KR102305725B1 - Energy-Sensitive Composition, Cured Product and Its Production Method - Google Patents

Abstract

The present invention provides an energy-sensitive composition having excellent thermogravimetric stability, and a cured product obtained by curing the same, and a method for producing the cured product. The present invention relates to (P1) a cationic and/or acid catalytically polymerizable and/or crosslinkable compound, (P2) a compound that increases its solubility in a developer under the action of an acid, and (Px) radical polymerizable or crosslinked compound There is provided an energy-sensitive composition comprising at least one compound component (P) selected from the group consisting of a compound of the nature (Q) and a sulfonium salt represented by the formula (a1).

Description

Energy-Sensitive Composition, Cured Product and Its Production Method {Energy-Sensitive Composition, Cured Product and Its Production Method}

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

Conventionally, it is proposed to contain an epoxy compound in the encapsulant for organic EL display elements or the energy-sensitive composition for wafer-level lenses. For example, in Patent Document 1, an energy-sensitive resin capable of suppressing the generation of outgas, which is a factor of deterioration of an organic EL display element, has an epoxy group or an oxetanyl group, and an ether bond and an ester other than the epoxy group or oxetanyl group. An energy-sensitive resin composition that does not contain a bond has been proposed. In addition, Patent Document 2 includes an alicyclic epoxy compound having a specific structure as an energy-sensitive resin with excellent transparency and curability by suppressing yellowing even in a high-temperature environment, a siloxane compound having two or more glycidyl groups in the molecule, and a curing agent. An energy-sensitive resin composition is proposed.

International Publication No. 2015/064410 International Publication No. 2015/129503

However, in the energy-sensitive composition so far, weight stability in a high-temperature environment is calculated|required.

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

MEANS TO SOLVE THE PROBLEM The present inventors discovered that thermogravimetric stability improved by using the sulfonium salt which has a specific structure, and came to complete this invention.

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

(Wherein, R ¹ and R ² independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (a2), R ¹ and R ² are bonded to each other to form a ring with the atoms in the formula, , R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, X ⁻ represents a monovalent anion, provided that R ¹ and R ² are not an alkyl group which may be simultaneously substituted with a halogen atom.)

(Wherein, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ represents an optionally substituted alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a thienyl group, or a thienyl group. A carbonyl group, a furanyl group, a furanylcarbonyl group, a selenophenyl group, a selenophenylcarbonyl group, a heterocyclic aliphatic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxy (poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, represents a nitro group or a halogen atom, and m1 represents an integer of 0 or more)

(wherein R ⁵ is 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 aryl group An oxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or an alkylene group optionally substituted with a halogen atom; A group represented by the following formula (a5) is represented, and R ⁶ is 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 hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom represents an optionally substituted alkyl group or a group represented by the following formula (a6), A ² represents a single bond, S, O, a sulfinyl group, or a carbonyl group, n1 represents 0 or 1)

(Wherein, R ⁷ and R ⁸ are independently 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, Heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom represents an alkylene group or a group represented by the following formula (a5), R ⁹ and R ¹⁰ independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the formula (a2), R ⁹ and R ¹⁰ are may be bonded to each other to form a ring together with the atoms in the formula, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, X ^- is the same as above, n2 represents 0 or 1, provided that R ⁹ and R ¹⁰ are not an alkyl group which may be simultaneously substituted with a halogen atom.)

(Wherein, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ represents an optionally substituted alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. , arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted represents an amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more)

(Wherein, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an optionally substituted alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. , arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, represents a hydroxy (poly)alkyleneoxy group, an optionally substituted amino group, cyano group, nitro group, or halogen atom, and m3 represents an integer of 0 or more)

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

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

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

1 is a TG/DSC curve showing the thermogravimetric change of Example 3.
2 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 7.
3 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 8;
4 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 9.
5 is a TG/DSC curve showing the thermogravimetric change of a reference example.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described in detail, this invention is not limited at all to the following embodiment, It can implement, adding appropriate change within the range of the objective of this invention.

In this specification, for example, a description such as "A and/or B", "A and/or B", "A and/or B" such as "cationically and/or acid catalytically" is "A and at least one selected from the group consisting of "B". where A and B are arbitrary terms.

<Energy Sensitive Composition>

The energy-sensitive composition according to the present invention is (P1) a cationic and/or acid-catalyzed polymerizable and/or cross-linkable compound, (P2) a compound that increases its solubility in a developer under the action of an acid, and (Px) ) at least one compound component (P) selected from the group consisting of radically polymerizable or crosslinkable compounds and (Q) a sulfonium salt represented by the formula (a1).

The energy-sensitive composition according to the present invention comprises a compound component (P) and a sulfonium salt (Q) by including a sulfonium salt (hereinafter also referred to as "sulfonium salt (Q)") represented by the formula (a1) Among them, since the concentration of protons increases with temperature increase, sequential polymerization in the compound component (P) continuously proceeds to promote polymerization, and it is estimated that there are few monomers decomposed by heat. Accordingly, it is assumed that the energy-sensitive composition according to the present invention has improved weight stability against heat. In addition, the mode in which the sulfonium salt (Q) generates protons includes a mode in which protons are generated by decomposition of the sulfonium salt (Q) itself, and an mode in which hydrogen is extracted from components in the system to generate protons. do.

[(P1) Cationic and/or acid-catalyzed polymerizable and/or cross-linkable compound]

Cationic and/or acid-catalyzed polymerizable and/or cross-linkable compounds {hereinafter also referred to as "compound (P1)"} may be cationic polymerized by, for example, a cation containing an alkyl group or an aryl group, or by a proton. compounds that can be Examples of these include cyclic ethers, particularly epoxy compounds and oxetane compounds, and additionally vinyl ether compounds and hydroxy-containing compounds. Also, lactone compounds and cyclic thioether compounds and vinylthioether compounds can be used. However, in the present specification, when the compound having an ethylenically unsaturated group (vinyl group) is a compound having an epoxy group and/or oxetanyl group (epoxy/oxetanyl group-containing/vinyl group-containing compound), compound (P1) In the case of compounds other than those (epoxy/oxetanyl group-free/vinyl group-containing compound), it is referred to as compound (Px). As used herein, "epoxy" generally includes oxetanyl and alicyclic epoxy as well as oxiranyl, unless otherwise specified.

Further examples include amino plastics or phenolic resor resins. These are in particular melamine resins, urea resins, epoxy resins, phenol resins, acrylic resins, polyester resins and alkyd resins, but especially mixtures of acrylic resins, polyester resins or alkyd resins with melamine resins. Moreover, as these, modified surface coating resin (For example, an acrylic modified polyester resin, an acrylic modified alkyd resin, etc.) is mentioned. The term surface coating resin preferably includes amino resins. Examples of these include etherified and non-etherified melamine resins, urea resins, guanidine resins, and biuret resins. For curing surface coatings comprising etherified amino resins {e.g. methylated melamine resins or butylated melamine resins (N-methoxymethyl-melamine or N-butoxymethyl-melamine) or methylated/butylated glycoluril} Acid catalysts are particularly important.

When compound (P1) is an epoxy compound, if it is a compound which has at least one epoxy group in a molecule|numerator, although it will not specifically limit, Preferably it is a compound which has at least two epoxy groups in a molecule|numerator. The epoxy compound can be selected from the various compounds which have the epoxy group conventionally mix|blended with the curable composition. Although the low molecular weight compound which has an epoxy group which is a non-polymer may be sufficient as an epoxy compound, and the polymer which has an epoxy group may be sufficient, a non-polymer is preferable. As the non-polymer having an epoxy group, an aliphatic epoxy compound not containing an aromatic group is preferable from the viewpoint of excellent thermogravimetric stability of a cured product formed using the energy-sensitive composition. In an aliphatic epoxy compound, the aliphatic epoxy compound which has an alicyclic epoxy group is preferable at the point which superposition|polymerization advances sequentially by ring-opening polymerization and polymerization is accelerated|stimulated.

Specific examples of the aliphatic epoxy compound having an alicyclic epoxy group include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxy) Cyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclo Hexane carboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4' -Epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) ), di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalate dioctyl, and epoxycyclohexahydrophthalic acid di-2 - The epoxy resin which has an ethylhexyl and tricyclodecene oxide group, and the compound represented by following formula (P1-1) - (P1-5) are mentioned. Among the specific examples of these aliphatic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (P1-1) to (P1-4) are preferable, and the following formulas ( The alicyclic epoxy compounds represented by P1-1) to (P1-2) are more preferable. These alicyclic epoxy compounds may be used individually or may be used in mixture of 2 or more types. As the compound component (P) to the compound (P1), especially when it is desired to reduce the outgas, the alicyclic epoxy compound represented by the formula (P1-1), the alicyclic epoxy compound represented by the formula (P1-2); And it is preferable to include at least one of the group consisting of an alicyclic epoxy compound represented by the formula (P1-8), and the ratio in the whole of the compound component (P) to the compound (P1) may be 1 to 99 mass%. , 10-90 mass%, 20-80 mass%, 30-70 mass%, 40-60 mass%, and the like. In addition, the combined use of the alicyclic epoxy compound represented by the formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) can reduce outgassing and reduce the viscosity of the energy-sensitive composition. desirable. When using together the alicyclic epoxy compound represented by the formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2), the alicyclic epoxy compound represented by the formula (P1-1) and the formula (P1- It does not specifically limit as content of the alicyclic epoxy compound represented by Formula (P1-1) with respect to the total amount with the alicyclic epoxy compound represented by 2), For example, 1-99 mass % may be sufficient, and 10-90 Mass %, 20-80 mass %, 30-70 mass %, 40-60 mass %, etc. may be sufficient.

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

Examples of the linking group Z include a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, a divalent group selected from the group consisting of -C(CF ₃ ) ₂ -, and -R ^a19 -O-CO- and a group in which a plurality of these groups are bonded, among which -R ^a19 -O-CO- is preferred. do.

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

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

As the compound represented by the formula (P1-1), a compound that does not easily form a conjugated structure (particularly, a π-electron conjugated structure) by dehydrogenation can obtain a cured product having excellent transparency in addition to thermogravimetric stability. Preferably, an alicyclic epoxy compound, specifically, a compound in which two alicyclic epoxy groups in one molecule are bonded through a linking group containing a quaternary carbon and/or a hetero atom is preferable.

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

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

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

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

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

In the formula (P1-1), when R ^a1 to ^{R a12} are an organic group, the organic group is not particularly limited as long as the object of the present invention is not impaired. and a group containing a hetero atom such as a halogen atom, an oxygen atom, an atom, a nitrogen atom or a silicon atom together with a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

As the organic group, a group consisting of a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a group consisting of a halogenated hydrocarbon group, a carbon atom, an oxygen atom, and a halogen atom, and a group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a halogen atom are preferable. do. 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. 1-20 are preferable, as for carbon atom number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexa chain alkyl groups such as decyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; chain alkenyl groups such as a vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group an aryl group such as a group and a phenanthryl group; and aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group.

Specific examples of the halogenated hydrocarbon group include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2, 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, purple halogenated chain alkyl groups such as a luoronyl group and a perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bro halogenated cycloalkyl groups such as a mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, halogenated aryl groups such as 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group and 4-fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3-fluoro halogenated aralkyl groups such as a phenylmethyl group and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a hydroxy group such as a 4-hydroxy-n-butyl group. chain alkyl group; halogenated cycloalkyl groups such as a 2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group, and a 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-di hydroxyaryl groups such as a hydroxyphenyl group, a 3,4-dihydroxyphenyl group, and a 3,5-dihydroxyphenyl group; hydroxyaralkyl groups such as a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, and a 4-hydroxyphenylmethyl group; Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group Group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyl group chain alkoxy groups such as siloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (aryloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, 3-n-butenyloxy group, etc. of a chain alkenyloxy group; Phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, bi aryloxy groups such as phenyl-2-yloxy group, antholyloxy group, and phenanthryloxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; Methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n Alkoxyalkyl groups such as -propyl group, 3-n-propoxy n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy n-butyl group ; Methoxymethoxy group, ethoxymethoxy group, n-propoxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n -propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and alkoxy alkoxy groups such as 4-n-propoxy n-butyloxy group; alkoxyaryl groups such as a 2-methoxyphenyl group, a 3-methoxyphenyl group, and a 4-methoxyphenyl group; alkoxyaryloxy groups such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; aliphatic acyl groups such as a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, and a decanoyl group; aromatic acyl groups such as a benzoyl group, an α-naphthoyl group, and a β-naphthoyl group; ethoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and chain alkyloxycarbonyl groups such as n-decyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group, and β-naphthoxycarbonyl group; Aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and decanoyloxy group ; aromatic acyloxy groups such as benzoyloxy group, α-naphthoyloxy group, and β-naphthoyloxy group.

R ^a1 to ^{R a18} are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, in particular, an energy-sensitive composition Since the hardened|cured material obtained by using is excellent in mechanical properties, it is more preferable that ^{R a1- R a18 are all hydrogen atoms.}

Formula (P1-2) ~ (P1-5) of, R ^a1 ~R ^a12 is the same as R ^a1 ~R ^a12 in equation (P1-1). In formulas (P1-2) and (P1-4), ^{as a divalent group formed when R a2} and R ^a10 are bonded to each other, for example, -CH ₂ -,-C(CH ₃ ) ₂ - can be heard Examples of the divalent group formed when ^{R a2} and R ^a8 are bonded to each other in the formula (P1-3) _{include —CH 2} —, —C(CH ₃ ) ₂ —.

Among the alicyclic epoxy compounds represented by formula (P1-1), specific examples of preferred compounds include alicyclic epoxy compounds represented by the following formulas (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 formula (P1-2), specific examples of preferred compounds include bicyclononadiene diepoxide and dicyclononadiene diepoxide represented by the following formula (P1-2a). .

^{Sspiro[3-oxatricyclo[3.2.1.0 2,4} ]octane-6,2'-oxirane] etc. are mentioned as a specific example of a preferable compound among the alicyclic epoxy compounds represented by Formula (P1-3). can

Specific examples of preferred compounds among the alicyclic epoxy compounds represented by formula (P1-4) include 4-vinylcyclohexenedioxide, dipentenedioxide, limonenedioxide, and 1-methyl-4-(3-methyloxirane). -2-yl)-7-oxabicyclo[4.1.0]heptane and the like.

Among the alicyclic epoxy compounds represented by Formula (P1-5), 1,2,5,6-diepoxycyclooctane etc. are mentioned as a specific example of a preferable compound.

Examples of non-polymers having an epoxy group that can be used as the compound (P1) other than the alicyclic epoxy compound having an alicyclic epoxy group described above include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, epoxyalkyl (meth)acrylates such as 3,4-epoxybutyl (meth)acrylate and 6,7-epoxyheptyl (meth)acrylate; 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyl epoxyalkyloxyalkyl (meth)acrylates such as oxy-n-hexyl (meth)acrylate and 6-glycidyloxy-n-hexyl (meth)acrylate; bifunctional 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 epoxy resins, such as a phenol novolak-type epoxy resin, a brominated phenol novolak-type epoxy resin, an ortho cresol novolak-type epoxy resin, a bisphenol A novolak-type epoxy resin, and a bisphenol AD novolak-type epoxy resin; Cyclic aliphatic epoxy resins, such as an epoxidized product of a dicyclopentadiene type phenol resin; aromatic epoxy resins such as epoxidized products of naphthalene-type phenol resins; 9,9-bis[4-(glycidyloxy)phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene; 9,9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-flu Orene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, and 9,9-bis(6-glycidyloxynaphthalen 2-yl)-9H- fluorene, 9,9-bis(6-glycidyloxynaphthalen 1-yl)-9H-fluorene, 9,9-bis(5-glycidyloxynaphthalen 1-yl)-9H-fluorene, etc. 9,9-bis(glycidyloxynaphthyl)fluorenes; 9,9-bis[6-(2-glycidyloxyethoxy)naphthalen-2-yl]-9H-fluorene, 9,9-bis[6-(2-glycidyloxypropoxy)naphthalene- 2-yl]fluorene, 9,9-bis[5-(2-glycidyloxyethoxy)naphthalen-1-yl]fluorene, 9,9-bis[5-(2-glycidyloxypro 9,9-bis(glycidyloxyalkoxynaphthyl)fluorenes such as poxy)naphthalen-1-yl]fluorene; 9,9-bis｛6-[2-(2-glycidyloxyethoxy)ethoxy]naphthalen-2-ylb-9H-fluorene, 9,9-biss6-[2-(2-(2-) Glycidyloxypropoxy)propoxy]naphthalen-2-yld-9H-fluorene, 9,9-bisb5-[2-(2-glycidyloxyethoxy)ethoxy]naphthalene-1- 9,9-bis such as monol-9H-fluorene and 9,9-bis#5-[2-(2-glycidyloxypropoxy)propoxy]naphthalen-1-yld-9H-fluorene (glycidyloxydialkoxynaphthyl)fluorenes; Epoxy group-containing fluorene compounds, such as; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl methaxylylenediamine, and tetraglycidylbisaminomethylcyclohexane; Heterocyclic epoxy resins, such as triglycidyl isocyanurate; Fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin 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-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol trifunctional epoxy resins, such as; tetrafunctional epoxy resins such as tetrahydroxyphenylethanetetraglycidylether, tetraglycidylbenzophenone, bisresorcinoltetraglycidylether, and tetraglycidoxybiphenyl, and 2,2-bis(hydroxy 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of oxymethyl)-1-butanol. A 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol is commercially available as EHPE-3150 (manufactured by Daicel).

In addition, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3-hydroxymethyloxetanyl methacrylate, bis-1-ethyl-3-oxetanylmethyl ether , 1,4-bis-3-ethyloxetan-3-ylmethoxymethylbenzene, 3-ethyl-3-2-ethylhexyloxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, etc. A compound having a nyl group (oxetane compound) is also preferably mentioned, and a monofunctional or bifunctional or more than monofunctional oxetane compound having one or two or more oxetanyl groups in one molecule is also preferably mentioned.

Among non-polymers having an epoxy group that can be used as the compound (P1) other than the aliphatic epoxy compound having an alicyclic epoxy group, from the viewpoint of high refractive index, it is preferably an epoxy group-containing fluorene compound, 9,9-bis(gly The following formula (P18) containing cidyloxynaphthyl) fluorenes is more preferable.

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

In the formula (P1-8), ^{as the condensed polycyclic aromatic hydrocarbon ring represented by ring Z 4} , a condensed bicyclic hydrocarbon ring (for example, a C8 to C20 condensed bicyclic hydrocarbon ring such as an indene ring or a naphthalene ring; Preferred examples include condensed 2 to 4 cyclic hydrocarbon rings such as C10 to C16 condensed bicyclic hydrocarbon ring) and condensed tricyclic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.). A naphthalene ring, an anthracene ring, etc. are mentioned as a preferable condensed polycyclic aromatic hydrocarbon ring, A naphthalene ring is especially preferable. ^{Further, the two rings Z 4} substituted at the 9-position of fluorene may be the same or different rings, and usually the same ring.

^{In addition, the substitution position of the ring Z 4} substituted at the 9th position of fluorene is not particularly limited, For example, the naphthyl group substituted at the 9th position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, etc. and it is particularly preferably a 2-naphthyl group.

In the above formula (P1-8) ^{, examples of the substituent represented by R P35} include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, and non-reactive substituents such as an aryl group (C6-C10 aryl group such as a phenyl group), etc.], and in particular a halogen atom, a cyano group, or an alkyl group (especially an alkyl group) in many cases. Examples of the alkyl group include C1-C6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group (eg, a C1-C4 alkyl group, particularly a methyl group). Furthermore, when k1 is plural (2 or more), R ^P35 may be mutually different and may be the same. ^{In addition, R P35} substituted for two benzene rings constituting fluorene (or fluorene skeleton) may be the same or different. In addition, the bonding position (substitution position) of ^{R P35} with respect to the benzene ring which comprises fluorene is not specifically limited. Preferred k1 is 0 to 1, especially 0. Furthermore, in the two benzene rings constituting fluorene, k1 may be the same as or different from each other.

^{As R P36} substituted for ring Z ⁴ , for example, an alkyl group (for example, a C1-C12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a C1-C8 alkyl group, more preferably a C1-C8 alkyl group preferably a C1-C6 alkyl group), a cycloalkyl group (eg, a C5-C8 cycloalkyl group such as a cyclohexyl group, preferably a C5-C6 cycloalkyl group, etc.), an aryl group (eg, a phenyl group, a tolyl group, A C6-C14 aryl group such as a xylyl group, preferably a C6-C10 aryl group, more preferably a C6-C8 aryl group, etc.), an aralkyl group (eg, a benzyl group, a C6-C10 aryl group such as a phenethyl group) a hydrocarbon group such as an aralkyl group formed by bonding a group and a C1-C4 alkyl group; Alkoxy group (For example, a C1-C8 alkoxy group such as a methoxy group, preferably a C1-C6 alkoxy group, etc.), a cycloalkoxy group (C5-C10 cycloalkyloxy group, etc.), an aryloxy group (C6-C10 aryl) oxy group etc.) and the like group -OR ^P38 [ ^{wherein R P38} represents a hydrocarbon group (hydrocarbon group in the above example); groups such as an alkylthio group (eg, a C1-C8 alkylthio group such as a methylthio group, preferably a C1-C6 alkylthio group, etc.)-SR ^P38 ( ^{wherein R P38} is the same as above); an acyl group (for example, a C1-C6 acyl group such as an acetyl group); an alkoxycarbonyl group (eg, an alkoxycarbonyl group formed by bonding a carbonyl group to a C1-C4 alkoxy group such as an ethoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); hydroxyl group; nitro group; cyano group; Substituted amino groups (For example, dialkylamino groups, such as a dimethylamino group, etc.) etc. are mentioned.

Among these, R ^P36 is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, or the like, and particularly preferably R ^P36 is , a hydrocarbon group (eg, an alkyl group (eg, a C1-C6 alkyl group)), an alkoxy group (such as a C1-C4 alkoxy group), a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) .

Further, in the same ring Z ⁴ , when k2 is plural (2 or more), R ^P36 may be different from or the same as each other. In the two rings Z ⁴ , R ^P36 may be the same or different. Moreover, preferable k2 may be 0-8, Preferably it is 0-6 (for example, 1-5), More preferably, it is 0-4, Especially 0-2 (for example, 0-1) may be sufficient. Further, in the two rings Z ⁴ , k2 may be the same as or different from each other.

Further, in the formula (P1-8), R ^P37 is a hydrogen atom or a methyl group, and preferably R ^P37 is a hydrogen atom.

In said formula (P1-8), k3 may be 1 or more, for example, 1-4, Preferably 1-3, More preferably, 1-2, especially 1 may be sufficient. Furthermore, in each ring Z, k3 may be the same or different, and is usually the same in many cases. Further, the substitution position of the epoxy group-containing group is, it is sufficient not particularly limited, and a suitable substituted and the substitution position of the ring Z ^4. In particular, in the condensed polycyclic hydrocarbon ring, the epoxy group-containing group is often substituted at least in a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of the fluorene (for example, the 5-position, the 6-position of the naphthalene ring, etc.).

Specific examples of the compound represented by the formula (P1-8) include 9,9-bis(glycidyloxynaphthyl)fluorene [eg, 9,9-bis(6-glycidyloxy-) 2-naphthyl) fluorene, 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene, etc.] in the formula (P1-8), such as a compound in which k3 is 1; have.

(Polymer having an 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, and with respect to a polymer having a reactive functional group such as a hydroxyl group, a carboxy group, or an amino group, for example, epichloro What introduce|transduced the epoxy group using the compound which has an epoxy group like hydrin may be used. Further, a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in a side chain such as 1,2-polybutadiene can also be suitably used as the polymer having an epoxy group. Such a partial oxide contains the epoxy group produced|generated by oxidation of the unsaturated bond contained in a side chain.

From the viewpoint of easy availability, preparation, adjustment of the amount of epoxy groups in the polymer, etc., as a polymer having an epoxy group, a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group and an unsaturated aliphatic hydrocarbon group in the side chain Partial oxides of the polymer having it are preferred.

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

Among the polymers having an epoxy group, it is a homopolymer of (meth)acrylic acid ester having an epoxy group, or different from (meth)acrylic acid ester having an epoxy group, in terms of ease of preparation and applicability of the energy-sensitive composition to a substrate. Copolymers with monomers are preferred.

The (meth)acrylic acid ester which has an epoxy group may be (meth)acrylic acid ester which has a chain|strand-shaped aliphatic epoxy group, or the (meth)acrylic acid ester which has the alicyclic epoxy group mentioned later may be sufficient as it. Moreover, the (meth)acrylic acid ester which has an epoxy group may contain the aromatic group. From the viewpoint of transparency of the cured product formed using the energy-sensitive composition, among the (meth)acrylic acid esters having an epoxy group, an aliphatic (meth)acrylic acid ester having a chain aliphatic epoxy group and an aliphatic (meth)acrylic acid ester having an alicyclic epoxy group is preferable, and aliphatic (meth)acrylic acid ester having an alicyclic epoxy group is more preferable.

As an example of the (meth)acrylic acid ester which contains an aromatic group and has an epoxy group, 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. have.

Examples of the aliphatic (meth)acrylic acid ester having a chain aliphatic epoxy group include an oxy group (-O-CO-) in the ester group (-O-CO-), such as epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. (meth)acrylic acid ester in which a chain aliphatic epoxy group is bonded to -) is mentioned. The chain|strand-shaped aliphatic epoxy group which such (meth)acrylic acid ester has may contain 1 or several oxy group (-O-) in a chain|strand. Although the number of carbon atoms of a chain|strand-shaped aliphatic epoxy group is not specifically limited, 3-20 are preferable, 3-15 are more preferable, 3-10 are especially preferable.

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

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

In the formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^a22 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t is An integer of 0 to 10 is represented. As R ^a21 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a cyclohexylene group is preferable.

As the polymer having an epoxy group, any of a homopolymer of (meth)acrylic acid ester having an epoxy group and a copolymer of (meth)acrylic acid ester having an epoxy group and another monomer can be used. 70 mass % or more is preferable, as for content of the unit derived from the (meth)acrylic acid ester to have, 80 mass % or more is more preferable, 90 mass % or more is especially preferable, and it is most preferable that it is 100 mass %.

When the polymer having an epoxy group is a copolymer of (meth)acrylic acid ester having an epoxy group and another monomer, examples of the other monomer include unsaturated carboxylic acid, (meth)acrylic acid ester having no epoxy group, (meth)acrylamides, aryl compounds, Vinyl ethers, vinyl esters, styrenes, etc. are mentioned. These compounds can be used individually or in combination of 2 or more types. In terms of storage stability of the energy-sensitive composition and chemical resistance to alkali or the like of a cured product formed using the energy-sensitive composition, a copolymer of (meth)acrylic acid ester having an epoxy group and another monomer is a unit derived from an unsaturated carboxylic acid. It is preferable not to include

Examples of the unsaturated carboxylic acid include (meth)acrylic acid; (meth)acrylic acid amide; crotonic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the anhydrides of these dicarboxylic acids are mentioned.

As an example of the (meth)acrylic acid ester which does not have an epoxy group, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, t-octyl (meth)acrylate, etc. linear or branched alkyl (meth)acrylate; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate , furfuryl (meth) acrylate; (meth)acrylic acid ester which has group which has alicyclic skeleton is mentioned. Among the (meth)acrylic acid esters which do not have an epoxy group, the (meth)acrylic acid ester which has a group which has an alicyclic skeleton from the point of transparency of the hardened|cured material formed using an energy-sensitive composition is preferable.

In the (meth)acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, tetracyclododecyl group, etc. are mentioned.

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

In the formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. indicates. As R ^a24 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. R ^a25 is preferably a methyl group or an ethyl group.

Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl (meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

Examples of the aryl compound include aryl esters such as aryl acetate, aryl caproate, aryl caprylate, aryl laurate, aryl palmitate, aryl stearate, aryl benzoate, aryl acetoacetate, and aryl lactate; aryloxyethanol; and the like.

Examples of vinyl ethers include 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 alkyl vinyl ethers such as ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl. acetate, vinylacetoacetate, vinyllactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of styrenes include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene , alkyl styrene such as acetoxymethyl styrene; Alkoxy styrene, such as methoxy styrene, 4-methoxy-3- methyl styrene, and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro halo styrenes such as methyl styrene and 4-fluoro-3-trifluoromethyl styrene; and the like.

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

Although the polymer which has an unsaturated aliphatic hydrocarbon in a side chain is not specifically limited, 1,2-polybutadiene which has a vinyl group in a side chain is preferable from a thing easily available, synthesis|combination, etc.. By partially oxidizing 1,2-polybutadiene, an epoxidized polybutadiene having an oxiranyl group and a vinyl group in the side chain can be obtained. The ratio of the oxiranyl groups in such epoxidized polybutadiene is preferably from 10 to 70 mol%, more preferably from 10 to 50 mol%, and from 10 to 40 mol% with respect to the total number of moles of oxiranyl groups and vinyl groups. more preferably. As the epoxidized polybutadiene, JP-100 and JP-200 commercially available from Nippon Soda Co., Ltd. can be suitably used.

Although the molecular weight of the polymer which has an epoxy group demonstrated above is not specifically limited in the range which does not impair the objective of this invention, As a polystyrene conversion mass average molecular weight, 3,000-30,000 are preferable and 5,000-15,000 are more preferable.

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

(In formula (P1-6), R ^P31 to ^{R P33} are a linear, branched or cyclic alkylene group, an allylene group, -O-, -C(=O)-, -NH-, and a group consisting of a combination thereof. ^{E 1} to E ³ are epoxy group, oxetanyl group, ethylenically unsaturated group, alkoxysilyl group, isocyanate group, blocked isocyanate group, thiol group, carboxyl group, hydroxyl group and succinic anhydride At least one substituent or hydrogen atom selected from the group consisting of a group, provided ^{that at least one of E 1 to E 3} is at least one selected from the group consisting of an epoxy group and an oxetanyl group.)

In formula (P1-6), ^{it is preferable that at least one of the groups represented by R P31} and E ¹ , R ^P32 and E ² , and R ^P33 and E ³ is, for example, a group represented by the following formula (P1-6a). and more preferably at least two groups each represented by the following formula (P1-6a), and even more preferably any group represented by the following formula (P1-6a). It is preferable that the group represented by Formula (P1-6a) couple|bonded with one compound is the same group.

-L-C … … … … … … … (P1-6a)

(In formula (P1-6a), L is a linear, branched or cyclic alkylene group, allylene group, -O-, -C(=O)-, -NH-, and a group consisting of these combinations, and C is At least one member selected from the group consisting of an epoxy group and an oxetanyl group, in the formula (P1-6a), L and C may combine 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 allylene group as L is preferably an alkylene group having 5 to 10 carbon atoms. Allylene groups are preferred. In formula (P1-6a), L is preferably a group consisting of a linear C1-C3 alkylene group, a phenylene group, -O-, -C(=O)-, -NH-, and combinations thereof. and at least one of a phenylene group and a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, or at least one of -O-, -C(=O)- and NH- A group consisting of a combination is preferred.

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

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

Hereinafter, examples of the epoxy compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group and an alicyclic epoxy group are shown as examples of the compound represented by the formula (P1-6). is not limited to

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

The siloxane compound (B) can impart anti-yellowing properties (= heat resistance and transparency) to the resulting cured product when exposed to a high-temperature environment over a long period of time, has two or more glycidyl groups in the molecule, and furthermore has a siloxane bond (Si -O-Si) is a compound having a siloxane skeleton. As the siloxane skeleton in the siloxane compound (B), for example, a cyclic siloxane skeleton or a polysiloxane skeleton (for example, linear or branched silicone (linear or branched polysiloxane), cage-shaped or ladder-shaped poly Silsesquioxane etc.} etc. are mentioned.

As the siloxane compound (B), a compound having a cyclic siloxane skeleton represented by the following formula (B-1) (hereinafter referred to as "cyclic siloxane") in some cases) is preferred.

In formula (B-1), R ^B1 , R ^B2 represents a monovalent group or an alkyl group containing a glycidyl group. ^{However, among n R B1} and n R ^B2 in the compound represented by formula (B-1), at least two are monovalent groups containing a glycidyl group. In addition, n in Formula (B-1) represents an integer of 3 or more. ^{In addition, R B1} and R ^B2 in the compound represented by Formula (B-1) may be same or different. In addition, some ^RB1 may be same and may differ. A plurality of ^{RB2s may} be the same or different.

As the monovalent group containing the glycidyl group ^{, a glycidyl ether group represented by -DOR B3} [D represents an alkylene group and R ^B3 represents a glycidyl group] is preferable. Examples of the D (alkylene group) include a linear or branched alkylene group having 1 to 18 carbon atoms, such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. can

Examples of the alkyl group include a direct group 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. and a chain or branched alkyl group.

n in formula (B-1) represents an integer of 3 or more, and an integer of 3-6 is preferable at the point which is excellent especially in sclerosis|hardenability of an energy-sensitive composition, and the heat resistance and mechanical strength of hardened|cured material.

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

The epoxy equivalent of the siloxane compound (B) (according to J1SK 7236) is preferably 100 to 350, particularly preferably 150 to 300, and most preferably 200 to 270.

In the energy-sensitive composition of this embodiment, in addition to the siloxane compound (B), other siloxane compounds (for example, alicyclic epoxy group-containing cyclic siloxane; You may contain the organopolysilsesquioxane resin etc. which have at least two epoxy functional groups in 1 molecule described in the publication.

As a siloxane compound (B), the cyclic siloxane etc. which have 2 or more glycidyl groups in a molecule|numerator which are more specifically represented by a following formula are mentioned. Further, as the siloxane compound (B), for example, trade names "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" (above, Shin-Etsu Chemical) Commercial products, such as the industrial company make) can be used.

[(P2) A compound that increases its solubility in a developer under the action of an acid]

As an example of a compound (hereinafter also referred to as "compound (P2)") that increases its solubility in a developing solution under the action of an acid, for example, an oligomer, a polymer, a copolymer obtainable by copolymerization of the monomers exemplified below. can be heard

Acyclic or cyclic secondary and tertiary alkyl (meth) acrylates [eg, tert-butyl acrylate, tert-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- tert-Butyl ester, 8-ethyl-8-tricyclodecanyl (meth)acrylate, (2-tetrahydropyranyl)oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl)oxymethyltricyclododecane Methanol methacrylate, trimethylsilylmethyl (meth)acrylate, (2-tetrahydropyranyl)oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl)oxymethyltricyclododecanemethanol methacrylate, trimethylsilyl methyl (meth)acrylate], o-/m-/p-(3-oxocyclohexyloxy)styrene, o-/m-/p-(1-methyl-1-phenylethoxy)styrene, o- /m-/p-tetrahydropyranyloxystyrene, o-/m-/p-adamantyloxystyrene, o-/m-/p-cyclohexyloxystyrene, o-/m-/p-norbornyl Oxystyrene, acyclic or cyclic alkoxycarbonylstyrene [eg, o-/m-/p-tert-butoxycarbonylstyrene, o-/m-/p-(3-oxocyclohexyloxycarbonyl) ) 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 alkoxycarbonyloxystyrene [For example, 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-adamantyloxycarbonyl oxystyrene, o-/m-/p-cyclohexyloxycarbonyloxystyrene, o-/m-/p-norbornyloxycarbonyloxystyrene], acyclic or cyclic alkoxycarbon Nylalkoxystyrene [eg, o-/m-/p-butoxycarbonylethoxystyrene, p-tert-butoxycarbonylethoxystyrene, o-/m-/p-(3-oxocyclohexyl Siloxycarbonylethoxy)styrene, o-/m-/p-(1-methyl-1-phenylethoxycarbonylethoxy)styrene, o-/m-/p-tetrahydropyranyloxycarbonyl Toxystyrene, o-/m-/p-adamantyloxycarbonylethoxystyrene, o-/m-/p-cyclohexyloxycarbonylethoxystyrene, o-/m-/p-norbornyloxy carbonylethoxystyrene, trimethylsiloxystyrene, dimethyl(butyl)siloxystyrene], unsaturated alkyl acetates (eg, isopropenyl acetate, derivatives thereof), 5-norbornenyl-2-tert-butyl ester]

A monomer carrying an acid labile group having a low activation energy [for example, 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-methyl-ethoxy)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-ethoxyphenyl oxy)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-methyl oxy)-styrene, p- or m-(1-isopropoxy-1-methylethoxy)methylstyrene, p- or m-(1-isopropoxyethoxy)-styrene, p- or m-(1 -isopropoxyethoxy)methylstyrene, p- or m-(1-isopropoxy-1-methylpropoxy)styrene, p- or m-(1-isopropoxy-1-methylpropoxy)-methyl Styrene, 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-methyl-ethoxy)-styrene, p- or m- (1-tert-butoxy-1-methylethoxy)styrene, p- or m-(1-n-pentyloxy-1-methylethoxy)styrene, p- or m-(1-isoamyloxy-1 -methylethoxy)styrene, p- or m-(1-n-hexyloxy-1-methyl-ethoxy)styrene, p- or m-(1-cyclohexyloxy-1-methylethoxy) )styrene, p- or m-(1-trimethylsilyloxy-1-methylethoxy)styrene, p- or m-(1-trimethylsilyloxy-1-methylethoxy)-methylstyrene, p- or m- (1-benzyloxy-1-methylethoxy)styrene, p- or m-(1-benzyloxy-1-methylethoxy)methylstyrene, p- or m-(1-methoxy-1-methylethoxy) )styrene, p- or m-(1-methoxy-1-methylethoxy)-methylstyrene, p- or m-(1-trimethylsilyloxy-1-methylethoxy)-styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy)methylstyrene]

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

In addition, the monomer having an acid labile group is, if appropriate, other free radically polymerizable monomers not carrying an acid labile group [for example, styrene, acrylonitrile, methyl (meth)) in order to establish specific solubility and adhesion properties. acrylate, (meth)acrylic acid, 4-hydroxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-vinylcyclohexanol, norbornene, ethylnorbornene, maleic anhydride]. Alternatively, the acid labile group can only be introduced subsequently, in a polymer-like reaction. It is also known to the person skilled in the art that the prepolymer can be modified in a targeted manner prior to such a polymer-like reaction by, for example, partial hydrogenation, partial alkylation, partial acetylation. That is, the polymer having an acid-labile group does not need to be synthesized from a 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. -T. It is also possible to introduce acid labile crosslinking, as described in Schacht, N. Muenzel, P. Falcigno, H. Holzwarth and J. Schneider, J. Photopolymer Science and Technology, Vol. 9, (1996), 573-586. . Such an acid crosslinking system is preferable from the viewpoint of thermal stability. Moreover, such acid labile crosslinking can be obtained by reaction with a phenol group containing polymer (for example, 4-hydroxystyrene copolymer) with bi- and polyfunctional vinyl ether.

Examples other than the compound (P2) are monomer compounds (eg, carboxylic acid and phenol group-containing compounds) in which each of a carboxylic acid group or a phenolic OH group is blocked by an acid labile protecting group. Such acid labile blocking is, for example, tert-butyl ester group, 2-methyl-2-adamantyl ester group, 8-ethyl-8-tricyclodecanyl ester group, tetrahydropyranyl ester group or several It is possible to carry out by conversion of the carboxy group to another acid cleavable ester group. The phenolic OH group can be blocked according to known methods, for example, by conversion to an acid cleavable tert-butylcarbonate group, a silyl ether, an acetal group and a ketal group.

In addition, compound (P2) is an alicyclic copolymer, a copolymer containing a 4-hydroxy-phenyl group, a copolymer containing maleic anhydride, a copolymer containing acrylic acid, a copolymer containing an acrylic acid ester, and a copolymer containing a methacrylic acid ester. An energy-sensitive composition comprising at least one compound selected from the group consisting of, wherein these copolymers carry a functional group that increases the solubility of the polymer in an alkaline developer after reaction with an acid.

[(Px) radical polymerizable or crosslinkable compound]

The radically polymerizable or crosslinkable compound (also referred to as "compound (Px)" in this specification) includes, for example, an acrylate having a reactive functional group. The reactive functional group may be selected from the group consisting of, for example, a hydroxyl group, a thiol group, an isocyanate group, an anhydride group, a carboxy group, an amino group, and a blocked amino group. Examples of the OH group-containing unsaturated acrylate include hydroxyethyl acrylate and hydroxybutyl acrylate. Further, the compound (Px) may be of any desired structure (for example, it may contain units such as polyester, polyacrylate, polyether, etc.), but it may contain an ethylenically unsaturated double bond and further free contains an OH group, a COOH group, an NH ₂ group or an NCO group.

The compound (Px) can also be obtained by, for example, reacting acrylic acid or methacrylic acid with an epoxy functional oligomer. A typical example of an OH-functional oligomer having a vinylic double bond is,

As, CH ₂ =CHCOOH and

It is obtained by reaction with

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

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

(In the formula (Px-1), R ^P31 to ^{R P33} represent a linear, branched or cyclic alkylene group, an allylene group, -O-, -C(=O)-, -NH-, and combinations thereof. group, and each may be the same or different.E ^{4 to E 6} are between the compound (P1) and the compound represented by the formula (Px-1) or the compound represented by the formula (Px-1) It is a functional group or hydrogen atom that can radically polymerize or crosslink between each other, provided ^{that at least one of E 4 to E 6} is the above functional group.)

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

-L'-C' … … … … … … … … … … (Px-1a)

(In the formula (Px-1a), L' is a linear, branched or cyclic alkylene group, an allylene group, -O-, -C(=O)-, -NH-, and a group consisting of a combination thereof, and C ' is at least one 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 formula (Px-1a), L' and C' may combine 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 allyl having 5 to 10 carbon atoms as the allylene group as L'. Rengi is preferred. In formula (Px-1a), L' is preferably a group consisting of a linear C1-C6 alkylene group, a phenylene group, -O-, -C(=O)-, -NH-, and combinations thereof. and at least one of a phenylene group and a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, or a combination of these and at least one of -O-, -C(=O)- and NH- A group consisting of is preferred. When a branched alkylene group and a succinic anhydride group couple|bond to form a cyclic structure, cyclohexane-1,2- dicarboxylic acid anhydride is specifically mentioned.

Furthermore, in the energy-sensitive composition of this embodiment, the content of the compound component (P) is preferably 80 to 99.999 mass%, and 90 to 99.99 mass%, with respect to the entire composition (however, excluding the solvent). It is more preferable, and it is still more preferable that they are 92 mass % - 99.9 mass %. There exists a tendency for thermogravimetric stability to become favorable that content of a compound component (P) is in the said range.

As the compound component (P), a compound selected from the group consisting of compound (P1), compound (P2), and compound (Px) can be used alone or in combination of two or more. When using in combination of 2 or more types, it is preferable to contain compound (P1). In this case, 10 mass % or more is preferable in a compound component (P), as for content of a compound (P1), 30 mass % or more is more preferable, 50 mass % or more is still more preferable. When content of a compound (P1) is the said range, the improvement effect of thermogravimetric stability is especially large. In addition, when using an energy-sensitive composition for 3D printing, you may combine compound (Px) with compound (P1), In that case, it is preferable to use photoinitiators, such as a radical photoinitiator, together.

[(Q) a sulfonium salt represented by the formula (a1)]

The sulfonium salt represented by the formula (a1) (hereinafter also referred to as “sulfonium salt (Q)”) is a carbon atom ortho-positioned to the carbon atom to which A1 is bonded in the benzene ring in the formula (a1). It is characterized in that the methyl group is bonded. Since the sulfonium salt (Q) has a methyl group at the above position, it tends to generate protons and has high sensitivity to active energy rays such as ultraviolet rays as compared with conventional sulfonium salts.

In the formula (a1), any of R ¹ and R ² is preferably a group represented by the formula (a2). R ¹ and R ² may be the same as or different from each other. In the formula (a1), when R ¹ and R ² are bonded to each other to form a ring together with an atom in the formula, the formed ring is preferably a 3 to 10 membered ring including atoms, and a 5 to 7 membered ring more preferably. A polycyclic ring may be sufficient as the ring formed, and it is preferable that 5-7 membered rings condensed.

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

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

In the formula (a2), R ⁴ is preferably an alkyl group, hydroxyl group, alkylcarbonyl group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, optionally substituted amino group, or nitro group which may be substituted with a halogen atom, It is more preferable that they are an alkyl group optionally substituted with a halogen atom, an alkylcarbonyl group, or a thienylcarbonyl group. In the formula (a2), m1 ^{can be selected according to the type of ring Z 1} , for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2 .

In the formula (a3), R ⁵ represents an alkylene group or a group represented by the formula (a5), and the alkylene group may be substituted with a substituent. Examples of the substituent optionally substituted 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, and a heterocyclic group. hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom. have. R ⁵ is an alkylene group; an alkylene group substituted with a hydroxyl group, an optionally substituted amino group, or a nitro group; Or it is preferable that it is group represented by said Formula (a5).

In the formula (a3), R ⁶ represents an alkyl group or a group represented by the formula (a6), and the alkyl group may be substituted with a substituent. As a substituent which may substitute the said alkyl group, it is the same as that of the substituent which may substitute the alkylene group as ^{R<5> in the said Formula (a3).} R ⁶ is an alkyl group; an alkyl group substituted with a hydroxyl group, an optionally substituted amino group, or a nitro group; Or it is preferable that it is group represented by said Formula (a6).

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

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

In the formula (a4), R ⁷ and R ⁸ independently represent an alkylene group or a group represented by the formula (a5), and the alkylene group may be substituted with a substituent. As a substituent which may substitute the said alkylene group, it is the same as that of the substituent which may substitute the alkylene group as ^{R<5> in the said Formula (a3).} R ⁷ and R ⁸ are independently an alkylene group; an alkylene group substituted with a hydroxyl group, an optionally substituted amino group, or a nitro group; Alternatively, the group represented by the formula (a5) is preferable, and more preferably the group represented by the formula (a5). R ⁷ and R ⁸ may be the same as or different from each other.

In the formula (a4), any of R ⁹ and R ¹⁰ is preferably a group represented by the formula (a2). R ⁹ and R ¹⁰ may be the same as or different from each other.

In the formula (a4), when R ⁹ and R ¹⁰ are bonded to each other to form a ring together with the atoms in the formula, the formed ring is preferably a 3 to 10 membered ring including atoms, and a 5 to 7 membered ring more preferably. A polycyclic ring may be sufficient as the ring formed, and it is preferable that 5-7 membered rings condensed.

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

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

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

In the formula (a5), m2 ^{can be selected according to the type of ring Z 2} , for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2 do.

In the formula (a6), R ¹² is preferably an alkyl group, hydroxyl group, alkylcarbonyl group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, optionally substituted amino group, or nitro group which may be substituted with a halogen atom, It is more preferable that they are an alkyl group optionally substituted with a halogen atom, an alkylcarbonyl group, or a thienylcarbonyl group.

In the formula (a6), m3 ^{can be selected according to the type of ring Z 3} , for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2 do.

In the formula (a1), X ⁻ is a monovalent anion corresponding to an acid (HX) generated by irradiating the sulfonium salt (Q) with active energy (heat, visible light, ultraviolet light, electron beam, X-ray, etc.). When the sulfonium salt (Q) is used as the acid generator, a monovalent polyatomic anion is suitably exemplified ^{as X -} _{, MY a} ^- , (Rf) _b PF _{6 -b} ^- , R ^x1 _c BY _{4 -c} ^- An anion represented by , R ^x1 _{c GaY 4 -c} ^- , R ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ₃ C ^- , or (R ^x2 SO ₂ ) ₂ N ^- is more preferable. Moreover, a ^{halogen anion may be sufficient as X<->} , For example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc. are mentioned.

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

Y represents a halogen atom (a fluorine atom is preferable).

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 represented by Rf by fluorine substitution include a straight-chain alkyl group (methyl, ethyl, propyl, butyl, pentyl and octyl, etc.), a branched-chain alkyl group (isopropyl, isobutyl, sec-butyl and tert-butyl, etc.) and a cycloalkyl group ( cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl);

The ratio in which hydrogen atoms of these alkyl groups are substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably based on the number of moles of hydrogen atoms in the original alkyl group. is 100 mol%. When the substitution ratio by a fluorine atom exists in these preferable ranges, the photosensitivity of a sulfonium salt (Q) becomes more favorable. Particularly preferred Rf is CF ₃ ^- , CF ₃ CF ₂ ^- , (CF ₃ ) ₂ CF ^- , CF ₃ CF ₂ CF ₂ ^- , CF ₃ CF ₂ CF ₂ CF ₂ ^- , (CF ₃ ) ₂ CFCF ₂ ^- , CF ₃ CF ₂ (CF ₃ )CF ^— and (CF ₃ ) ₃ C ^— . The b pieces of Rf are independent of each other and, therefore, may be the same as or different from each other.

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

R ^x1 represents a phenyl group in which a part of hydrogen atoms are substituted with at least one element or an electron group.

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

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

R ^x2 represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group and the fluoroalkyl group are linear, branched or cyclic. may be used, 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 hydroxy group, an amino group which may be substituted (for example, those exemplified in the description below regarding the formulas (a2) to (a6)), a nitro group, and the like. .

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

When ^{the alkyl group, fluoroalkyl group or aryl group represented by R x2} has the above substituent, hetero atom, or functional group, the number of the substituent, hetero atom, or functional group may be one or two or more.

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

a represents the integer of 4-6.

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

As for c, the integer of 1-4 is preferable, More preferably, it is 4.

Examples of the anion represented by MY _a ^- _{include an anion represented by S b} F ₆ ^- , PF ₆ ^- or BF ₄ ^- .

As an anion represented by (Rf) _b PF _{6 -b} ^- _{, (CF 3} CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF Anion represented by ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^- and the like. Of these, (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₂ PF An anion represented by ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^{- is preferred.}

As the anion represented by ^{R x1} _c BY _{4 -c} ^{-, preferably}

R ^x1 _c BY _{4 -c} ^-

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

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

As an anion represented by ^{R x1} _c GaY _{4 -c} ^- _{, (C 6} F ₅ ) ₄ Ga ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- , (CF ₃ C ₆ H ₄ ) ₄ Ga ^- an anion represented by , (C ₆ F ₅ ) ₂ GaF ₂ ^- , C ₆ F ₅ GaF ₃ ^- or (C ₆ H ₃ F ₂ ) ₄ Ga ^{- .} Among these, an anion represented by _{(C 6} F ₅ ) ₄ Ga ⁻ or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^{− is preferable.}

Examples of the anion represented by R ^{x 2} SO ₃ ^- include a trifluoromethanesulfonic acid anion, a pentafluoroethanesulfonic acid anion, a heptafluoropropanesulfonic acid anion, a nonafluorobutanesulfonic acid anion, a pentafluorophenylsulfonic acid anion, and p-toluenesulfonic acid. an anion, a benzenesulfonic acid anion, a camphorsulfonic acid anion, a methanesulfonic acid anion, an ethanesulfonic acid anion, a propanesulfonic acid anion, a butanesulfonic acid anion, etc. are mentioned. Of these, preferred are trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, butanesulfonic acid anion, camphorsulfonic acid anion, benzenesulfonic acid anion, or p-toluenesulfonic acid anion.

As an anion represented by (R ^x2 SO ₂ ) ₃ C ^- _{, (CF 3} SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₃ F ₇ SO ₂ ) ₃ C ^- or ( and an anion represented by C ₄ F ₉ SO ₂ ) ₃ C ^{− .}

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

Examples of the monovalent polyatomic anion include MY _a ^- , (Rf) _b PF _{6 -b} -, R ^x1 _c BY _{4 -c} ^- , R ^x1 _c GaY _{4 -c} ^- , R ^x2 SO ₃ ^- , (R ^x2 SO _{2 )} ) ₃ C ^- or (R ^x2 SO ₂ ) ₂ N ^{- In} addition to the anion represented by _{, perhalogenate ions (ClO 4} ^- , BrO ₄ ^-, etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^- etc.), sulfuric acid ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^- etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^- etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^- etc.), hexa Fluorobismuth ion (BiF ₆ ^- ), Carboxylic acid ion (CH ₃ COO ^- , CF ₃ COO ^- , C ₆ H ₅ COO ^- , CH ₃ C ₆ H ₄ COO ^- , C ₆ F ₅ COO ^- , CF ₃ C ₆ H ₄ COO ^- etc.), aryl borate ion (B(C ₆ H ₅ ) ₄ ^- , CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ^- etc.), thiocyanate ion (SCN-) and nitrate ions (NO ₃ ⁻ ).

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

In the formulas (a2), (a5), and (a6), examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (such as a naphthalene ring) _8- C ₂₀ condensed polycyclic hydrocarbon ring 2, preferably C _{10- 16} 2 condensed cyclic hydrocarbon ring), tricyclic condensed aromatic hydrocarbon ring (e.g., anthracene ring, phenanthrene renhwan, etc.), such as from 2 to 4 condensed polycyclic aromatic hydrocarbon ring] and the like. It is preferable that it is a benzene ring or a naphthalene ring, and, as for an aromatic hydrocarbon ring, it is more preferable that it is a benzene ring.

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

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

In the formulas (a2) to (a6), the alkoxy group is a linear or branched chain alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy).

In the formulas (a2) to (a6), examples of the alkyl group exemplified by the alkylcarbonyl group include the aforementioned linear alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, or a branched chain alkyl group having 3 to 18 carbon atoms. A cycloalkyl group is mentioned, As an alkylcarbonyl group, a C2-C18 linear, branched or cyclic alkylcarbonyl group (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl) , 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl, and cyclohexanoyl); and the like.

In the formulas (a3) to (a6), examples of the arylcarbonyl group include an arylcarbonyl group having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

In the formulas (a2) to (a6), as the alkoxycarbonyl group, a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (ethoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl); .

In the formulas (a3) to (a6), examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

In the formulas (a3) to (a6), examples of the arylthiocarbonyl group include an arylthiocarbonyl group having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

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

In the formulas (a3) to (a6), as the arylthio group, an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenyl Thio, 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, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4- Benzoyl phenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-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).

In the formulas (a2) to (a6), the alkylthio group is a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio) , sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio) and the like).

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

In the formula (a2), as the heterocyclic aliphatic hydrocarbon group, a heterocyclic hydrocarbon group having 2 to 20 (preferably 4 to 20) carbon atoms (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidi) nyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.).

In the formulas (a3) to (a6), as the heterocyclic hydrocarbon group, a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, chia) Jolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phena zinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxatinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl); .

In the formulas (a3) to (a6), examples of the aryloxy group include an aryloxy group having 6 to 10 carbon atoms (phenoxy and naphthyloxy, etc.).

In the formulas (a2) to (a6), as the alkylsulfinyl group, a linear or branched chain sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl) , isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl, etc.) and the like.

In the formulas (a3) to (a6), examples of the arylsulfinyl group include an arylsulfinyl group having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

In the formulas (a2) to (a6), as the alkylsulfonyl group, a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl) phonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, and octadecylsulfonyl, etc.) and the like.

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

In the formulas (a2) to (a6), as the hydroxy (poly) alkyleneoxy group, HO (AO) _q ^- (wherein AO independently represents an ethyleneoxy group and/or a propyleneoxy group, and q is 1 The hydroxy (poly) alkyleneoxy group etc. represented by the integer of -5 are mentioned.

In the formulas (a2) to (a6), the optionally substituted amino group is an amino group (-NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methylethylamino, di Ethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, di phenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, and isopropylphenylamino);

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

The sulfonium salt (Q) can be synthesized, for example, according to the following scheme. Specifically, 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) is reacted with a compound represented by the following formula (b2) in the presence of a base such as potassium hydroxide, and the following formula A nitro compound represented by (b3) is obtained, followed by reduction in the presence of reduced iron to obtain an amine compound represented by the following formula (b4). This amine compound is reacted with a _{nitrite (for example, sodium nitrite) represented by MaNO 2} (wherein, Ma represents an alkali metal atom such as a metal atom, for example, a sodium atom) to obtain a diazo compound, Next, this diazo compound and CuX' (wherein, X' represents a halogen atom such as a bromine atom.

Hereinafter, the same applies.) The cuprous halide represented by the formula (b5) and the hydrogen halide represented by HX' are mixed, the reaction is advanced, and the halide represented by the following formula (b5) is obtained. A Grignard reagent is prepared from this 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, and a sulfonium salt represented by the following formula (b7) can get In addition, this sulfonium salt is mixed with Mb ⁺ X" ^- (wherein, Mb ⁺ represents a metal cation, for example, an alkali metal cation such as a potassium ion, and X" ^- represents a monovalent anion represented by X ^{- (provided that} A sulfonium salt represented by the following formula (b8) can be obtained by reacting with a salt represented by )) and performing salt exchange. Furthermore, in the following formulas (b2) to (b8), R ¹ to ^{R 3} and A1 are the same as in the formula (a1).

<Scheme>

Specific examples of the cation moiety of the sulfonium salt (Q) represented by the formula (a1) include the following. Specific examples of the anion moiety of the sulfonium salt (Q) represented by the formula (a1) include those previously known, such as those given in the description of ^{X − .} The sulfonium salt (Q) represented by the above formula (a1) can be synthesized according to the above scheme, and by further salt exchange if necessary, the cation moiety can be combined with the desired anion moiety, in particular R ^x1 _c BY _{4- c} ^- (wherein, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron accepting group, Y represents a halogen atom, and c represents an integer of 1 to 4) A combination is preferred.

Furthermore, in the energy-sensitive composition of this embodiment, the content of the sulfonium salt (Q) is preferably 0.001 to 20 mass%, and 0.01 to 10 mass%, based on the entire composition (however, excluding the solvent). It is more preferable, and it is still more preferable that it is 0.1-8 mass %. When the content of the sulfonium salt (Q) is within the above range, the thermogravimetric stability tends to be good. In particular, when the viscosity of the energy-sensitive composition is prepared to a low viscosity such as 1000 mPa·s (1000 cP) or less described later, the content of the sulfonium salt (Q) is the entire composition (however, excluding the solvent) may be within the above range, but may be 0.001 to 1 mass%, 0.005 to 0.1 mass%, or 0.008 to 0.05 mass%.

[Other ingredients]

(Other sulfonium salts, etc.)

The energy-sensitive composition of the present embodiment may contain an onium salt other than the sulfonium salt (Q) together with the sulfonium salt (Q).

As such an onium salt, for example, an onium salt ^{comprising an onium ion different from a monovalent anion represented by X −} in the formula (a1) and a cation other than ^{X − in the formula (a1), etc.} and a sulfonium salt (also referred to as "sulfonium salt (Q')" in this specification) is preferable. As the monovalent anion represented by ^{X − , the aforementioned R x1} _c BY _4-c ⁻ is preferable.

Examples of the sulfonium salt (Q') having a monovalent anion represented by R ^x1 _c BY _{4 -c} ^{- include a sulfonium salt represented by the following formula (a1').}

(Wherein, R ¹ , R ² , R ³ , A1 , R ^x1 , Y and c are the same as described above.)

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

Examples of the sulfonium salt (Q') include sulfonium salts represented by the above formula (a1) (wherein, R ¹ and R ² independently represent groups represented by the following formula (a2)).

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

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

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

(solvent)

The sulfonium salt (Q) may be previously dissolved in a solvent (S) which does not inhibit cationic polymerization in order to facilitate dissolution in the cationically polymerizable compound.

Examples of the solvent include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.); Esters (chain alkyl esters such as ethyl acetate, methyl propionate, ethyl propionate, methyl butanoate, ethyl butanoate, methyl pentanoate, ethyl pentanoate, methyl hexane, ethyl hexane, methyl heptanoate, and ethyl heptanoate; cyclopentyl acetate; Cyclohexyl acetate, cyclooctyl acetate, methyl cyclohexyl acetate, ethyl cyclohexyl acetate, propyl cyclohexyl acetate, isopropyl cyclohexyl acetate, butyl cyclohexyl acetate, isobutyl cyclohexyl acetate, acetate-s-butylcyclohexyl, acetate- cyclic alkyl esters such as t-butylcyclohexyl and pentylcyclohexyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone); β-keto ester compounds (methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate isopropyl, acetoacetate-n-butyl, α-acetylγ-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 (such as ethylene glycol monomethyl ether acetate ester, propylene glycol monomethyl ether acetate ester, propylene glycol monoethyl ether acetate ester, and diethylene glycol monobutyl ether acetate ester). Available.

In addition, you may use a conventionally well-known ketone type solvent, alcohol type solvent, an amide type solvent, and a hydrocarbon type solvent. Moreover, you may use the solvent known as a protic solvent and/or a basic solvent.

Examples of the protic solvent include alcohols such as monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol and diethylene glycol monomethyl ether and polyhydric alcohols such as ethylene glycol and glycerin; 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; and active methylene compounds such as acetylacetone and diethyl maronate.

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

When using a solvent, the use ratio of the solvent is, for example, 1-99 mass % is preferable with respect to the whole energy-sensitive composition of this embodiment, More preferably, it is 10-95 mass %.

(Alkali-soluble resin)

The energy-sensitive composition according to the present embodiment can contain alkali-soluble resin (A) as needed. Further, in the present specification, alkali-soluble resin refers to a resin film having a film thickness of 1 µm formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass%, and 2.38 mass% tetramethylammonium When immersed in hydroxide (TMAH) aqueous solution for 1 minute, it means to melt|dissolve with a film thickness of 0.01 micrometer or more.

As the alkali-soluble resin, with respect to a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and a monocarboxylic acid containing an unsaturated group, (a) dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and (b ) alkali-soluble resin (A1) obtained by reacting tetracarboxylic acid or its acid dianhydride, conventionally known resin (A2) having an alkali-soluble group such as a carboxyl group, a phenol hydroxyl group, or a sulfo group (-SO3H), etc. are mentioned. In this specification, Preferably alkali-soluble resin (A2) shows alkali-soluble resins other than alkali-soluble resin (A1). These alkali-soluble resins are preferable also when it is desired that the hardened|cured material obtained has heat resistance.

As alkali-soluble resin (A2), it is preferable to contain resin chosen from the group which consists of resin which has a card structure, resin which has phenolic hydroxyl group, carboxy group-containing resin, polyimide resin, and an epoxy resin.

It does not specifically limit as alkali-soluble resin (A2), Conventionally well-known alkali-soluble resin can be used. What has an ethylenically unsaturated group may be sufficient as this alkali-soluble resin, and the thing which does not have an ethylenically unsaturated group may be sufficient as it.

As alkali-soluble resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound and unsaturated carboxylic acid further react with polybasic acid anhydride can be used, for example.

Especially, resin represented by a following formula (f-1) is preferable. Resin represented by this formula (f-1) is preferable at the point with high photocurability itself.

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

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

In addition, in the said General formula (f-1), Y ^f represents the residue except the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, anhydride glutaric acid etc. are mentioned.

In addition, the following formula ^(f-1), Z f represents a residue other than two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

In addition, in the said General formula (f-1), m represents the integer of 0-20.

Moreover, as alkali-soluble resin which has an ethylenically unsaturated group, Polyester (meth)acrylate obtained by making (meth)acrylic acid react with the polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; Polyurethane (meth)acrylate obtained by making a polyol and the compound which has two isocyanate groups react, and then making (meth)acrylic acid react; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resor type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester An epoxy (meth)acrylate resin obtained by reacting (meth)acrylic acid with an epoxy resin such as a cidyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, or a dihydroxybenzene type epoxy resin can also be used.

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

On the other hand, as alkali-soluble resin having no ethylenically unsaturated group, resin obtained by copolymerizing at least an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound not having an alicyclic group, and an alicyclic group-containing unsaturated compound can be used.

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 the like. Among these, (meth)acrylic acid and maleic anhydride are preferable from points, such as copolymerization reactivity, alkali solubility of resin obtained, and availability. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

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, and 6,7-epoxyheptyl. (meth)acrylic acid epoxy such as (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 4-oxatetracyclo[6.2.1.0 ^2,7 0 ^3,5 ]undecanyl (meth)acrylate alkyl esters; α-alkyl acrylic acid epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl, and α-ethyl acrylic acid-6,7-epoxyheptyl; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, -Vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether are preferable. These epoxy group-containing unsaturated compounds can be used individually or in combination of 2 or more types.

As an alicyclic group-containing unsaturated compound, if it is an unsaturated compound which has an alicyclic group, it will not specifically limit. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specific examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formula.

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

It is preferable that it is 3-25 mass %, and, as for the ratio of the structural unit derived from the said unsaturated carboxylic acid in this alkali-soluble resin, it is more preferable that it is 5-25 mass %. Moreover, it is preferable that it is 71-95 mass %, and, as for the ratio of the structural unit derived from the said epoxy-group containing unsaturated compound, it is more preferable that it is 75-90 mass %. Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound is 1-25 mass %, It is more preferable that it is 3-20 mass %, It is still more preferable that it is 5-15 mass %. By setting it as said range, the hardened|cured material obtained can have sufficient heat resistance, making alkali solubility of resin obtained suitable.

It is preferable that it is 1000-40000, and, as for the mass average molecular weight of alkali-soluble resin, it is more preferable that it is 2000-30000. By setting it as said range, the hardened|cured material obtained can have sufficient heat resistance.

Moreover, silicon-containing resin may be sufficient as carboxyl group-containing resin in alkali-soluble resin (A2), For example, the siloxane resin containing the following structural unit is mentioned. What contains the structural unit represented by a following formula (A2-1) may be sufficient.

In the formula (A2-1), R ^r1 is an organic group having at least one carboxy group in its structure. The carboxyl group is preferably bonded to the Si atom through a linking group, and the linking group is, for example, an alkylene group, a cycloalkylene group, or an allylene group, which may be a straight or branched chain having 1 to 10 carbon atoms, or a combination of these 2 is the flag of the family

The coupling group may have an ether bond, an amino bond, an amide bond, or a vinyl bond, and it is preferable to have an amide bond. R ^r1 includes, for example, the following, but is not limited thereto. Furthermore, * in the following formula means the terminal of the bond of ^{R r1} couple|bonded with Si in formula (A2-1).

The ratio of the structural unit of Formula (A2-1) in silicon-containing resin is 1-90 mass %, for example. Silicon-containing resin may have a conventionally well-known structural unit other than (A2-1).

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

When an 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, and 20% by mass or less with respect to the entire energy-sensitive composition (however, excluding the solvent). It is more preferable, and it is still more preferable that it is 15 mass % or less, As long as it is in these ranges, as a lower limit of content, more than 0 mass % may be sufficient, for example, 3 mass % or more and 5 mass % or more may be sufficient. By setting it as said range, the hardened|cured material obtained can have sufficient heat resistance.

(Surfactants)

The energy-sensitive composition according to the present embodiment may contain a surfactant if necessary. As surfactant, a fluorochemical surfactant, silicone type surfactant, etc. are mentioned, for example.

(metal oxide particles)

The energy-sensitive composition according to the present embodiment may contain metal oxide particles as necessary. Thereby, adjustment of a refractive index is possible, and low-reflectivity and/or highly transparent hardened|cured material can be obtained. Examples of the metal oxide particles include at least one type of metal oxide particles selected from aluminum, zirconium, titanium, zinc, indium, tin, antimony, lanthanum, cerium, neodium, gadolinium, holmium, lutetium, hafnium, and tantalum. . An oxide of zirconium, titanium, or cerium can be preferably used, and from the viewpoint of increasing the refractive index, titanium oxide or cerium oxide is particularly preferable. The shape of these metal oxide particles is not particularly limited, and those having an average particle diameter of 1 to 200 nm by dynamic scattering method can be used, and more preferably 3 to 100 nm. The content rate of the metal oxide particles is, for example, 1-120 mass%, preferably 3-110 mass%, and more preferably 5-100 mass%, among the components excluding the solvent of the energy-sensitive composition.

In addition, in the energy-sensitive composition according to the present embodiment, if necessary, known additives (radical photopolymerization initiator, sensitizer, pigment, dispersant, filler, antistatic agent, flame retardant, defoaming agent, flow regulator, light stabilizer, antioxidant, adhesion-imparting agents, ion supplements, color inhibitors, solvents, non-reactive resins, radically polymerizable compounds, etc.) may be contained.

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.

[characteristic]

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

As described above, by including the sulfonium salt (Q), in the system containing the compound component (P) and the sulfonium salt (Q), the concentration of protons increases, and sequential polymerization in the compound component (P) continues to proceed and it is presumed that the polymerization is promoted. As a result, the energy-sensitive composition according to the present embodiment exhibits a small reduction in weight, preferably 10% or less, even when the temperature is raised to 230°C.

The energy-sensitive composition which concerns on this embodiment is used for the sealing material for organic electroluminescent display elements, or the curable composition for wafer-level lenses, and it is preferable. The energy-sensitive composition according to this embodiment exhibits good curability, particularly photocurability, and has excellent weight stability even when exposed to high temperatures and maintains quality over a long period of time. It is preferable to be used for a lens. Moreover, since it is provided with both thermal reactivity and photoreactivity, it is used for the composition for 3D printing and is preferable. The method of using the energy-sensitive composition which concerns on this embodiment for the sealing material for organic electroluminescent display elements, the curable composition for wafer-level lenses, the composition for 3D printing, or the composition for inkjet printing is also one of this invention.

In addition, the energy-sensitive composition according to the present embodiment is prepared as a coating liquid, for example, and applied to an object to be coated such as a polyimide film using a spin coater, dip coater, bar coater, slit coater or the like coating device. By post-curing, a hard coat can be formed. The coating solution is a thin film such as, for example, a film thickness of 10 mm 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. It is possible to suppress the degree of deformation such as curl of the coated object. The film thickness of the to-be-coated object may be 10 micrometers or more, for example.

In addition, in general, in order to lower the viscosity of the composition, a low molecular weight compound (P1), for example, an epoxy monomer is used. On the other hand, as the low molecular weight compound is blended, the heat resistance tends to decrease and outgas is easily generated. . However, it was confirmed that the energy sensitive composition which concerns on this embodiment is excellent in heat resistance and can reduce generation|occurrence|production of an outgas even if a viscosity is low by including a sulfonium salt (Q). In addition, unexpectedly, even if the amount of addition of the sulfonium salt (Q) is small compared to the amount of a general cationic polymerization initiator, etc., the effect of lowering the viscosity of the energy-sensitive composition, improving heat resistance, and reducing the generation of outgas is obtained. was confirmed by

Since the energy-sensitive composition according to the present embodiment is low-viscosity, excellent in heat resistance and capable of reducing the generation of outgas, it is preferably used also for inkjet printing requiring low-viscosity ink. From the viewpoint of productivity, etc., when apply|coating to a comparatively large area, for example, an inkjet ink is used preferably for displays, such as a touch panel, and is used suitably for uses, such as a sealing material for organic electroluminescent display elements. The composition for inkjet printing containing the energy-sensitive composition according to the present embodiment has a viscosity of 1000 mPa·s (1000 cP) or less at 25°C and a shear rate of 20 (1/s), and the content of the sulfonium salt (Q) It is preferable that it is 0.001-1 mass % with respect to this whole composition (however, the solvent is excluded).

<Manufacturing method of wafer level lens>

A wafer level lens can be manufactured by molding (eg, a casting molding method, an injection molding method) the above-mentioned energy-sensitive composition. Further, the wafer level lens mold may be any of metal, glass, and plastic.

The casting molding method includes a simultaneous molding method and a single piece molding method, each having 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 aligned in a certain direction, and is cured by heating and/or light irradiation.

Step 2: The wafer-level lens mold is removed and annealed to obtain a cured product having a shape in which a plurality of wafer-level lenses are combined.

Step 3: A wafer-level lens is obtained by separating a cured product having a shape in which a plurality of wafer-level lenses are combined.

(reformed molding method)

Step 1: Pour the energy-sensitive composition into a wafer-level lens mold having a single lens shape, and cure by heating and/or light irradiation.

Step 2: The wafer-level lens mold is removed and annealed to obtain a wafer-level lens.

(Injection molding method)

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

Step 2: The wafer level lens mold is removed, annealed, and a burr is removed to obtain a wafer level lens.

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

By the annealing treatment, internal warpage can be removed. The annealing treatment is preferably performed, for example, by heating at a temperature of 100 to 200°C for about 30 minutes to 1 hour.

In the co-molding method, the energy-sensitive composition is preferably low in viscosity and excellent in fluidity in view of excellent filling properties to the mold. In the co-molding method, the energy-sensitive composition used has a viscosity at 25° C. and a shear rate of 20 (1/s), for example, about 0.05 to 5 Pa·s, preferably 0.1 to 2 Pa·s. . The energy-sensitive composition having a viscosity in the above range has excellent fluidity, bubbles hardly remain, and can be filled in a mold while suppressing an increase in injection pressure. That is, it is excellent in applicability|paintability and filling property, and it is excellent in workability|operativity throughout the molding operation|work.

The cured product of the energy-sensitive composition has excellent heat resistance even in a high-temperature environment of about 100 to 250°C. Therefore, even if it anneals after removing from a metal mold|die, the wafer-level lens which has the outstanding lens center position precision can be manufactured efficiently. 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 combined are overlapped, and the position of the cutting line is determined based on the uppermost cured product and cut, without damaging the wafer-level lens. It can be separated, and a wafer level lens or its laminated body can be manufactured efficiently at low cost.

The wafer-level lens obtained by the energy-sensitive composition of the present embodiment can prevent yellowing and maintain high transparency even when exposed for a long period of time under a high-temperature environment. Therefore, for example, an imaging lens of a camera (in-vehicle camera, digital camera, PC camera, mobile phone camera, surveillance camera, etc., especially wafer level camera), spectacle lens, light beam condensing lens, light diffusion As a lens etc., it can use suitably as a wafer level lens for in-vehicle cameras which especially heat resistance is calculated|required.

Furthermore, since the wafer-level lens obtained by the energy-sensitive composition of this embodiment is excellent in heat resistance, when mounted on a circuit board, it can be mounted by soldering by reflow. Therefore, the camera having such a wafer-level lens can be directly mounted on a printed circuit board (PCB) based on the same solder reflow process as the surface mounting of other electronic components, and very efficient product manufacturing is possible.

<Cured material>

The cured product according to the present invention is energy sensitive comprising at least one compound component (P) selected from the group consisting of the above-described compound (P1), compound (P2), and compound (Px) and a sulfonium salt (Q) It is the hardened|cured material which hardened|cured the composition. As described above, the cured product according to the present invention has excellent weight stability against heat. This is because the concentration of protons in the system containing the compound component (P) and the sulfonium salt (Q) increases by including the sulfonium salt (Q) in the energy-sensitive composition, so sequential polymerization in the compound component (P) is It is presumed that this is because the polymerization proceeds continuously, and there are few monomers that are decomposed by heat. The cured product is suitable, for example, as a sealing material for an organic EL display element, a wafer level lens, the above-mentioned hard coat, and the like. It is also suitable for flexible devices.

The hardened|cured material of this embodiment can also be set as the hardened|cured material with a high refractive index by selecting the component of an energy-sensitive composition. Preferred components from the viewpoint of obtaining a cured product having a high refractive index include, for example, metal oxide particles and an epoxy group-containing fluorene compound as the compound (P1), and these can be used alone or in combination of two or more, high refractive index It is preferable to use metal oxide particle|grains from the point of formation. The refractive index of the obtained cured product can obtain a high refractive index of 1.7 or more as a refractive index at a wavelength of 633 nm, for example, and when metal oxide particles are used, a high refractive index of 1.75 or more and further 1.8 or more is possible. Although the upper limit of the refractive index in the said wavelength 633 nm is not specifically limited, For example, they are 1.9 or less, 1.85 or less.

<Method for producing cured product>

The method for producing a cured product according to the present invention comprises at least one compound component (P) selected from the group consisting of the above-described compound (P1), compound (P2), and compound (Px) and a sulfonium salt (Q) polymerizing and/or crosslinking the energy sensitive composition. Since the energy-sensitive composition is energy-sensitive, it can be cured by polymerization and/or crosslinking by imparting active energy. The active energy to be imparted may be any one as long as it has energy to induce decomposition of the sulfonium salt (Q), and examples thereof include heat, visible light, ultraviolet rays, electron beams, and X-rays.

<Inkjet Ink>

The energy-sensitive composition according to the present embodiment has a viscosity of, for example, a value measured using an E-type viscometer at 25°C, and is 5000 mPa·s (5000 cP) or less, preferably 100 mPa·s (100 cP) When preparing low as follows, it can use suitably as an inkjet ink. The viscosity of the energy-sensitive composition of this embodiment used as an inkjet ink may be, for example, 1 mPa·s (1 cP) or more, or 10 mPa·s (10 cP) or more, as long as it is within the above range. It is preferable that the said energy-sensitive composition used as an inkjet ink is content of the sulfonium salt (Q) in the case of preparing to the above-mentioned low viscosity.

[Example]

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

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

In Examples 1-3 and Comparative Examples 1-9, the compound (P1) shown below, a sulfonium salt, etc. were mixed at the compounding ratio shown in Table 1, and the liquid mixture was produced. In addition, in Table 1, the unit of a compounding ratio is a mass part.

<Material>

[Compound (P1)]

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

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

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

[sulfonium salt]

○ Sulfonium salt represented by the following formula (Q1)

○ A sulfonium salt represented by the following formula (z1)

○ A sulfone compound represented by the following formula (z2)

○ Triphenylsulfoniumtetrakis(pentafluorophenyl)borate

[Evaluation 1]

The mixed solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 9 were subjected to a differential thermal/thermogravimetry apparatus (TG/DTA-6200, manufactured by Seiko Instruments) at 20° C. under the condition of a temperature increase rate of 10° C./min in an air stream. The temperature was raised to 250° C., and a TG/DSC curve was obtained. In the obtained TG curve, the weight reduction rate from the peak value was computed. The results are shown in Table 1. In addition, evaluation of a weight reduction rate is based on the following reference|standard.

○: Weight reduction rate of 10% or less

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

×: weight reduction rate of 40% or more

In addition, the TG/DSC curves obtained in Example 3 and Comparative Examples 7, 8 and 9 are shown in Figs. Moreover, the TG/DSC curve when the temperature of compound (P1) represented by Formula (P1-2a) alone was raised under the same conditions is shown in FIG. 5 as a reference example.

[Review]

As shown in the TG curves shown in Table 1 and FIGS. 1 to 4, in Examples 1 to 3 using the compound (P1) and the sulfonium salt (Q), the weight reduction rate was 10% or less, compared with Comparative Examples 1 to 9 It showed good high heat resistance. Moreover, in the DSC curve of Example 3 shown in FIG. 1, gentle peaks were seen at 110.6 degreeC and 222.3 degreeC. It is estimated that this is a peak indicating that the epoxy group of the compound (P1) is ring-opened and polymerization is proceeding sequentially, and it is inferred that polymerization is proceeding from a low temperature around 110°C. In contrast, sharp peaks were observed in the DSC curves of the comparative examples shown in FIGS. 2 to 4 . This is presumed to be a peak indicating that the sulfonium salt represented by the formula (z1) or the sulfone compound represented by the formula (z2) is decomposed, and it is presumed that the weight reduction rate increases accordingly. For example, as shown in FIG. 2, in Comparative Example 7, the weight decreased by about 65% at around 170°C. As shown in Fig. 3, in Comparative Example 8, the weight is decreased by about 30% around 150°C. As shown in FIG. 4 , in Comparative Example 9, the weight decreased by about 50% at around 170°C. In addition, from the result of FIG. 5, a sharp peak was seen at 50° C. or lower in the DSC curve alone with the compound (P1) represented by the formula (P1-2a), and at 50° C. or lower, it is expressed by the formula (P1-2a) It was confirmed that the decomposition of the compound (P1) used as the compound (P1) started, and the weight decreased from around 100°C until about 80% decreased at around 165°C.

[Evaluation 2]

The mixture obtained by changing the mass ratio of the mixed solution obtained in Example 1 to the compound of formula (P1-1a): the sulfonium salt of the formula (Q1) = 99:1 was applied on a glass substrate with a spin coater on a 20 μm thick coating film obtained ^{For example, after irradiating ghi rays with an exposure dose of 1000 mJ/cm 2} using HMW-532D (manufactured by ORC), the transmittance of the film at a wavelength of 400 nm was measured using MCPD-3000 (manufactured by Otsuka Electronics). did. The transmittance was 99.6%.

[Review]

From this result, in Examples 6 to 9 to be described later, the transmittance of the hard coat formed by coating the coating solution containing the same compound (P1) and sulfonium salt (Q) as in Example 1 on a polyimide film. It is suggested that there will be no adverse effect on

<<Examples 4 and 5>>

Bis-1-ethyl-3-oxetanylmethyl ether, which is an alicyclic epoxy compound represented by the formula (P1-1a) or an oxetane compound represented by the following formula (P1-7a) as the compound (P1), and The sulfonium salt represented by the formula (Q1) was mixed at the compounding ratio shown in Table 2, and the resulting mixture was ^{exposed (broadband) at an exposure dose of 100 mJ/cm 2} using an ultraviolet curing machine, followed by Example 4 at 150° C., 2 Post-baking was performed for minutes, and curing was attempted under curing conditions of not performing post-baking in Example 5, but the mixtures of Examples 4 and 5 were cured without generating a tack. . In addition, in Table 2, the unit of a compounding ratio is a mass part.

[Review]

From the results of Examples 4 and 5, even when using an oxetane compound as a compound component (P) - a compound (P1), it was confirmed that favorable sclerosis|hardenability was exhibited by mix|blending a sulfonium salt (Q). Moreover, it was confirmed from the result of Example 5 that even if it used together an oxetane compound and an alicyclic epoxy compound as a compound (P1), exhibiting favorable sclerosis|hardenability.

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

First, polyimide films 1 to 4 made of polyimide were prepared as follows.

[Method for Producing Polyimide Film 1]

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

0.03 g (0.03 wt%) of amorphous silica particles having OH groups bonded to the surface were added to N,N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, followed by ultrasonication until the solvent became transparent, and then 100 g of solid powder polyimide was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13 wt% solution. The solution thus obtained was applied to a stainless plate, cast to a thickness of 340 μm, dried with hot air at 130° C. for 30 minutes, and then the film was peeled from the stainless plate and fixed to the frame with pins. The frame to which the film was fixed was placed in a vacuum oven, and then slowly heated from 100° C. to 300° C. for 2 hours, cooled slowly, and separated from the frame to obtain a polyimide film. Thereafter, as a final heat treatment step, heat treatment was further performed at 300° C. for 30 minutes. The film thickness of the obtained polyimide film 1 was 50 micrometers, the total light transmittance was 88 %, and yellowness (YI) was 2.5.

[Method for Producing Polyimide Film 2]

On one side of polyimide film 1, a solution of 2 wt% of polysilazane (MOPS-1800, manufactured by Az Materials) having a weight average molecular weight of 2000 g/mol in dibutyl ether (DBE) was applied with a wire. Then, it was dried at a temperature of about 80° C. to form a polysilazane film having a thickness of 300 nm. Thereafter, after standing at room temperature for about 5 minutes, the polysilazane film is thermally cured at a temperature of about 250° C. to form a silicon oxide layer, and polyimide film 2 having a structure of a colorless transparent polyimide film/silicon oxide layer is prepared prepared. The film thickness of the obtained polyimide film 2 was 50 micrometers, the total light transmittance was 92 %, and yellowness (YI) was 1.0.

[Method for Producing Polyimide Film 3]

1000 g of N-methylpyrrolidone (NMP) was added to a 3 L separable flask equipped with an oil bath and equipped with a stirring bar while nitrogen gas was introduced, and 3,3-(diaminodiphenyl)sulfone (referred to as diamine 1) 232.4 g of pyromellitic dianhydride was added while stirring, and then 218.12 g of pyromellitic dianhydride was added, followed by stirring at room temperature for 30 minutes. This was heated to 50° C. and stirred for 12 hours, then 105.6 g of both terminal amine-modified methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400)) was dissolved in 298 g of NMP, and a dropping funnel was used. Thus, it was added dropwise. After heating up to 80 degreeC and stirring for 1 hour, the oil bath was removed, and it returned to room temperature, and the NMP solution of a transparent polyamic acid (it is also described hereafter as varnish) was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid was 84000.

The varnish is applied to an alkali-free glass substrate (thickness 0.7 mm) with a bar coater, leveled at room temperature for 5 minutes to 10 minutes, and a vertical curing oven (manufactured by Koyo Lindbergh, model). VF-2000B) at 140°C for 60 minutes, further heated at 350°C for 60 minutes under a nitrogen atmosphere (oxygen concentration: 100 ppm), left still at room temperature for 24 hours, the resin film is peeled from the glass, and polyimide A film was made. The film thickness of the obtained polyimide film 3 was 20 micrometers, the total light transmittance was 88 %, and yellowness (YI) was 7.0.

[Method for Producing Polyimide Film 4]

(Synthesis of imidazole compound (d))

First, 30 g of a cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added in methanol. Then, the methanol solution was stirred at 40°C. Methanol was distilled off, and the residue was suspended in 200 g of water. 200 g of tetrahydrofuran was mixed with the obtained suspension and stirred, and the aqueous phase was liquid-separated. After adding and stirring 4 g of hydrochloric acid under ice cooling, 100 g of ethyl acetate was mixed and stirred. After allowing the liquid mixture to stand, the oil phase was fractionated. The target substance was crystallized from the oil phase, the precipitate was collect|recovered, and the imidazole compound (d) of the following structure was obtained.

(Preparation of tetracarboxylic dianhydride)

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

(Preparation of polyamic acid)

First, a 30 ml three-necked flask was heated with a heat arm and dried sufficiently. Next, the atmospheric gas in the three necked flask was replaced with nitrogen, and the inside of the three necked flask was made into nitrogen atmosphere. In a 3-neck flask, 0.2045 g (0.90 mmol: Nippon Sunyang Pharmaceutical Co., Ltd.: DABAN) of 4,4'-diaminobenzanilide was added, and then N,N,N',N'-tetramethylurea (TMU) was added. 3.12 g was added. The contents of the three-neck flask were stirred to obtain a slurry liquid in which aromatic diamine (DABAN) was dispersed in TMU.

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

(Addition step of imidazole compound (d))

To the reaction solution obtained as described above, the imidazole compound (d) synthesized under a nitrogen atmosphere (0.206 g, 5.6 parts by mass relative to the case where the reaction solution was 100 parts by mass) was added. Next, the reaction solution was stirred at 25°C for 12 hours to obtain a liquid composition containing the imidazole compound (d) and polyamic acid. The polyimide precursor composition which added 1.5 mass parts of silane coupling agents represented by a following formula as an additive with respect to 100 mass parts of solid content in the said composition was obtained.

(Preparation of polyimide film)

The thickness of the coating film after heat curing of the polyimide precursor composition obtained as described above on a glass substrate (large slide glass, trade name "S9213" manufactured by Matsunami Chozo Industry Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm) It was spin-coated so that it might become 13 micrometers, and the coating film was formed. Next, the glass substrate on which the coating film was formed was placed on a hot plate at 60 DEG C, left still for 2 hours, and the solvent was removed from the coating film by evaporation.

After removal of the solvent, the glass substrate on which the coating film was formed was put into an inert oven in which nitrogen was flowing at a flow rate of 3 L/min.

In an inert oven, under a nitrogen atmosphere (oxygen concentration of 100 ppm), after standing at a temperature condition of 25°C for 0.5 hours, heated at a temperature condition of 135°C for 0.5 hours, and further under a temperature condition of 300°C (final heating temperature) ), the coating film was hardened by heating, and the polyimide coated glass in which the thin film (polyimide film) which consists of polyimide was coated on the said glass substrate was obtained.

The obtained polyimide coated glass was immersed in hot water at 90°C to peel the polyimide film from the glass substrate to obtain a polyimide film 4 (a film having a size of 76 mm in length, 52 mm in width, and 13 µm in thickness).

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

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

In addition, the value (unit: %) of the total light transmittance of the film, and the yellowness (YI) were measured in JIS K7361-1 (published in 1997) using the product name "Hazemeter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device. It calculated|required by performing the measurement based on it.

[Preparation of coating solution]

An energy photosensitive composition containing the compound (P1) represented by the formula (P1-1a) and the sulfonium salt represented by the formula (Q1) in a mass ratio of 99:1 as a solvent (propylene glycol monomethyl ether acetate (PGMEA)) was dissolved to prepare a coating solution 1 having a solvent ratio of 80% by mass.

[Preparation of coating liquid for comparison]

A photosensitive composition containing an acryl monomer (dipentaerythritol hexaacrylate) and a polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone) in a mass ratio of 99:1 is dissolved in a solvent (PGMEA), the solvent ratio A coating solution 2 for comparison used as this 80% by mass was prepared.

[Evaluation 3]

Each of the coating solution 1 and the coating solution 2 for comparison was applied to one side of the polyimide films 1 to 4 attached to the wafer by a spin coater, and then dried at a temperature of 80° C. to obtain a 4 μm thick coating film. ^{Thereafter, the coating layer was irradiated at 100 mJ/cm 2} using an ultraviolet curing machine having a wavelength of 365 nm to obtain each polyimide film having a hard coat (cured film) formed on one side. Each obtained polyimide film was peeled from the wafer, and the external appearance was observed visually.

[Results and considerations]

In all of the polyimide films 1 to 4 (Examples 6 to 9) in which the hard coat was formed using the coating solution 1 according to the present example, the transparency of the film did not deteriorate, and the film curl due to curing of the coating solution or the hard coat. It was confirmed that the degree of was small and the cure shrinkage was small.

On the other hand, in the polyimide films 1-4 (Comparative Examples 10-13) in which the hard coat was formed using the coating liquid 2 for comparison, it discolored slightly yellow, and the curl by hardening of the coating liquid or hard coat was large. It was confirmed that the hard coat made of the coating solution 1 according to this example had a smaller cure shrinkage rate than the hard coat made of the coating solution 2, and the degree of deformation of the polyimide film to be applied was suppressed.

[Evaluation 4]

In evaluation 3, the value of the surface resistance of each hard coat formed on the polyimide films 1 to 4 was measured by Hiresta MCP-HT450 (manufactured by Mitsubishi Analytech), probe UR-100, and a measurement voltage of 1,000 V. Any surface resistance value ^{exceeded 1ㅧ10 15} Ω.

From this result, it was confirmed that the coating liquid 1 concerning this Example can form a hard coat with high surface resistance.

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

In Examples 10 to 14 and Comparative Examples 14 to 15, the compounds (P1-1a) and (P1-2a), the sulfonium salt (Q1) used in Examples 1 and 3, the compound (P1-6d) shown below, and sulfo The nium salt etc. (z3) were mixed in the compounding ratio shown in Table 1, and the liquid mixture was produced. In addition, in Table 3, the unit of a compounding ratio is a mass part.

<Material>

[Compound (p1-6d)]

[sulfonium salt, etc. (z3)]

[Evaluation 5]

The viscosity of the liquid mixture obtained in Examples 10-14 and Comparative Examples 14-15 was measured at 25 degreeC and 1-100 rpm conditions using the E-type viscometer. The results are shown in Table 3. In addition, the viscosity of compound (P1-1a) is about 60 mPa·s (60 cP), the viscosity of compound (P1-2a) is about 20 mPa·s (20 cP), and the viscosity of compound (P1-6d) is 200 It was about mPa·s (200 cP).

0.3 g of the mixture obtained in Examples 10 to 14 and Comparative Examples 14 to 15 was precisely sealed in a glass vial, and exposed to light at an exposure ^{dose of 1500 mJ/cm 2 using an ultraviolet irradiator (HMW-532 D, manufactured by ORC).} , and post-baking at 100°C for 15 minutes and at 85°C for 100 hours to prepare each sample.

Each of the above samples was set in a headspace sampler (Turbo Matrix ATD, manufactured by Perkin Elmer), heated at 100° C. for 30 minutes, and then out using a gas chromatography mass spectrometer (Clarus 580, manufactured by Perkin Elmer). Gas was measured. The results are shown in Table 3. In addition, the measured value (area %) of the comparative example 14 in a table|surface is shown with the relative value which made 100.

[Review]

As shown in Table 3, Example 10 using the compound (P1-1a) and the sulfonium salt (Q1) compared with Comparative Example 14 not using the sulfonium salt (Q1) had the same viscosity and the amount of outgas generated little was confirmed. Similarly, Example 14 using the compound (P1-1a), the compound (P1-6d), and the sulfonium salt (Q1) compared with Comparative Example 15 not using the sulfonium salt (Q1) had the same viscosity as the outgas was found to be low.

Moreover, as can be seen from the results of Examples 10 and 11, it was confirmed that the amount of the sulfonium salt (Q1) was effective in reducing the outgas by reducing the viscosity of the mixed solution (energy-sensitive composition) even in a very small amount. Similarly, as can be seen from the results of Examples 12 and 13, it was confirmed that the amount of the sulfonium salt (Q1) was effective in reducing the outgas by reducing the viscosity of the mixed solution (energy-sensitive composition) even in a very small amount.

From the results of Examples 11 and 12, when the total content of the compound component (P) to the compound (P1) is the same, as the compound component (P) to the compound (P1), the compound (P1) rather than the compound (P1-1a) alone It was confirmed that using -1a) and compound (P1-2a) together reduced the viscosity of the liquid mixture (energy-sensitive composition) and had an effect of reducing outgas. From this, when it is preferable to use together the alicyclic epoxy compound represented by the above-mentioned formula (P1-1) and the alicyclic epoxy compound represented by a formula (P1-2) as a compound component (P) - a compound (P1) It is suggested that there is

<<Examples 15-24>>

[Preparation of energy-sensitive composition of high refractive index]

In Examples 15 to 24, the cationic and/or acid catalytically polymerizable and/or crosslinkable compound (P1) and sulfonium salt etc. shown below were mixed in the compounding ratio shown in Table 4, and energy-sensitive composition was produced. In addition, in Table 4, the unit of a compounding ratio is a mass part, and the compounding ratio of a solvent is mass ratio. In Example 23, it was prepared by further adding 10 parts by mass of cerium oxide (average particle size: 50 nm) to 100 parts by mass of the total of the component (P1) and (Q1) of Example 15. In Example 24, 100 mass parts of titanium oxide (average particle diameter: 5-10 nm) was further added with respect to 100 mass parts of total of (P1) component and (Q1) of Example 15, and it was prepared. In Examples 15-23, the amount of solvent was adjusted so that the density|concentration of the component except a solvent might become 20 mass %. In Example 24, the solvent amount was adjusted so that the density|concentration of the component except a solvent might be 10 mass %.

<Material>

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

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

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

[Alkali-soluble resin]

○ Preparation of alkali-soluble resin (A1a)

First, in a 500 ml four-necked flask, 0.34 mol of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 0.68 mol of acrylic acid, 139.0 g of propylene glycol monomethyl ether acetate and tetraethylammonium bromide (TEAB) ) was added and reacted by stirring for 20 hr under heating at 100 to 105°C. Then, 0.12 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 0.27 mol of 1,2,3,6-tetrahydrophthalic anhydride were added into the flask, and heated at 120 to 125° C. for 8 hours. It was stirred and reacted. Furthermore, 0.28 mol of glycidyl methacrylate was thrown in, it stirred under heating at 100-105 degreeC for 8 hours, and alkali-soluble resin (A1a) was obtained. The solid content concentration of the obtained alkali-soluble resin (A1a) was 57.0 wt%, the acid value (solid content conversion) was 82 mgKOH/g, and Mw by GPC analysis was 3500.

○ Preparation of alkali-soluble resin (A2a)

First, in a 500 ml four-neck flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid are put Then, it was dissolved by heating at 90-100° C. while blowing air at a rate of 25 ml/min. Then, while the solution was in a cloudy state, the temperature was gradually increased, and the solution was completely dissolved by heating at 120°C. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring was continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (f-4) which is colorless and transparent and is solid.

Next, 600 g of 3-methoxybutyl acetate was added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually increased. Thus, the reaction was carried out at 110 to 115°C for 4 hours. After confirming disappearance of an acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, it was made to react at 90 degreeC for 6 hours, and alkali-soluble resin (A2a) which has a card|card structure was obtained. The disappearance of the acid anhydride group was confirmed by the IR spectrum.

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

[additive]

○ (Add-1)

Polyether-modified polydimethylsiloxane [manufactured by Bick Chemie Japan, BYK302]

○ (Add-2)

Perfluoroalkyl group-containing oligomer [manufactured by DIC, F-477]

[solvent]

○ (S1) cyclohexyl acetate

○ (S2) Diethylene glycol monobutyl ether acetate ester

○ (S3) Propylene glycol monomethyl ether acetate ester

○ (S4) Diethylene glycol methyl ethyl ether

○ (S5) N-methylpyrrolidone

[Evaluation 6]

Each of the energy-sensitive compositions of Examples 15 to 24 was applied to a glass substrate using a spin coater, pre-baked at 100° C. for 120 seconds, and exposure (broadband) at an exposure ^{dose of 100 mJ/cm 2 using an ultraviolet curing machine.} After that, a post-baking process was performed at 150°C for 20 minutes (230°C for Example 24, for 20 minutes). The film thickness of the cured film of Examples 15-23 was 500 nm, and Example 24 was 50 nm. Each cured film has heat resistance. About each cured film, the refractive index in wavelength 633nm was measured. In all compositions, it was confirmed that the composition had a refractive index of 1.7 or higher and a high refractive index. In particular, the cured film of Example 23 to which cerium oxide which is a metal oxide particle was added had a refractive index of 1.75 or more, and in Example 24 to which titanium oxide was added, it was 1.8 or more, and both were able to achieve high refractive index (transparency).

In addition, with respect to heat resistance, each energy-sensitive composition of Examples 15 to 24 was applied to a glass substrate using a spin coater, prebaked at 100° C. for 120 seconds, and exposure amount 100 mJ/cm ^{2 using an ultraviolet curing machine.} After exposure (broadband) to , a post-baking treatment was performed at 230°C for 20 minutes to obtain a cured film having a cured film thickness of about 50 nm. The film thickness change rate when each cured film was further heated up to 250 degreeC was 10 % or less, and it was confirmed that there exists heat resistance.

Claims (7)

(P1) cationic and/or acid catalytically polymerizable and/or crosslinkable compounds;
(P2) a compound that increases its solubility in a developer under the action of an acid, and
(Px) radically polymerizable or crosslinkable compound
At least one compound component (P) selected from the group consisting of,
(Q) a sulfonium salt represented by the following formula (a1)
An energy-sensitive composition comprising a.

(Wherein, R ¹ and R ² independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (a2), and R ¹ and R ² are bonded to each other to form a ring together with the sulfur atom in the formula. may be, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, X ⁻ represents a monovalent anion, provided that , R ¹ and R ² are not an alkyl group which may be simultaneously substituted with a halogen atom.)

(Wherein, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ represents an optionally substituted alkyl group 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, or a thienylcarbonyl group. , furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy (poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro represents a group or a halogen atom, and m ¹ represents an integer of 0 or more)

(wherein R ⁵ is 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 aryl group An oxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or an alkylene group optionally substituted with a halogen atom; A group represented by the following formula (a5) is represented, and R ⁶ is 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 hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom represents an optionally substituted alkyl group or a group represented by the following formula (a6), A ² represents a single bond, S, O, a sulfinyl group, or a carbonyl group, n1 represents 0 or 1)

(Wherein, R ⁷ and R ⁸ are independently 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, Heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom represents an alkylene group or a group represented by the following formula (a5), R ⁹ and R ¹⁰ independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the formula (a2), R ⁹ and R ¹⁰ may combine with each other to form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, X ^- is the same as above, n2 represents 0 or 1, However, R ⁹ and R ¹⁰ are not an alkyl group which may be simultaneously substituted with a halogen atom.)

(Wherein, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ represents an optionally substituted alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. , arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted represents an amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more)

(Wherein, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an optionally substituted alkyl group with a halogen atom, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, or an acyloxy group. , arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, represents a hydroxy (poly)alkyleneoxy group, an optionally substituted amino group, cyano group, nitro group, or halogen atom, and m3 represents an integer of 0 or more) The method according to claim 1,
The compound component (P) is the compound (P1),
The (P1) compound is an epoxy compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, and an alicyclic epoxy group, an energy-sensitive composition. The method according to claim 1,
The sulfonium salt is an ^{energy-sensitive composition, wherein the monovalent anion represented by X −} is a boron-containing anion represented by the following general formula.
R ^x1 _c BY _4-c ^-
(wherein, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4) The method according to claim 1,
The energy-sensitive composition, wherein in the thermogravimetric measurement (TG) in which the temperature is raised to 230°C at a temperature increase rate of 10°C/min in the air stream, the weight loss rate from the peak value is 10% or less. A method of using the energy-sensitive composition of any one of claims 1 to 4 in an encapsulant for an organic EL display device or a curable composition for a wafer-level lens. A cured product obtained by curing the energy-sensitive composition of any one of claims 1 to 4. A method for producing a cured product, comprising polymerizing and/or crosslinking the energy-sensitive composition of any one of claims 1 to 4.

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