrylate having a chain aliphatic epoxy group or an aliphatic (meth) acrylate having an alicyclic epoxy group, and more preferably an aliphatic (meth) acrylate having an alicyclic epoxy group.

Examples of the (meth) acrylate containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, 2-glycidyloxyphenyl (meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, and 2-glycidyloxyphenylmethyl (meth) acrylate.

Examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include (meth) acrylates having an oxy group (-O-) in which a chain aliphatic epoxy group is bonded to an ester group (-O-CO-), such as an alkylene oxide (meth) acrylate and an alkylene oxide oxyalkyl (meth) acrylate. Such a (meth) acrylate may have a chain aliphatic epoxy group containing 1 or more oxy groups (-O-) in the chain. The number of carbon atoms of 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 aliphatic epoxy group include epoxy alkyl (meth) acrylates such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate and the like; epoxyalkyloxyalkyl (meth) acrylates such as 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate.

Specific examples of the aliphatic (meth) acrylate having an alicyclic epoxy group include compounds represented by the following formulas (a2-1) to (a 2-15). Among these, preferred are compounds represented by the following formulae (a2-1) to (a2-5), and more preferred are compounds represented by the following formulae (a2-1) to (a 2-3).

In the above formula, R^a20Represents a hydrogen atom or a methyl group, R^a21Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a22Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10. As R^a21The alkylene group is preferably a linear or branched alkylene group, and is preferably, for example, a methylene group, an ethylene group, a propylene group, a1, 4-butylene group, an ethylethylene group, a1, 5-pentylene group, or a1, 6-hexylene group. As R^a22For example, methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene, phenylene, cyclohexylene are preferable.

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

When the polymer having an epoxy group is a copolymer of a (meth) acrylate having an epoxy group and another monomer, examples of the other monomer include an unsaturated carboxylic acid, a (meth) acrylate having no epoxy group, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of 2 or more. The copolymer of the (meth) acrylate having an epoxy group and another monomer preferably does not contain a unit derived from an unsaturated carboxylic acid, from the viewpoint of storage stability of the energy-sensitive composition and chemical resistance of a cured product formed using the energy-sensitive composition to alkali or the like.

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

Examples of the (meth) acrylate having no epoxy group include linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and tert-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; (meth) acrylate containing a group having an alicyclic skeleton. Among the (meth) acrylates having no epoxy group, a (meth) acrylate having a group having an alicyclic skeleton is preferable in view of transparency of a 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 a single ring or a plurality of rings. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.

Examples of the (meth) acrylate containing a group having an alicyclic skeleton include compounds represented by the following formulas (a3-1) to (a 3-8). Among these, preferred are compounds represented by the following formulae (a3-3) to (a3-8), and more preferred are compounds represented by the following formulae (a3-3) or (a 3-4).

In the above formula, R^a23Represents a hydrogen atom or a methyl group, R^a24Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a25Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R^a24The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a1, 4-butylene group, an ethylethylene group, a1, 5-pentylene group, or a1, 6-hexylene group. As R^a25Preferably, methyl and ethyl are used.

Examples of the (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N-dialkyl (meth) acrylamide, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and the like.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and so on.

Examples of the vinyl ethers include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and the like; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; and so on.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of the styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and so on.

(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, and 1, 2-polybutadiene having a vinyl group in a side chain is preferable from the viewpoint of easy availability, easy synthesis, and the like. By partially oxidizing 1, 2-polybutadiene, epoxidized polybutadiene having an oxetanyl group and a vinyl group in the side chain can be obtained. The ratio of the oxetanyl group in the epoxidized polybutadiene is preferably 10 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 10 to 40 mol%, based on the total number of moles of the oxetanyl group and the vinyl group. As the epoxidized polybutadiene, JP-100 and JP-200 sold by Nippon Caoda corporation can be suitably used.

The molecular weight of the polymer having an epoxy group described above is not particularly limited within a range not interfering with the object of the present invention, and is preferably 3,000 to 30,000, more preferably 5,000 to 15,000, as a weight average molecular weight in terms of polystyrene.

Examples of the compound (P1) include compounds represented by the following formula (P1-6).

(in the formula (P1-6), R^P31～R^P33The alkylene group may be the same or different and may be a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (═ O) -, -NH-, or a group formed by a combination thereof. E¹～E³Is at least 1 substituent selected from the group consisting of an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group and a succinic anhydride group, or a hydrogen atom. Wherein E is¹～E³At least 1 of them is at least 1 selected from the group consisting of epoxy groups and oxetanyl groups. )

In the formula (P1-6), for the structural formula represented by R^P31And E¹、R^P32And E²And R^P33And E³As the group represented, for example, at least 1 is preferably a group represented by the following formula (P1-6a), more preferably at least 2 are each a group represented by the following formula (P1-6a), and still more preferably all 3 are each represented by the following formula (P1-6a)A group. The groups represented by the formula (P1-6a) bonded in 1 compound are preferably the same group.

-L-C(P1-6a)

(in the formula (P1-6a), L represents a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (═ O) -, -NH-, or a group formed by a combination thereof, and C represents at least 1 member 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 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-, or a group formed of a combination thereof, and is preferably at least 1 of a linear alkylene group having 1 to 3 carbon atoms and a phenylene group such as a methylene group, or a group formed of a combination thereof and at least 1 of-O-, -C (═ O) -and NH-.

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

(in the formula (P1-6b), R^P34Is a hydrogen atom or a methyl group. )

Examples of the compound represented by the formula (P1-6) include epoxy compounds having at least 1 group selected from the group consisting of an oxetanyl group, an oxetanyl group and an alicyclic epoxy group, but the present invention is not limited to these.

Examples of the compound (P1) include a siloxane compound having 2 or more glycidyl groups in the molecule (hereinafter, also referred to as "siloxane compound (B)").

The siloxane compound (B) is a compound which can impart yellowing resistance (heat-resistant transparency) for preventing yellowing of the resulting cured product when exposed to a high-temperature environment for a long period of time, and has 2 or more glycidyl groups in the molecule and further has a siloxane skeleton composed of siloxane bonds (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 or branched polysiloxane), a cage-type or ladder-type polysilsesquioxane, and the like), and the like.

Among these, the siloxane compound (B) is preferably a compound having a cyclic siloxane skeleton represented by the following formula (B-1) (hereinafter, may be referred to as "cyclic siloxane") because of excellent curability and particularly excellent heat resistance and transparency of the resulting cured product.

In the formula (B-1), R^B1、R^B2Means containing glycidolMonovalent radicals of radicals or alkyl radicals. Wherein n R's in the compound represented by the formula (B-1)^B1And n R^B2At least 2 of them are monovalent glycidyl group-containing groups. In addition, n in the formula (B-1) represents an integer of 3 or more. R in the compound represented by the formula (B-1)^B1、R^B2May be the same or different. In addition, a plurality of R^B1May be the same or different. Plural R^B2And may be the same or different.

The glycidyl group-containing monovalent group is preferably-D-O-R^B3The glycidyl ether group [ D ] represents an alkylene group, R^B3Represents a glycidyl group]. Examples of the D (alkylene) group include linear or branched alkylene groups having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a1, 2-ethylene group, and a1, 3-propylene group.

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

N in the formula (B-1) represents an integer of 3 or more, and among them, an integer of 3 to 6 is preferable from the viewpoint of excellent curability of the energy-sensitive composition and heat resistance and mechanical strength of a cured product.

The number of glycidyl groups in the molecule of the siloxane compound (B) is 2 or more, and from the viewpoint of curability of the energy-sensitive composition, heat resistance of the cured product, and mechanical strength, 2 to 6 are preferable, and 2 to 4 are particularly preferable.

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

The energy-sensitive composition of the present embodiment may contain other siloxane compounds (for example, alicyclic epoxy group-containing cyclic siloxane, alicyclic epoxy group-containing polysiloxane resin described in jp 2008-a 248169, and organopolysiloxane resin having at least 2 epoxy functional groups in 1 molecule described in jp 2008-a 19422) in addition to the siloxane compound (B).

More specifically, examples of the siloxane compound (B) include cyclic siloxanes having 2 or more glycidyl groups in the molecule represented by the following formula. Further, as the silicone compound (B), commercially available products such as those having the trade names "X-40-2701", "X-40-2728", "X-40-2738" and "X-40-2740" (manufactured by shin-Etsu chemical industries, Ltd.) can be used.

[ (P2) Compounds whose solubility in the developer increases under the action of an acid ]

Examples of the compound (hereinafter, also referred to as "compound (P2)") having increased solubility in the developer by the action of an acid include oligomers, polymers and copolymers obtainable by copolymerization of the monomers listed below.

Acyclic or cyclic secondary and tertiary alkyl (meth) acrylates [ e.g., t-butyl acrylate, t-butyl methacrylate, 3-oxocyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl methacrylate, 5-norbornene-2-t-butyl (meth) acrylate, 8-ethyl-8-tricyclodecanyl (meth) acrylate, 2-tetrahydropyranyl) oxonorbornyl acrylate, 2-tetrahydropyranyl) oxymethyltricyclodecanyl methacrylate, trimethylsilylmethyl (meth) acrylate, 2-tetrahydropyranyl) oxonorbornyl acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and mixtures thereof, (2-tetrahydropyranyl) oxymethyltricyclodecanemethanol methacrylate, (trimethylsilylmethyl (meth) acrylate ], o/m/p (3-oxocyclohexyloxy) styrene, o/m/p (1-methyl-1-phenylethoxy) styrene, o/m/p-tetrahydropyranyloxy styrene, o/m/p-adamantyloxy styrene, o/m/p-cyclohexyloxy styrene, o/m/p-norbornyloxy styrene, acyclic or cyclic alkoxycarbonylstyrenes [ e.g. o/m/p-tert-butoxycarbonyl styrene, o/m/p (3-oxocyclohexyloxy carbonyl) styrene, o/m/p (1-methyl-1-phenylethoxycarbonyl) styrene, O/m/p-tetrahydropyranyloxycarbonylstyrene, o/m/p-adamantyloxycarbonylstyrene, o/m/p-cyclohexyloxycarbonylstyrene, o/m/p-norbornyloxycarbonylstyrene ], acyclic or cyclic alkoxycarbonyloxystyrenes [ e.g., o/m/p-tert-butoxycarbonyloxystyrene, o/m/p (3-oxocyclohexyloxycarbonyloxy) styrene, o/m/p (1-methyl-1-phenylethoxycarbonyloxy) -styrene, o/m/p-tetrahydropyranyloxycarbonyloxystyrene, o/m/p-adamantyloxycarbonyloxystyrene, o/m/p-cyclohexyloxycarbonyloxystyrene, o/m/p-adamantyloxystyrene, o/m/p-isobutoxycarbonyloxystyrene, o/p-butyloxycarbonyloxystyrene, o-n, O/m/p-norbornyloxycarbonyloxystyrenes ], acyclic or cyclic alkoxycarbonylalkoxystyrenes [ 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 (e.g., isopropenyl acetate, derivatives thereof), 5-norbornenyl-2-tert-butyl acetate

Monomers with acid-labile groups having low activation energy [ e.g.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) methylstyrene, p-or m- (1-methoxyethoxy) styrene, p-or m- (1-methoxyethoxy) -methylstyrene, p-or m- (1-ethoxy-1-methylethoxy) styrene, p-or m- (1-ethoxy-1-methylethoxy) methylstyrene, p-or m- (1-ethoxy-1-methylpropoxy) 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-ethoxyethoxy) methylstyrene, p-or m- (1-methylethoxy) styrene, p-or m-1-methylstyrene, p-or m-propoxyethoxy-1-methylstyrene, p-or m-1-methylethoxy) styrene, p-or m-1-ethoxystyrene, p-1-methylethoxy-styrene, p-1-methyl-styrene, m-1-ethoxystyrene, p-or m-1-methyl-one, 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-methylethoxy) styrene, p-or m- (1-n-butoxyethoxy) styrene, p-or m- (1-isobutoxy-1-methylethoxy) -styrene, p-or m- (1-tert-butoxy-1-methylethoxy) styrene, p-or m- (1-tert-isopropoxy-1-methylethoxy) styrene, p-or m- (1-isopropoxy-methylpropoxy) styrene, p-or m- (1-isopropoxy-1-methylpropoxy) styrene, p-isopropyloxy) styrene, p-or m- (1-isopropyloxy) styrene, p-isopropyloxy) styrene, m, p-isopropyloxy-methyl-styrene, m, p-1-isopropyloxy, m, p-isopropyloxy, p-1-isopropyloxy, m, p-methyl-styrene, p-isopropyloxy, m, p, m, p-1-styrene, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p, m, p-or m- (1-n-pentyloxy-1-methylethoxy) styrene, p-or m- (1-isopentyloxy-1-methylethoxy) styrene, p-or m- (1-n-hexyloxy-1-methylethoxy) styrene, p-or m- (1-cyclohexyloxy-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-methylethoxy) styrene, p-or m-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-methylethoxy) methylstyrene ]

The compound (P2) may be a polymer having an alkoxyalkyl ester acid labile group. Examples of polymers having alkoxyalkyl ester acid labile groups are explicitly disclosed in US5225316 and EP 829766. 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.Photoplaster Sci.technology. Vol.10, No.4(1997), pp.571-578, J.Photoplaster Sci.technology. Vol.12, No.4(1999) pp.591-599 and "Proceedings of SPIE", Advances in Resist Technology and Processing XVII, Vol.3999, Part, One, 579-590,28 Fech. 1-2000. However, the polymer suitable for the composition of the present embodiment is not limited to these.

In addition, the monomer having an acid labile group can be copolymerized with other free radical polymerizable monomers [ e.g., styrene, acrylonitrile, methyl (meth) acrylate, (meth) acrylic acid, 4-hydroxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-vinylcyclohexanol, norbornene, ethylnorbornene, maleic anhydride ] having no acid labile group, if appropriate, in order to achieve specific solubility and adhesion. Alternatively, the acid labile groups may be introduced continuously only in a polymer-analogous reaction. The prepolymers can be modified in the targeted manner by, for example, partial hydrogenation, partial alkylation, partial acetylation before the analogous reaction of the polymers, as is also known to the person skilled in the art. That is, the polymer having an acid labile group is not necessarily synthesized from the monomer by copolymerization in all cases.

For example, H.T.Schacht, P.Falcigno, N.Muenzel, R.Schulz and A.Medina, ACS Symp.Ser.706(Micro-and Nanopatterning Polymers), pp.78-94,1997; H. acid-labile cross-linking structures were introduced as described in T.Schacht, N.Muenzel, P.Falcigno, H.Holzwarth and J.Schneider, J.Photopolamer Science and Technology, Vol.9, (1996), 573-. From the viewpoint of thermal stability, the acid crosslinking system structure is preferable. In addition, the acid-labile cross-linked structure can be obtained by the reaction of di-and polyfunctional vinyl ethers with a polymer containing a phenol group (e.g., 4-hydroxystyrene copolymer).

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

The compound (P2) in the energy-sensitive composition is at least 1 compound selected from the group consisting of alicyclic copolymers, copolymers containing 4-hydroxyphenyl groups, copolymers containing maleic anhydride, copolymers containing acrylic acid, copolymers containing acrylic ester, and copolymers containing methacrylic ester, and these copolymers have a functional group that increases the solubility of the polymer in an alkaline developer after the reaction with an acid.

[ (Px) radically polymerizable or crosslinkable Compounds ]

Examples of the radical polymerizable or crosslinkable compound (also referred to as "compound (Px)" in the present specification) include acrylates having a reactive functional group. The reactive functional group may 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, for example. Examples of the unsaturated acrylate containing an OH group include hydroxyethyl acrylate and hydroxybutyl acrylate. The compound (Px) may have any desired structure (for example, it may contain a unit such as a polyester, a polyacrylate, or a polyether) and contains an ethylenically unsaturated double bond and a free OH group, a COOH group, or NH₂Or NCO groups.

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

it can pass through CH₂CHCOOH and

is obtained by the reaction of (1).

Another possible method for obtaining the compound (Px) is, for example, the reaction of an oligomer containing only 1 epoxy group and having a free OH group at other positions in the molecule.

The compound (Px) may be a compound represented by the following formula (Px-1).

(in the formula (Px-1), R^P31～R^P33The alkylene group may be the same or different and may be a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (═ O) -, -NH-, or a group formed by a combination thereof. E⁴～E⁶Is a functional group or a hydrogen atom capable of radical polymerization or crosslinking between the compound (P1) and the compound represented by the formula (Px-1) or between the compounds represented by the formula (Px-1). Wherein E is⁴～E⁶At least 1 of which is the functional group. )

In the formula (Px-1), for R^P31And E⁴、R^P32And E⁵And R^P33And E⁶As the group represented, for example, at least 1 is preferably a group represented by the following formula (Px-1a), more preferably at least 2 are each a group represented by the following formula (Px-1a), and still more preferably each is a group represented by the following formula (Px-1 a). The groups represented by the formula (Px-1a) bonded to 1 compound are preferably the same group.

-L’-C’(Px-1a)

(wherein in the formula (Px-1a), L 'represents a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (═ O) -, -NH-, or a group formed by a combination thereof, and C' represents at least 1 substituent selected from the group consisting of an ethylenically unsaturated group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a thiol group, a carboxyl group, a hydroxyl group, a pyrazolyl group, an alkoxy group, a ketone group, a lactone ring, and a succinic anhydride group.) in addition, in the formula (Px-1a), 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 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 a group formed of a combination thereof, and is preferably a group formed of at least 1 of a linear alkylene group having 1 to 6 carbon atoms such as a methylene group and a phenylene group, or a combination thereof with at least 1 of-O-, -C (═ O) -and NH-. When the branched alkylene group is bonded to the succinic anhydride group to form a cyclic structure, specific examples thereof include cyclohexane-1, 2-dicarboxylic anhydride.

The content of the compound component (P) in the energy-sensitive composition of the present embodiment is preferably 80 to 99.999% by mass, more preferably 90 to 99.99% by mass, and still more preferably 92 to 99.9% by mass, based on the entire composition (excluding the solvent). When the content of the compound component (P) is within the above range, the thermal weight stability tends to be good.

The compound component (P) may be used alone 1 compound selected from the group consisting of the compound (P1), the compound (P2), and the compound (Px), or may be used in combination of 2 or more. When 2 or more compounds are used in combination, it is preferable to include 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. When the content of the compound (P1) is in the above range, the effect of improving the thermal weight stability is particularly large. When the energy-sensitive composition is used for 3D printing, the compound (P1) and the compound (Px) may be combined, and 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 represented by the above formula (a1) (hereinafter also referred to as "sulfonium salt (Q)") is characterized in that it is contained in the benzene ring of the above formula (a1) relative to a¹A methyl group is bonded to a carbon atom adjacent to the bonded carbon atom. Since the sulfonium salt (Q) has a methyl group at the above-mentioned position, protons are more easily generated than conventional sulfonium salts, and the sensitivity to active energy rays such as ultraviolet rays is high.

In the above formula (a1), R is preferably¹And R²All of which are groups represented by the above formula (a 2). R¹And R²May be the same or different from each other.

In the above formula (a1), R¹And R²When bonded to each other and form a ring together with the sulfur atom in the formulaThe ring preferably has a 3-to 10-membered ring including a sulfur atom, and more preferably a 5-to 7-membered ring. The ring to be formed may be a polycyclic ring, and preferably a ring formed by fusing 5 to 7 membered rings.

In the above formula (a1), R³The group represented by the above formula (a3) is preferable.

In the above formula (a1), A¹Preferably S or O, more preferably S.

In the above formula (a2), R⁴Preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furylcarbonyl group, a selenophenylcarbonyl group, an amino group which may be substituted, or a nitro group which may be substituted by a halogen atom, and more preferably 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 in accordance with ring Z¹The selection of (3) 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), R⁵Represents an alkylene group which may be substituted with a substituent, or a group represented by the formula (a5) described above. Examples of the substituent which may substitute for 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, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom. R⁵Preferably an alkylene group; alkylene substituted with a hydroxyl group, an amino group which may be substituted, or a nitro group; or a group represented by the above formula (a 5).

In the above formula (a3), R⁶Represents an alkyl group which may be substituted with a substituent or a group represented by the above formula (a 6). The substituent which may be substituted for the alkyl group is the same as that for R in the above formula (a3)⁵The same applies to the substituents which may be substituted by alkylene. R⁶Preferably an alkyl group; alkyl substituted with hydroxy, amino which may be substituted, or nitro; or a group represented by the above formula (a 6).

In the above formula (a3)，A²Preferably S or O, more preferably S.

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

In the above formula (a4), R⁷And R⁸Independently represents an alkylene group which may be substituted with a substituent, or a group represented by the above formula (a 5). The substituent which may be substituted for the alkylene group is the same as that for R in the above formula (a3)⁵The same applies to the substituents which may be substituted by alkylene. R⁷And R⁸Independently preferably an alkylene group; alkylene 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 a group represented by the above formula (a 5). R⁷And R⁸May be the same or different from each other.

In the above formula (a4), R is preferably⁹And R¹⁰All of which are groups represented by the above formula (a 2). R⁹And R¹⁰May be the same or different from each other.

In the above formula (a4), R⁹And R¹⁰When they are bonded to each other and form a ring together with the sulfur atom in the formula, the ring to be formed preferably contains 3 to 10 members, more preferably 5 to 7 members, rings including the sulfur atom. The ring to be formed may be a polycyclic ring, and preferably a ring formed by fusing 5 to 7 membered rings.

In the above formula (a4), A³Preferably S or O, more preferably S.

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

In the above formula (a5), R¹¹Preferred is an alkyl group which may be substituted with a halogen atom, a hydroxyl group, an amino group which may be substituted, or a nitro group, and more preferred is an alkyl group which may be substituted with a halogen atom.

In the above formula (a5), m2 may be in accordance with ring Z²The selection of (3) 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), R¹²Preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furylcarbonyl group, a selenophenylcarbonyl group, an amino group which may be substituted, or a nitro group which may be substituted by a halogen atom, more preferably an alkyl group, a hydroxyl group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an amino group which may be substituted, or a nitro group which may be substituted by a halogen atomAlkyl, alkylcarbonyl, or thienylcarbonyl.

In the above formula (a6), m3 may be in accordance with ring Z³The selection of (3) 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 rays, electron beams, X-rays, and the like). When sulfonium salt (Q) is used as the acid generator, X is^-Suitable examples thereof include monovalent polyatomic anions, more preferably MY_a ^-、(Rf)_bPF_6-b ^-、R^x1 _cBY_4-c ^-、R^x1 _cGaY_4-c ^-、R^x2SO₃ ^-、(R^x2SO₂)₃C^-Or (R)^x2SO₂)₂N^-The anion shown. In addition, X^-The anion may be a halogen anion, and examples thereof include fluoride ion, chloride ion, bromide ion, iodide ion, and the like.

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 which forms Rf by substitution with fluorine include a linear alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, and octyl), a branched alkyl group (e.g., isopropyl, isobutyl, sec-butyl, and tert-butyl), and a cycloalkyl group (e.g., cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl). The ratio of replacement of hydrogen atoms of these alkyl groups by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100% based on the number of moles of hydrogen atoms of the original alkyl group. When the substitution ratio based on fluorine atoms is within the above-described preferred range, the photosensitivity of the sulfonium salt (Q) becomes better. Rf is particularly preferably CF₃-、CF₃CF₂ ^-、(CF₃)₂CF^-、CF₃CF₂CF₂ ^-、CF₃CF₂CF₂CF₂ ^-、(CF₃)₂CFCF₂ ^-、CF₃CF₂(CF₃)CF^-And (CF)₃)₃C^-. b Rf's are independent of each other and may be the same or different.

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

R^x1Represents a phenyl group in which a part of the hydrogen atom is substituted with at least 1 element or an electron-withdrawing group. Examples of such 1 element include a halogen atom, and include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, preferred is a phenyl group in which at least 1 hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group. c number of R^x1Are independent of each other and thus may be the same as or different from each other.

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

R^x2The alkyl group and the fluoroalkyl group may be linear, branched or cyclic, and the alkyl group, the fluoroalkyl group or the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group, an amino group which may be substituted (for example, amino groups exemplified in the following description with respect to the formulae (a2) to (a 6)), and a nitro group.

In addition, R^x2The carbon chain in the alkyl group, fluoroalkyl group, or aryl group may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. In particular, R^x2The carbon chain in the alkyl group or fluoroalkyl group represented may have a divalent functional group (for example, an ether bond, a carbonyl bond, an ester bond, an amino bond, an amide bond, an imide bond, a sulfonyl bond, an amide bond, a sulfonimide bond, a urethane bond, or the like).

R^x2When the alkyl, fluoroalkyl or aryl group represented by the above-mentioned group has a substituent, hetero atom or functional groupThe number of the substituent, the heteroatom, or the functional group may be 1, or 2 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 to 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, and more preferably 4.

As MY_a ^-Examples of the anion represented by the formula (I) include SbF₆ ^-、PF₆ ^-Or BF₄ ^-The anions shown, and the like.

As (Rf)_bPF_6-b ^-Examples of the anion include (CF)₃CF₂)₂PF₄ ^-、(CF₃CF₂)₃PF₃ ^-、((CF₃)₂CF)₂PF₄ ^-、((CF₃)₂CF)₃PF₃ ^-、(CF₃CF₂CF₂)₂PF₄ ^-、(CF₃CF₂CF₂)₃PF₃ ^-、((CF₃)₂CFCF₂)₂PF₄ ^-、((CF₃)₂CFCF₂)₃PF₃ ^-、(CF₃CF₂CF₂CF₂)₂PF₄ ^-Or (CF)₃CF₂CF₂CF₂)₃PF₃ ^-The anions shown, and the like. Of these, (CF) is preferred₃CF₂)₃PF₃ ^-、(CF₃CF₂CF₂)₃PF₃ ^-、((CF₃)₂CF)₃PF₃ ^-、((CF₃)₂CF)₂PF₄ ^-、((CF₃)₂CFCF₂)₃PF₃ ^-Or ((CF)₃)₂CFCF₂)₂PF₄ ^-The anion shown.

As R^x1 _cBY_4-c ^-The anion represented is preferably:

R^x1 _cBY_4-c ^-

(in the formula, R^x1Represents 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, there may be mentioned (C)₆F₅)₄B^-、((CF₃)₂C₆H₃)₄B^-、(CF₃C₆H₄)₄B^-、(C₆F₅)₂BF₂ ^-、C₆F₅BF₃ ^-Or (C)₆H₃F₂)₄B^-The anions shown, and the like. Of these, (C) is preferable₆F₅)₄B^-Or ((CF)₃)₂C₆H₃)₄B^-The anion shown.

As R^x1 _cGaY_4-c ^-Examples of the anion represented are (C)₆F₅)₄Ga^-、((CF₃)₂C₆H₃)₄Ga^-、(CF₃C₆H₄)₄Ga^-、(C₆F₅)₂GaF₂ ^-、C₆F₅GaF₃ ^-Or (C)₆H₃F₂)₄Ga^-The anions shown, and the like. Of these, (C) is preferred₆F₅)₄Ga^-Or ((CF)₃)₂C₆H₃)₄Ga^-The anion shown.

As R^x2SO₃ ^-Examples of the anion include trifluoromethylSulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, p-toluenesulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, butanesulfonic acid anion, and the like. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion are preferable.

As (R)^x2SO₂)₃C^-Examples of the anion include (CF)₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₃F₇SO₂)₃C^-Or (C)₄F₉SO₂)₃C^-The anions shown, and the like.

As (R)^x2SO₂)₂N^-Examples of the anion include (CF)₃SO₂)₂N^-、(C₂F₅SO₂)₂N^-、(C₃F₇SO₂)₂N^-Or (C)₄F₉SO₂)₂N^-The anions shown, and the like.

As monovalent polyatomic anions, other than MY_a ^-、(Rf)_bPF_6-b ^-、R^x1 _cBY_4-c ^-、R^x1 _cGaY_4-c ^-、R^x2SO₃ ^-、(R^x2SO₂)₃C^-Or (R)^x2SO₂)₂N^-In addition to the anions shown, perhalogenated acid ion (ClO) may be used₄ ^-、BrO₄ ^-Etc.), halogenated sulfonic acid ions (FSO)₃ ^-、ClSO₃ ^-Etc.), sulfuric acid ion (CH)₃SO₄ ^-、CF₃SO₄ ^-、HSO₄ ^-Etc.), carbonate ion (HCO)₃ ^-、CH₃CO₃ ^-Etc.), aluminate ions (AlCl)₄ ^-、AlF₄ ^-Etc.), hexafluorobismuthate ion (BiF)₆ ^-) Carboxylic acid ion (CH)₃COO^-、CF₃COO^-、C₆H₅COO^-、CH₃C₆H₄COO^-、C₆F₅COO^-、CF₃C₆H₄COO^-Etc.), arylboronic acid ion (B (C)₆H₅)₄ ^-、CH₃CH₂CH₂CH₂B(C₆H₅)₃ ^-Etc.), thiocyanate ions (SCN)^-) And nitrate ion (NO)₃ ^-) And the like.

These X' s^-Among these, MY is preferable from the viewpoint of cationic polymerization performance_a ^-、(Rf)_bPF_6-b ^-、R^x1 _cBY_4-c ^-、R^x1 _cGaY_4-c ^-And (R)^x2SO₂)₃C^-The anion represented by (A) is more preferably SbF₆ ^-、PF₆ ^-、(CF₃CF₂)₃PF₃ ^-、(C₆F₅)₄B^-、((CF₃)₂C₆H₃)₄B^-、(C₆F₅)₄Ga^-、((CF₃)₂C₆H₃)₄Ga^-And (CF)₃SO₂)₃C^-More preferably R^x1 _cBY_4-c ^-。

In the above formulae (a2), (a5) and (a6), examples of the aromatic hydrocarbon ring include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring [ for example, a condensed bicyclic hydrocarbon ring (for example, C such as naphthalene ring)_8-20Fused bicyclic hydrocarbon ring, preferably C_10-16Fused bicyclic hydrocarbon ring), fused tricyclic aromatic hydrocarbon ring (e.g.Anthracene ring, phenanthrene ring, etc.) or the like, and 2 to 4-ring aromatic hydrocarbon rings]And the like. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and 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 formulae (a1) to (a6), examples of the alkyl group include a straight-chain alkyl group having 1 to 18 carbon atoms (e.g., a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, and an n-octadecyl group), a branched-chain alkyl group having 3 to 18 carbon atoms (e.g., an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, and an isooctadecyl group), and a cycloalkyl group having 3 to 18 carbon atoms (e.g., a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 4-decylcyclohexyl group). 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 or an alkyl group substituted with a halogen atom. Examples of the alkyl group substituted with a halogen atom include a group (monofluoromethyl group, difluoromethyl group, trifluoromethyl group, etc.) obtained by substituting at least 1 hydrogen atom in the above-mentioned straight-chain alkyl group, branched-chain alkyl group, or cycloalkyl group with a halogen atom. In the alkyl group which may be substituted by halogen atoms, for R¹、R²、R⁹Or R¹⁰Trifluoromethyl is particularly preferred, for R⁴、R⁶、R¹¹Or R¹²In particular, methyl is preferable.

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

In the above formulas (a2) to (a6), examples of the alkyl group in the alkylcarbonyl group include the above straight-chain alkyl group having 1 to 18 carbon atoms, branched-chain alkyl group having 3 to 18 carbon atoms, or cycloalkyl group having 3 to 18 carbon atoms, and examples of the alkylcarbonyl group include straight-chain, branched-chain or cyclic alkylcarbonyl group having 2 to 18 carbon atoms (e.g., acetyl, propionyl, butyryl, 2-methylpropionyl, heptanoyl, 2-methylbutyryl, 3-methylbutyryl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl, and cyclohexanoyl).

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

In the formulae (a2) to (a6), examples of the alkoxycarbonyl group include a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an octyloxycarbonyl group, a tetradecyloxycarbonyl group, and an octadecyloxycarbonyl group).

In the formulae (a3) to (a6), examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 to 11 carbon atoms (e.g., a phenoxycarbonyl group and a naphthyloxycarbonyl group).

In the formulae (a3) to (a6), examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (e.g., phenylthiocarbonyl group and naphthyloxycarbonyl group).

In the formulae (a2) to (a6), examples of the acyloxy group include a linear or branched acyloxy group having 2 to 19 carbon atoms (e.g., an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an octylcarbonyloxy group, a tetradecylcarbonyloxy group, and an octadecylcarbonyloxy group).

In the formulae (a3) to (a6), examples of the arylthio group include arylthio groups having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl ] phenylthio, 4- [4- (phenylthio) phenoxy ] phenylthio, a, 4- [4- (phenylthio) phenyl ] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio, 4- (p-isopropylbenzoyl) phenylthio, and 4- (p-tert-butylbenzoyl) phenylthio), and the like).

In the formulae (a2) to (a6), examples of the alkylthio group include a linear or branched alkylthio group having 1 to 18 carbon atoms (e.g., a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, an isopentylthio group, a neopentylthio group, a tert-pentylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an isooctadecylthio group).

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

In the formula (a2), examples of the heterocyclic aliphatic hydrocarbon group include heterocyclic hydrocarbon groups having 2 to 20 (preferably 4 to 20) carbon atoms (e.g., pyrrolidinyl, tetrahydrofuryl, tetrahydrothienyl, piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.).

In the above formulas (a3) to (a6), examples of the heterocyclic hydrocarbon group include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (e.g., thienyl, furyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, indolyl, benzofuryl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromyl, dibenzothienyl, xanthenoyl, thioxanthonyl, dibenzofuranyl, etc.).

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

In the formulae (a2) to (a6), examples of the alkylsulfinyl group include a linear or branched sulfinyl group having 1 to 18 carbon atoms (e.g., methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl).

In the formulae (a3) to (a6), examples of the arylsulfinyl group include an arylsulfinyl group having 6 to 10 carbon atoms (e.g., a phenylsulfinyl group, a tolylsulfinyl group, and a naphthylsulfinyl group).

In the formulae (a2) to (a6), examples of the alkylsulfonyl group include a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (e.g., a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, a pentylsulfonyl group, an isopentylsulfonyl group, a neopentylsulfonyl group, a tert-pentylsulfonyl group, an octylsulfonyl group, and an octadecylsulfonyl group).

In the formulae (a3) to (a6), examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (e.g., phenylsulfonyl group, tolylsulfonyl group (tosyl group), and naphthylsulfonyl group).

In the above formulae (a2) to (a6), the hydroxy (poly) alkyleneoxy group is represented by HO (AO)_qA hydroxy (poly) alkyleneoxy group represented by (wherein AO independently represents an ethyleneoxy group and/or a propyleneoxy group, and q represents an integer of 1 to 5).

In the formulae (a2) to (a6), examples of the amino group which may be substituted include an amino group (-NH)₂) And a substituted amino group (A) having 1 to 15 carbon atomsAlkylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.), and the like.

In the above formulae (a3) and (a4), examples of the alkylene group include a linear or branched alkylene group having 1 to 18 carbon atoms (methylene, 1, 2-ethylene, 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, hexadecane-1, 16-diyl, etc.), etc.

The sulfonium salt (Q) can be synthesized, for example, according to the following synthesis 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 a nitro compound represented by the following formula (b3), and then the nitro compound is reduced in the presence of reduced iron to obtain an amine compound represented by the following formula (b 4). Reacting the amine compound with MaNO₂(in the formula, Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom) to obtain a diazo compound, and then the diazo compound, cuprous halide represented by CuX ' (in the formula, 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 a halide represented by the following formula (b 5). 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 compoundTo a sulfonium salt represented by the following formula (b 7). Further, the sulfonium salt is reacted with Mb⁺X”^-(in the formula, Mb⁺Representing metal cations, e.g. alkali metal cations such as potassium ions, X "^-Is represented by X^-Monovalent anions of (wherein halogen anions are excluded). ) The salt represented by (b) is reacted with a salt to perform salt exchange, whereby a sulfonium salt represented by the following formula (b8) can be obtained. In the following formulae (b2) to (b8), R is¹～R³And A¹The same as in the above formula (a 1).

< synthetic route >

Specific examples of the cation portion of the sulfonium salt (Q) represented by the above formula (a1) include the following. Specific examples of the anion portion of the sulfonium salt (Q) represented by the formula (a1) include those represented by the formula X^-Examples of the anion portion include conventionally known anion portions. The sulfonium salt (Q) represented by the above formula (a1) can be synthesized according to the above synthesis route, and by further salt exchange as necessary, the cation portion can be combined with a desired anion portion, particularly preferably with R^x1 _cBY_4-c ^-(in the formula, R^x1Represents 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. ) Combinations of anions as indicated.

The content of the sulfonium salt (Q) in the energy-sensitive composition of the present embodiment is preferably 0.001 to 20 mass%, more preferably 0.01 to 10 mass%, and still more preferably 0.1 to 8 mass%, based on the entire composition (excluding the solvent). When the content of the sulfonium salt (Q) is within the above range, the thermal weight stability tends to be good. In particular, when the viscosity of the energy-sensitive composition is adjusted to a low viscosity of, for example, 1000mPa · s (1000cP) or less as described later, the content of the sulfonium salt (Q) may be in the above range, 0.001 to 1% by mass, 0.005 to 0.1% by mass, or 0.008 to 0.05% by mass, relative to the entire composition (excluding the solvent).

[ 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).

As the onium salt, for example, X in the above formula (a1)^-A monovalent anion represented by the formula (a1) and X in the formula (a1)^-Sulfonium salts (also referred to as "sulfonium salts (Q')" in this specification) are preferred among onium salts formed from onium ions other than onium ions having different cations. As X^-The monovalent anion represented by R is preferably the above-mentioned anion^x1 _cBY_4-c ^-。

As having R^x1 _cBY_4-c ^-The monovalent anion sulfonium salt (Q ') is represented by, for example, a sulfonium salt represented by the following formula (a 1').

(in the formula, R¹、R²、R³、A¹、R^x1Y and c are as described above. )

Specific examples of the cation portion of the sulfonium salt (Q ') represented by the above formula (a 1') include the following.

The sulfonium salt (Q') may be represented by the above formula (a1) (wherein R is¹And R²Independently represents a group represented by the following formula (a 2'). ) Sulfonium salts are shown.

(in the formula, ring Z¹And m1 is as above^4’Represents an aryl group. )

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

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

(solvent)

In order to facilitate dissolution of the sulfonium salt (Q) in the cationically polymerizable compound, the sulfonium salt (Q) may be dissolved in advance in a solvent (S) that does not interfere with cationic polymerization.

Examples of the solvent include carbonates (1, 2-propylene carbonate, ethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.); esters (linear alkyl esters such as ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl valerate, ethyl valerate, methyl hexanoate, ethyl hexanoate, methyl heptanoate, and ethyl heptanoate; cyclic alkyl esters such as cyclopentyl acetate, cyclohexyl acetate, cyclooctyl acetate, methylcyclohexyl acetate, ethylcyclohexyl acetate, propylcyclohexyl acetate, isopropylcyclohexyl acetate, butylcyclohexyl acetate, isobutylcyclohexyl acetate, sec-butylcyclohexyl acetate, tert-butylcyclohexyl acetate, and pentylcyclohexyl acetate; cyclic alkyl esters such as ethyl lactate, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, delta-valerolactone, and epsilon-caprolactone); 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 monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.), and the like, and may be used alone or in combination of 2 or more.

In addition, conventionally known ketone solvents, alcohol solvents, amide solvents, and hydrocarbon solvents can be used. In addition, solvents known as protic solvents and/or basic solvents may also be used.

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

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

When a solvent is used, the proportion of the solvent used is, for example, preferably 1 to 99% by mass, and more preferably 10 to 95% by mass, based on 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 the present specification, the alkali-soluble resin means the following resin: a resin film having a film thickness of 1 μm was formed on a substrate using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass%, and the resin having a film thickness of 0.01 μm or more was dissolved when immersed in a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute.

Examples of the alkali-soluble resin include alkali-soluble resins (a1) obtained by reacting (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof with a reactant of an epoxy compound having 2 glycidyl ether groups derived from bisphenols and a monocarboxylic acid having an unsaturated group; having carboxyl groups, phenolic hydroxyl groups, or sulfonic acid groups (-SO)₃H) And the like alkali-soluble groups (a 2). In the present specification, the alkali-soluble resin (a2) preferably represents an alkali-soluble resin other than the alkali-soluble resin (a 1). These alkali-soluble resins are also preferable when the resulting cured product is desired to have heat resistance.

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.

As the alkali-soluble resin (a2), there is no particular limitation, and 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 further reacting a reactant of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

Among them, a resin represented by the following formula (f-1) is preferable. The resin represented by the formula (f-1) is preferably high in photocurability.

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

In the above general formula (f-2), R^f1Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R^f2Each independently represents a hydrogen atom or a methyl group, W^fRepresents a single bond or a group represented by the following formula (f-3).

In the above general formula (f-1), Y^fThe residue is obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic Anhydride include maleic Anhydride, succinic Anhydride, itaconic Anhydride, phthalic Anhydride, tetrahydrophthalic Anhydride, hexahydrophthalic Anhydride, methyl endomethylenetetrahydrophthalic Anhydride, Chlorendic Anhydride (Chlorendic Anhydride), methyl tetrahydrophthalic Anhydride, glutaric Anhydride, and the like.

In the above general formula (f-1), Z^fThe residue is obtained by removing 2 acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, and the like.

In the general formula (f-1), m represents an integer of 0 to 20.

In addition, as the alkali-soluble resin having an ethylenically unsaturated group, the following resins may also be used: polyester (meth) acrylates obtained by reacting (meth) acrylic acid with polyester prepolymers obtained by condensing polyhydric alcohols with monobasic acids or polybasic acids; a urethane (meth) acrylate obtained by reacting a polyol with a compound having 2 isocyanate groups and then reacting the resulting product with (meth) acrylic acid; epoxy (meth) acrylate resins obtained by reacting (meth) acrylic acid with epoxy resins (bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol or cresol Novolac type epoxy resins, Resol type epoxy resins, trisphenol methane type epoxy resins, polycarboxylic acid polyglycidyl esters, polyol polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, dihydroxybenzene type epoxy resins, and the like).

In the present specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" refers to both acrylate and methacrylate.

On the other hand, as the alkali-soluble resin having no ethylenically unsaturated group, a resin obtained by copolymerizing at least an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic group-containing unsaturated compound can be used.

Examples of the unsaturated carboxylic acid 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; anhydrides of these dicarboxylic acids; and so on. Among them, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, easiness of obtaining, and the like. These unsaturated carboxylic acids may be used alone or in combination of 2 or more.

Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, and 4-oxatetracyclo- [6.2.1.0 (meth) acrylate^2,7 0^3,5]Epoxy alkyl (meth) acrylates such as undecyl esters; epoxy alkyl esters of α -alkylacrylates such as α -ethylacrylate, α -n-propylacrylate, α -n-butylacrylate, and 6, 7-epoxyheptyl α -ethylacrylate; ortho vinylbenzyl glycidyl etherGlycidyl ethers such as m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; and so on. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferable from the viewpoint of copolymerization reactivity, strength of the cured resin, and the like. These epoxy group-containing unsaturated compounds may be used alone or in combination of 2 or more.

The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulae.

In the above formula, R^a3Represents a hydrogen atom or a methyl group, R^a4Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R^a5Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R^a4The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a1, 4-butylene group, an ethylethylene group, a1, 5-pentylene group, or a1, 6-hexylene group. As R^a5For example, methyl and ethyl are preferable.

The proportion of the structural unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, more preferably 5 to 25% by mass. The proportion of the structural unit derived from the epoxy group-containing unsaturated compound is preferably 71 to 95% by mass, more preferably 75 to 90% by mass. The proportion of the structural unit derived from the alicyclic group-containing unsaturated compound is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 15% by mass. By setting the amount to the above range, not only the alkali solubility of the obtained resin can be appropriate, but also the obtained cured product can have sufficient heat resistance.

The weight average molecular weight of the alkali-soluble resin is preferably 1000-40000, and more preferably 2000-30000. By setting the amount to the above range, the obtained cured product can have sufficient heat resistance.

The carboxyl group-containing resin in the alkali-soluble resin (a2) may be a silicon-containing resin, and examples thereof include siloxane resins containing the following structural units.

The silicone resin may contain a structural unit represented by the following formula (A2-1).

In the formula (A2-1), R^r1Is an organic group having at least 1 carboxyl group in its structure. The carboxyl group is preferably bonded to the Si atom via a linking group, and the linking group is, for example, a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group, an arylene group, or a divalent group obtained by combining these groups.

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^r1Examples include, but are not limited to, the following. In the following formula, R is bonded to Si in formula (A2-1)^r1The end of the chemical bond of (1).

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

The weight average molecular weight of the silicon-containing resin is, for example, 300 to 100000, and more preferably 500 to 70000.

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 20% by mass or less, and further preferably 15% by mass or less with respect to the entire energy-sensitive composition (excluding the solvent), and when the content is within the above range, the lower limit of the content may be more than 0% by mass, and may be, for example, 3% by mass or more and 5% by mass or more. By setting the amount to the above range, the obtained cured product can have sufficient heat resistance.

(surfactant)

The energy-sensitive composition according to the present embodiment may contain a surfactant, if necessary. Examples of the surfactant include a fluorine-based surfactant and a polysiloxane-based surfactant.

(Metal oxide particles)

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

The energy-sensitive composition according to the present embodiment may contain known additives (e.g., radical photopolymerization initiator, sensitizer, pigment, dispersant, filler, antistatic agent, flame retardant, defoaming agent, flow control agent, light stabilizer, antioxidant, adhesion imparting agent, ion trapping agent, coloring inhibitor, solvent, non-reactive resin, and radical polymerizable compound) as needed.

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

[ Properties ]

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

As described above, it is presumed that the sulfonium salt (Q) is contained, whereby the concentration of protons is increased in the system containing the compound component (P) and the sulfonium salt (Q), so that the stepwise polymerization in the compound component (P) continues and the polymerization is promoted. Thus, the energy-sensitive composition according to the present embodiment preferably has a weight loss rate as low as 10% or less even when the temperature is raised to 230 ℃.

The energy-sensitive composition according to the present embodiment is preferably used for a sealing material for an organic EL display device or a curable composition for a wafer-level lens. The energy-sensitive composition according to the present embodiment exhibits not only good curability (particularly, photocurability), but also excellent weight stability even when exposed to high temperatures, and can maintain quality for a long period of time, and therefore is preferably used for sealing materials for organic EL display elements or wafer level lenses. The method of using the energy-sensitive composition according to the present embodiment in a sealing material for an organic EL display element, a curable composition for a wafer-level lens, a composition for 3D printing, or a composition for inkjet printing is also one aspect of the present invention.

In addition, the energy-sensitive composition according to the present embodiment can form a hard coat layer, for example, by: the composition is prepared into a coating solution, and the coating solution is applied to an object to be coated such as a polyimide film by a coating apparatus such as a spin coater, a dip coater, a bar coater, or a slit coater, and then cured. Even if the coating liquid is a thin film having a film thickness of, for example, 10mm or less, preferably 100 μm or less, for example, 50 μm or less, 30 μm or less, 20 μm or less, and further 15 μm or less, the degree of deformation such as curling of the coating object due to curing of the coating liquid or the hard coat layer can be suppressed. The film thickness of the coating object may be, for example, 10 μm or more.

In addition, in general, a low molecular weight compound (P1), for example, an epoxy monomer, is used in order to reduce the viscosity of the composition, but the heat resistance is more likely to be reduced and the generation of outgas is more likely to occur as the low molecular weight compound is blended. However, it was confirmed that the energy-sensitive composition according to the present embodiment contains the sulfonium salt (Q), and thus has excellent heat resistance even when the viscosity is low, and can reduce the generation of outgas. Surprisingly, even if the addition amount of the sulfonium salt (Q) is smaller than that of a general cationic polymerization initiator or the like, the effects of reducing the viscosity of the energy-sensitive composition, improving the heat resistance, and reducing the generation of outgas can be obtained, which has been confirmed by experiments described later.

The energy-sensitive composition according to the present embodiment is not only low in viscosity but also excellent in heat resistance and can reduce the generation of outgas, and therefore, can be preferably used also in inkjet printing requiring a low-viscosity ink. The inkjet ink can be preferably used for a display device such as a touch panel when applied to a large area from the viewpoint of productivity or the like, and can be preferably used for applications such as a sealing material for an organic EL display element. Preferably, the ink jet printing composition containing the energy-sensitive composition according to the present embodiment has a viscosity of 1000mPa · s (1000cP) or less at 25 ℃ and a shear rate of 20(l/s), and the content of the sulfonium salt (Q) is 0.001 to 1% by mass based on the entire composition (excluding the solvent).

< method for producing wafer level lens >

Wafer-level lenses can be made by molding (e.g., casting, injection molding) the energy-sensitive compositions described above. The wafer-level lens mold may be made of any of metal, glass, and plastic.

The cast molding method includes a simultaneous molding method and a single-piece molding method, and includes the following steps.

(Simultaneous Molding method)

Step 1: the 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 predetermined direction, and is cured by heating and/or light irradiation

And a step 2: removing the wafer level lens mold, and annealing to obtain a cured product having a shape formed by connecting a plurality of wafer level lenses

Step 3: cutting a cured product having a shape obtained by connecting a plurality of wafer level lenses into individual pieces to obtain wafer level lenses

(Single sheet Molding method)

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

And a step 2: unloading the wafer level lens mould, and carrying out annealing treatment to obtain the wafer level lens

(injection Molding method)

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

And a step 2: unloading the wafer level lens mould, carrying out annealing treatment, and cutting off burrs to obtain the wafer level lens

The heat treatment in the above step may be performed at a temperature of about 100 to 200 ℃ (preferably 120 to 160 ℃), for example, for a short time (e.g., about 1 to 10 minutes, preferably 1 to 3 minutes). As the light source for the light irradiation, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam, a laser, or the like can be used. After the light irradiation, for example, the curing reaction may be further performed by performing a heat treatment at a temperature of about 50 to 180 ℃.

The internal strain may be removed by an annealing process. The annealing treatment is preferably performed at a temperature of 100 to 200 ℃ for about 30 minutes to 1 hour, for example.

In the simultaneous molding method, the energy-sensitive composition preferably has a low viscosity and excellent flowability in view of excellent filling properties into a mold. The energy-sensitive composition usable in the simultaneous molding method has a viscosity of, for example, about 0.05 to 5 pas, preferably 0.1 to 2 pas, at 25 ℃ and at a shear rate of 20 (1/s). The energy-sensitive composition having the viscosity within the above range is excellent in fluidity, hardly causes bubbles to remain, and can be filled into a mold while suppressing an increase in injection pressure. Namely, the coating property and the filling property are excellent, and the workability is excellent throughout the molding operation.

A cured product of the energy-sensitive composition has excellent heat resistance even in a high-temperature environment of about 100 to 250 ℃. Therefore, even if the annealing treatment is performed after the lens is removed from the mold, a wafer level lens having excellent lens center position accuracy can be efficiently manufactured. Therefore, in step 3 of the 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 positions of the cutting lines are determined based on the uppermost cured product, and the cured products are cut, whereby the wafer level lenses can be separated without being damaged, and the wafer level lenses or the laminated body thereof can be manufactured at low cost and efficiently.

The wafer-level lens obtained from the energy-sensitive composition of the present embodiment can be prevented from yellowing even when exposed to a high-temperature environment for a long period of time, and can maintain high transparency. Therefore, for example, the lens can be suitably used as a photographing lens, a spectacle lens, a beam converging lens, a light diffusing lens, and the like of a camera (a camera such as an in-vehicle camera, a digital camera, a camera for a PC, a camera for a mobile phone, and a monitoring camera, particularly, a wafer-level camera), and can be particularly suitably used as a wafer-level lens for an in-vehicle camera requiring heat resistance.

Further, since the wafer-level lens obtained from the energy-sensitive composition of the present embodiment is excellent in heat resistance, solder mounting can be performed by reflow (reflow) when the wafer-level lens is mounted on a circuit board. 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 surface mounting of other electronic components, and a product can be manufactured very efficiently.

< cured product >

The cured product according to the present invention is a cured product obtained by curing an energy-sensitive composition containing at least 1 compound component (P) selected from the group consisting of the compound (P1), the compound (P2), and the compound (Px), and a sulfonium salt (Q). As described above, the cured product according to the present invention has excellent weight stability against heat. This is presumably because, by containing the sulfonium salt (Q) in the energy-sensitive composition, the concentration of protons is increased in the system containing the compound component (P) and the sulfonium salt (Q), and therefore, the stepwise polymerization of the compound component (P) continues, the polymerization is promoted, and the amount of the monomer decomposed by heat is small. The cured product is suitable for use 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 use in flexible devices.

In addition, the cured product of the present embodiment can be prepared as a cured product having a high refractive index by selecting the components of the energy-sensitive composition. From the viewpoint of obtaining a cured product having a high refractive index, preferable examples of the component include metal oxide particles and an epoxy group-containing fluorene compound as the compound (P1), and these may be used alone or in combination of 2 or more, and from the viewpoint of increasing the refractive index, the metal oxide particles are preferably used. The refractive index of the cured product obtained can be, for example, a high refractive index of 1.7 or more as the refractive index at a wavelength of 633nm, and when the metal oxide particles are used, the high refractive index can be 1.75 or more, and further 1.8 or more. The upper limit of the refractive index at the wavelength of 633nm is not particularly limited, and is, for example, 1.9 or less, 1.85 or less, or the like.

< method for producing cured product >

The method for producing a cured product according to the present invention comprises: and (b) a step of polymerizing and/or crosslinking an energy-sensitive composition containing at least 1 compound component (P) selected from the group consisting of the compound (P1), the compound (P2), and the compound (Px), and a sulfonium salt (Q). Energy-sensitive compositions are energy-sensitive and therefore can be cured by polymerization and/or crosslinking by the application of active energy. The active energy to be imparted may be any energy that can induce the decomposition of the sulfonium salt (Q), and examples thereof include heat, visible light, ultraviolet light, electron beam, and X-ray.

< ink jet ink >

The energy-sensitive composition according to the present embodiment can be preferably used as an inkjet ink when the viscosity is adjusted to a low value, for example, 5000mPa · s (5000cP) or less, preferably 100mPa · s (100cP) or less as measured at 25 ℃ with an E-type viscometer. When the viscosity of the energy-sensitive composition of the present embodiment used as an inkjet ink is within the above range, it may be, for example, 1mPa · s (1cP) or more, or 10mPa · s (10cP) or more. For the energy-sensitive composition used as an inkjet ink, the sulfonium salt (Q) content is preferably an amount at which the viscosity is adjusted to the above-mentioned low viscosity.

Examples

The present invention will be described in further detail below by way of examples of the present invention, but the present invention is not limited to the following examples.

< examples 1 to 3 and comparative examples 1 to 9 >)

In examples 1 to 3 and comparative examples 1 to 9, a compound (P1) shown below and a sulfonium salt and the like were mixed at a mixing ratio shown in table 1 to prepare a mixed solution. In table 1, the unit of the mixing ratio is part by mass.

< materials >

[ 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 ]

A sulfonium salt represented by the following formula (Q1)

A sulfonium salt represented by the following formula (z1)

A sulfone compound represented by the following formula (z2)

Triphenylsulfonium tetrakis (pentafluorophenyl) borate (triphenylsulfonium borate)

[ evaluation 1]

The mixed liquids obtained in examples 1 to 3 and comparative examples 1 to 9 were heated from 20 ℃ to 250 ℃ in an air stream at a heating rate of 10 ℃ per minute by a differential thermal/thermogravimetry apparatus (TG/DTA-6200, manufactured by Seiko Instruments) to obtain a TG/DSC curve. In the obtained TG curve, the weight reduction rate of weight reduction from the peak was calculated. The results are shown in table 1. The weight loss rate was evaluated according to the following criteria.

Good: the weight loss rate is less than 10%

And (delta): the weight reduction rate is higher than 10% and lower than 40%

X: the weight reduction rate is more than 40%

Fig. 1 to 4 show TG/DSC curves obtained in example 3 and comparative examples 7, 8, and 9. FIG. 5 shows a TG/DSC curve of the compound represented by the formula (P1-2a) (P1) alone at elevated temperatures under the same conditions as a reference example.

[ Table 1]

[ examination ]

As shown in table 1 and the TG curves shown in fig. 1 to 4, in examples 1 to 3 using the compound (P1) and the sulfonium salt (Q), the weight loss rate was 10% or less, and the heat resistance was high as compared with comparative examples 1 to 9. In the DSC curve of example 3 shown in FIG. 1, gentle peaks were observed at 110.6 ℃ and 222.3 ℃. It is presumed that this is a peak showing the progress of the ring opening of the epoxy group of the compound (P1) and the polymerization proceeds from a low temperature around 110 ℃. In contrast, in the DSC curves of the comparative examples shown in fig. 2 to 4, sharp peaks were observed. It is estimated that this is a peak showing decomposition of the sulfonium salt represented by the formula (z1) or the sulfone compound represented by the formula (z2), and thus the weight reduction rate is estimated to be increased. For example, as shown in FIG. 2, in comparative example 7, the weight was reduced by about 65% at around 170 ℃. As shown in FIG. 3, in comparative example 8, the weight was reduced by about 30% at around 150 ℃. As shown in FIG. 4, in comparative example 9, the weight was reduced by about 50% at around 170 ℃. From the results shown in FIG. 5, it was confirmed that in the case of the compound represented by the formula (P1-2a) (P1) alone, a sharp peak was observed at 50 ℃ or lower in a DSC curve, and that the compound represented by the formula (P1-2a) (P1) began to decompose at 50 ℃ or lower, and the weight decreased from around 100 ℃ to around 165 ℃ by about 80%.

[ evaluation 2]

The compound obtained by changing the mass ratio of the mixed solution obtained in example 1 to the formula (P1-1a) was applied onto a glass substrate by a spin coater: sulfonium salt of formula (Q1) ═ 99: 1 to obtain a coating film having a thickness of 20 μm, using HMW-532D (manufactured by ORC) at 1000mJ/cm²The film was irradiated with ghi line, and then the transmittance at a wavelength of 400nm of the film was measured using MCPD-3000 (Otsuka electronic Co., Ltd.). The transmittance was 99.6%.

[ examination ]

From these results, it was found that in examples 6 to 9 described later, the transmittance of a hard coat layer formed by applying the same coating liquid containing the compound (P1) and the sulfonium salt (Q) as in example 1 to a polyimide film was not adversely affected.

< examples 4 and 5>

An alicyclic epoxy compound represented by the formula (P1-1a) or an oxetane compound represented by the formula (P1-7a), which is the compound (P1), bis-1-ethyl-3-oxetanyl ether and a sulfonium salt represented by the formula (Q1) were mixed at a mixing ratio shown in Table 2, and the obtained mixture was cured by an ultraviolet curing machine at 100mJ/cm²After exposure to light (broad band), in example 4, post-baking was performed at 150 ℃ for 2 minutes, and in example 5, curing was attempted under curing conditions in which post-baking was not performed, and as a result, both of the mixtures of examples 4 and 5 were cured without causing stickiness. In table 2, the unit of the mixing ratio is part by mass.

[ Table 2]

[ examination ]

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), the sulfonium salt (Q) was incorporated to exhibit good curability. From the results of example 5, it was confirmed that even when 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, polyimide films 1 to 4 made of polyimide were prepared as follows.

[ method for producing polyimide film 1]

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

0.03g (0.03 wt%) of amorphous silica particles having OH groups bonded to the surface thereof was put into N, N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, and subjected to ultrasonic treatment until the solvent became transparent, and then 100g of the polyimide as a solid component powder was dissolved in 670g 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 ℃ for 30 minutes, and then the film was peeled off from the stainless steel plate and fixed to a frame with a needle. And (3) putting the frame fixed with the film into a vacuum oven, slowly heating the frame from 100 ℃ to 300 ℃ in 2 hours, then slowly cooling the frame, and separating the frame to obtain the polyimide film. Then, as a final heat treatment step, heat treatment was further performed at 300 ℃ for 30 minutes. The polyimide film 1 thus obtained had a film thickness of 50 μm, a total light transmittance of 88%, and a Yellowness Index (YI) of 2.5.

[ method for producing polyimide film 2]

On one surface of the polyimide film 1, a solution obtained by dissolving 2 wt% of polysilazane (MOPS-1800, manufactured by Az Materials Co.) having a weight average molecular weight of 2000g/mol in dibutyl ether (DBE) was applied by wire bar coating, and then dried at a temperature of about 80 ℃ to form a polysilazane film having a thickness of 300 nm. Then, after leaving at room temperature for about 5 minutes, the polysilazane film was thermally cured at a temperature of about 250 ℃ to form a silicon oxide layer, thereby producing a polyimide film 2 having a structure of a colorless transparent polyimide film/silicon oxide layer. The polyimide film 2 thus obtained had a film thickness of 50 μm, a total light transmittance of 92%, and a Yellowness Index (YI) of 1.0.

[ method for producing polyimide film 3]

To a 3L separable flask equipped with a stir bar having an oil bath, 1000g of N-methylpyrrolidone (NMP) was added while introducing nitrogen gas, 232.4g of 3,3- (diaminodiphenyl) sulfone (referred to as diamine 1) was added with stirring, and 218.12g of pyromellitic dianhydride was then added and stirred at room temperature for 30 minutes. After the temperature was raised to 50 ℃ and the mixture was stirred for 12 hours, 105.6g 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 298g of NMP, and the solution was added dropwise thereto using a dropping funnel. After the temperature was raised to 80 ℃ and stirring was carried out for 1 hour, the oil bath was taken out and the temperature was returned to room temperature, whereby a transparent NMP solution of polyamic acid (hereinafter, also referred to as varnish) was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid was 84000.

The varnish was applied to an alkali-free glass substrate (thickness: 0.7mm) by a bar coater, homogenized (leveling) at room temperature for 5 to 10 minutes, heated at 140 ℃ for 60 minutes in a vertical curing oven (model name VF-2000B, manufactured by Koyolindberg Co., Ltd.), further heated at 350 ℃ for 60 minutes in a nitrogen atmosphere (oxygen concentration: 100ppm), and allowed to stand at room temperature for 24 hours to peel off the resin film from the glass, thereby producing a polyimide film. The thickness of the obtained polyimide film 3 was 20 μm, the total light transmittance was 88%, and the Yellowness (YI) was 7.0.

[ method for producing polyimide film 4]

(Synthesis of imidazole Compound (d))

First, 30g of a cinnamic acid derivative of the following formula was dissolved in 200g of methanol, and then 7g of potassium hydroxide was added to the methanol. Next, the methanol solution was stirred at 40 ℃. The methanol was distilled off and the residue was suspended in 200g of water. 200g of tetrahydrofuran was mixed with the obtained suspension, followed by stirring, and the aqueous phase was separated. Under ice-cooling, 4g of hydrochloric acid was added thereto, followed by stirring, and then 100g of ethyl acetate was mixed and stirred. Standing the mixed solution, and then separating an oil phase. Crystals of the objective substance were precipitated from the oil phase, and the precipitates were collected to obtain an imidazole compound (d) having the following structure.

(preparation of tetracarboxylic dianhydride)

A tetracarboxylic dianhydride represented by the following formula (norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride) was prepared according to the method described in synthesis example 1, and example 2 of international publication No. 2011/099518.

(preparation of Polyamic acid)

First, a 30ml three-necked flask was heated with a heat gun (heat gun) and sufficiently dried. Then, the atmosphere in the three-necked flask was replaced with nitrogen gas to make the atmosphere in the three-necked flask nitrogen gas. To a three-necked flask, 0.2045g of 4,4 ' -diaminobenzanilide (0.90 mmol: DABAN, manufactured by NIPPON PURE MEDICINE) was added, followed by 3.12g of N, N, N ', N ' -Tetramethylurea (TMU). The contents of the three-necked flask were stirred to obtain a slurry solution in which an aromatic Diamine (DABAN) was dispersed in TMU.

Next, 0.3459g (0.90mmol) of tetracarboxylic dianhydride represented by the above formula was added to the three-necked flask, and then the content of the flask was stirred at room temperature (25 ℃) for 12 hours under a nitrogen atmosphere to obtain a reaction solution. The polyamic acid was formed as described above to be 15 mass% (TMU solvent: 85 parts by mass) in the reaction solution.

(step of adding imidazole Compound (d))

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

(preparation of polyimide film)

The polyimide precursor composition obtained as described above was spin-coated on a glass substrate (large glass slide, trade name "S9213" manufactured by Sonlang Nitri industries, Ltd., length: 76mm, width 52mm, thickness 1.3mm) so that the thickness of the coating film after heat curing became 13 μm, to form a coating film. Next, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ℃ and left standing for 2 hours, and the solvent was evaporated from the coating film to remove the solvent.

After the solvent was removed, the glass substrate on which the coating film was formed was put into an inert oven (inert oven) through which nitrogen gas was passed at a flow rate of 3L/min. The glass substrate was allowed to stand in an inert oven under a nitrogen atmosphere (oxygen concentration: 100ppm) at a temperature of 25 ℃ for 0.5 hour, then heated at a temperature of 135 ℃ for 0.5 hour, and further heated at a temperature of 300 ℃ (final heating temperature) for 1 hour to cure the coating film, thereby obtaining a polyimide-coated glass having a thin film (polyimide film) made of polyimide coated on the glass substrate.

The polyimide-coated glass thus obtained was immersed in hot water at 90 ℃ to peel the polyimide film from the glass substrate, thereby obtaining a polyimide film 4 (a film having a length of 76mm, a width of 52mm, and a thickness of 13 μm).

In order to identify the molecular structure of the resin as a material of the obtained polyimide film, an IR spectrum of a sample of the polyimide film was measured using an IR meter (trade name: FT/IR-4100, manufactured by Nippon spectral Co., Ltd.). As a result of the measurement, it was found that the IR spectrum of the resin as the material of the polyimide film was 1696.2cm^-1Stretching vibration of imide carbonyl group C ═ O was observed. From the molecular structure identified based on the results and the like, it was confirmed that the obtained polyimide film was indeed a film made of a polyimide resin.

The polyimide film 4 thus obtained had a total light transmittance of 88% and a Yellowness Index (YI) of 3.5.

The total light transmittance value (unit:%) and the Yellowness (YI) of the film were determined by measurement in accordance with JIS K7361-1 (published 1997) using a haze meter NDH-5000, a trade name of Nippon Denshoku industries, Ltd.

[ preparation of coating solution ]

The ratio of 99: 1 mass ratio of the compound (P1) represented by the formula (P1-1a) and the sulfonium salt represented by the formula (Q1) were dissolved in a solvent (propylene glycol monomethyl ether acetate (PGMEA)), and a coating solution 1 having a solvent ratio of 80 mass% was prepared.

[ preparation of coating solution for comparison ]

The ratio of 99: 1 (mass ratio) in a solvent (PGMEA), a photosensitive composition containing an acrylic monomer (dipentaerythritol hexaacrylate) and a polymerization initiator (1-hydroxycyclohexylphenylketone) was dissolved, and a coating solution 2 for comparison was prepared in which the ratio of the solvent was 80 mass%.

[ evaluation 3]

The coating solution 1 and the comparative coating solution 2 were applied to one surface of each of the polyimide films 1 to 4 bonded to the wafer by a spin coater, and then dried at 80 ℃ to obtain a coating film having a thickness of 4 μm. Then, an ultraviolet curing machine having a wavelength of 365nm was used at 100mJ/cm²The coating layer was irradiated with light to obtain each polyimide film having a hard coat layer (cured film) formed on one surface thereof. Each of the polyimide films obtained was peeled from the wafer, and the appearance was visually observed.

[ results and examination ]

In the polyimide films 1 to 4 (examples 6 to 9) in which the hard coat layer using the coating liquid 1 was formed according to the present example, the transparency of the film was not reduced, and the degree of curling of the film due to curing of the coating liquid or the hard coat layer was small, and it was confirmed that the curing shrinkage was small.

In contrast, the polyimide films 1 to 4 (comparative examples 10 to 13) on which the hard coat layer using the comparative coating liquid 2 was formed were yellow to some extent, and the curl due to curing of the coating liquid or the hard coat layer was large. It is considered that the hard coat layer formed from the coating liquid 1 according to the present example has a smaller cure shrinkage than the hard coat layer formed from the coating liquid 2, and it was confirmed that the degree of deformation of the polyimide film to be coated was suppressed.

[ evaluation 4]

The surface resistance values of the hard coat layers formed on the polyimide films 1 to 4 in evaluation 3 were measured at a measurement voltage of 1,000V using Hiresta MCP-HT450 (manufactured by Mitsubishi Analyticch) with a probe UR-100. Surface resistance values higher than 1 × 10¹⁵Ω。

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

< examples 10 to 14 and comparative examples 14 to 15 >)

In examples 10 to 14 and comparative examples 14 to 15, the compounds (P1-1a), (P1-2a), sulfonium salt (Q1), the compounds (P1-6d) shown below, sulfonium salt and the like (z3) used in examples 1 and 3 were mixed at the mixing ratios shown in Table 1 to prepare mixed solutions. In table 3, the unit of the blending ratio is parts by mass.

< materials >

[ 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 at 25 ℃ and 1 to 100rpm using an E-type viscometer. The results are shown in Table 3. The viscosity of the compound (P1-1a) was about 60 mPas (60cP), the viscosity of the compound (P1-2a) was about 20 mPas (20cP), and the viscosity of the compound (P1-6d) was about 200 mPas (200 cP).

0.3g of the mixed solution obtained in examples 10 to 14 and comparative examples 14 to 15 was precisely weighed into a glass vial (glass visual), sealed, and irradiated with an ultraviolet irradiation device (HMW-532D, ORC Co.) at 1500mJ/cm²The exposure was carried out at the exposure of (1) and post-baking was carried out at 100 ℃ for 15 minutes and 85 ℃ for 100 hours to prepare each sample.

Each of the samples was set in a headspace sampler (turbo matrix ATD, manufactured by PerkinElmer), heated at 100 ℃ for 30 minutes, and then the exhaust gas was measured by a gas chromatograph mass spectrometer (Clarus580, manufactured by PerkinElmer). The results are shown in Table 3. In the table, the relative values obtained when the measured value (area%) of comparative example 14 was taken as 100 are shown.

[ Table 3]

[ examination ]

As shown in table 3, it was confirmed that example 10 using the compound (P1-1a) and the sulfonium salt (Q1) had a viscosity comparable to that of comparative example 14 not using the sulfonium salt (Q1) and also had a small amount of outgas. Similarly, it was confirmed that example 14 using the compound (P1-1a), the compound (P1-6d) and the sulfonium salt (Q1) had a viscosity comparable to that of comparative example 15 not using the sulfonium salt (Q1) and also had a small amount of outgas.

Further, from the results of examples 10 and 11, it was confirmed that even if the amount of the sulfonium salt (Q1) was extremely small, the viscosity of the mixed solution (energy-sensitive composition) was reduced and the exhaust gas was reduced. Similarly, from the results of examples 12 and 13, it was confirmed that even if the amount of the sulfonium salt (Q1) was extremely small, the viscosity of the mixed solution (energy-sensitive composition) was reduced and the exhaust gas was reduced.

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) was the same, the viscosity of the mixed solution (energy-sensitive composition) was reduced and the exhaust gas was reduced when the compound (P1-1a) and the compound (P1-2a) were used in combination as the compound component (P) or the compound (P1), as compared with when the compound (P1-1a) was used alone as the compound component (P) or the compound (P1). As a result, it is sometimes preferable to use the alicyclic epoxy compound represented by the above formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) in combination as the compound component (P) or the compound (P1).

< examples 15 to 24 >)

[ preparation of energy-sensitive composition having high refractive index ]

In examples 15 to 24, the following polymerizable and/or crosslinkable compound (P1) based on the cationic and/or acid catalytic system and sulfonium salt were mixed at the mixing ratio shown in table 4 to prepare an energy-sensitive composition. In table 4, the unit of the blending ratio is part by mass, and the blending ratio of the solvent is a mass ratio. In example 23, the cerium oxide (average particle diameter: 50nm) was further added in an amount of 10 parts by mass based on 100 parts by mass of the total of the (P1) component and (Q1) in example 15. In example 24, the titanium oxide was further added in an amount of 100 parts by mass (average particle diameter: 5 to 10nm) based on 100 parts by mass of the total of the components (P1) and (Q1) in example 15. In examples 15 to 23, the solvent amount was adjusted so that the concentration of the components other than the solvent became 20 mass%. In example 24, the amount of the solvent was adjusted so that the concentration of the components other than the solvent became 10 mass%.

[ Table 4]

< materials >

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

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

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

[ alkali-soluble resin ]

Preparation of alkali-soluble resin (A1a)

First, a 500ml four-necked flask was charged with 0.34mol of 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, 0.68mol of acrylic acid, 139.0g of propylene glycol monomethyl ether acetate and 2.15g of tetraethylammonium bromide (TEAB), and the mixture was stirred and reacted at 100 to 105 ℃ for 20 hours. Then, 0.12mol of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 0.27mol of 1,2,3, 6-tetrahydrophthalic anhydride were charged into the flask, and the mixture was stirred and reacted under heating at 120 to 125 ℃ for 8 hours. Further, 0.28mol of glycidyl methacrylate was charged and stirred at 100 to 105 ℃ for 8 hours to obtain an alkali-soluble resin (A1 a). The alkali-soluble resin (A1a) thus obtained had a solid content concentration of 57.0% by weight, an acid value (in terms of solid content) of 82mgKOH/g, and an Mw based on GPC analysis of 3500.

Preparation of alkali-soluble resin (A2a)

First, a 500mL four-necked flask was charged with 235g of bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110mg of tetramethylammonium chloride, 100mg of 2, 6-di-t-butyl-4-methylphenol, and 72.0g of acrylic acid, and dissolved by heating at 90 to 100 ℃ while blowing air at a rate of 25 mL/min. Then, the temperature was gradually increased while the solution was kept cloudy, and the solution was heated to 120 ℃ to be completely dissolved. At this time, the solution gradually became transparent and viscous, and the stirring was continued in this state. During this time, the acid value was measured, and stirring with heating was continued until the acid value was less than 1.0 mgKOH/g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature to obtain a colorless, transparent and solid bisphenol fluorene type epoxy acrylate represented by the following formula (f-4).

Then, to 307.0g of the bisphenol fluorene type epoxy acrylate obtained as described above, 600g of 3-methoxybutyl acetate was added and dissolved, and then 80.5g of benzophenone tetracarboxylic dianhydride and 1g of tetraethylammonium bromide were mixed, and the temperature was gradually increased to perform a reaction at 110 to 115 ℃ for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90 ℃ for 6 hours to obtain an alkali-soluble resin having a Cardo structure (A2 a). The disappearance of the acid anhydride group was confirmed by IR spectroscopy.

The alkali-soluble resin having a Cardo structure (A2a) corresponds to the compound represented by the above general formula (f-1).

[ additives ]

·(Add-1)

Polyether-modified polydimethylsiloxane (BYK 302, BYK Chemie Japan Co., Ltd.)

·(Add-2)

Oligomer having perfluoroalkyl group [ DIC Co., Ltd.; F-477 ]

[ solvent ]

Cyclohexylacetate (S1)

(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, prebaked at 100 ℃ for 120 seconds, and cured at 100mJ/cm using an ultraviolet curing machine²Exposure to light (broad band) was carried out, and then, post-baking treatment was carried out at 150 ℃ for 20 minutes (example 24 at 230 ℃ for 20 minutes). The cured films of examples 15 to 23 had a film thickness of 500nm, and example 24 had a film thickness of 50 nm. Each cured film has heat resistance. The refractive index at a wavelength of 633nm was measured for each cured film. 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 as metal oxide particles was added 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, and high refractive index (transparency) was achieved.

Regarding the heat resistance, the energy-sensitive compositions of examples 15 to 24 were applied to a glass substrate using a spin coater, prebaked at 100 ℃ for 120 seconds, and cured at 100mJ/cm using an ultraviolet curing machine²Exposure (broad band) with the exposure dose, and post-baking treatment at 230 ℃ for 20 minutes to obtain a cured film having a cured film thickness of about 50 nm. The heat resistance was confirmed by the film thickness change rate of 10% or less when the temperature of each cured film was further raised to 250 ℃.

Claims (8)

1. An energy-sensitive composition comprising:

at least 1 compound component (P) selected from the group consisting of

(Q) a sulfonium salt represented by the following formula (a1),

the group consisting of:

(P1) a polymerizable and/or crosslinkable compound based on a cationic and/or acid-catalytic system,

(P2) a compound whose solubility in a developer increases by the action of an acid, and

(Px) radically polymerizable or crosslinkable compound

The structure of the utility model is that the material,

in the formula (a1), R¹And R²Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (a2), R¹And R²May be bonded to each other and form a ring together with the sulfur atom in the formula R³Represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A¹Denotes S, O, or Se, X^-Represents a monovalent anion, wherein R¹And R²Not both alkyl groups which may be substituted by halogen atoms,

in formula (a2), ring Z¹Represents a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, R⁴Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a thienyl group, a thienylcarbonyl group, a furyl carbonyl group, a selenophenyl group, a selenophenylcarbonyl group, a heterocyclic aliphatic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, m1 represents an integer of 0 or more,

in the formula (a3), R⁵Represents an alkylene group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom represented by the following formula (a5), R⁶Represents an alkyl group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom, or a group represented by the following formula (a6)²Represents a single bond, S, O, a sulfinyl group, or a carbonyl group, n1 represents 0 or 1,

in the formula (a4), R⁷And R⁸Independently represents an alkylene group which may be substituted with a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom represented by the following formula (a5), R⁹And R¹⁰Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the formula (a2), R⁹And R¹⁰Can mutually communicateBonded and forming a ring together with the sulfur atom in the formula A³Represents a single bond, S, O, sulfinyl, or carbonyl, X^-As mentioned above, n2 represents 0 or 1, wherein R⁹And R¹⁰Not both alkyl groups which may be substituted by halogen atoms,

in formula (a5), ring Z²Represents an aromatic hydrocarbon ring, R¹¹Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, m2 represents an integer of 0 or more,

in formula (a6), ring Z³Represents an aromatic hydrocarbon ring, R¹²Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more.

2. An energy-sensitive composition comprising:

at least 1 compound component (P) selected from the group consisting of

(Q) a sulfonium salt represented by the following formula (a1),

the group consisting of:

(P1) a polymerizable and/or crosslinkable compound based on a cationic and/or acid-catalytic system,

(P2) a compound whose solubility in a developer increases by the action of an acid, and

(Px) radically polymerizable or crosslinkable compound

The structure of the utility model is that the material,

in the formula (a1), R¹And R²Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (a2), R¹And R²May be bonded to each other and form a ring together with the sulfur atom in the formula R³Represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A¹Denotes S, O, or Se, X^-Represents a monovalent anion, wherein R¹And R²Not both alkyl groups which may be substituted by halogen atoms,

in formula (a2), ring Z¹Represents an aromatic hydrocarbon ring, R⁴Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a thienyl group, a thienylcarbonyl group, a furyl carbonyl group, a selenophenyl group, a selenophenylcarbonyl group, a heterocyclic aliphatic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, m1 represents an integer of 0 or more,

in the formula (a3), R⁵Represents an alkylene group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom represented by the following formula (a5), R⁶Represents an alkyl group which may be substituted by a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom, or a group represented by the following formula (a6)²Represents a single bond, S, O, a sulfinyl group, or a carbonyl group, n1 represents 0 or 1,

in the formula (a4), R⁷And R⁸Independently represents an alkylene group which may be substituted with a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group or a halogen atom represented by the following formula (a5), R⁹And R¹⁰Independently represents an alkyl group which may be substituted with a halogen atom or a group represented by the formula (a2), R⁹And R¹⁰May be bonded to each other and form a ring together with the sulfur atom in the formula A³Represents a single bond, S, O, sulfinyl, or carbonyl, X^-As mentioned above, n2 represents 0 or 1, wherein R⁹And R¹⁰Not both alkyl groups which may be substituted by halogen atoms,

in formula (a5), ring Z²Represents an aromatic hydrocarbon ring, R¹¹Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, m2 represents an integer of 0 or more,

in formula (a6), ring Z³Represents a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, R¹²Represents an alkyl group which may be substituted by a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, an amino group which may be substituted, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more.

3. The energy-sensitive composition of claim 1 or 2, wherein the compound component (P) is the (P1) compound,

the compound (P1) is an epoxy compound having at least 1 group selected from the group consisting of an oxetanyl group, an oxetanyl group and an alicyclic epoxy group.

4. The energy-sensitive composition of claim 1 or 2, wherein in the sulfonium salt, the X^-The monovalent anion is represented by a boron-containing anion represented by the following general formula,

R^x1 _cBY_4-c ^-

in the formula, R^x1Represents 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.

5. The energy-sensitive composition according to claim 1 or 2, wherein a weight reduction rate of weight reduction from a peak value in Thermogravimetry (TG) of raising a temperature to 230 ℃ at a temperature raising rate of 10 ℃/min in an air stream 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 any one of claims 1 to 5.

8. A method for producing a cured product, the method comprising the step of polymerizing and/or crosslinking the energy-sensitive composition according to any one of claims 1 to 5.

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