JP7316398B2 - ENERGY-SENSITIVE COMPOSITION, CURED PRODUCT AND METHOD FOR PRODUCING CURED PRODUCT - Google Patents

Description

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

Conventionally, it has been proposed to contain an epoxy compound in a sealant for an organic EL display device or an energy sensitive composition for a wafer level lens. For example, Patent Document 1 discloses that an energy-sensitive resin capable of suppressing the generation of outgassing that causes deterioration of an organic EL display element has an epoxy group or an oxetanyl group, and an ether group other than the epoxy group or the oxetanyl group. An energy sensitive resin composition free of bonds and ester bonds has been proposed. In addition, Patent Document 2 describes an alicyclic epoxy compound having a specific structure and two or more glycidyl groups in the molecule as an energy-sensitive resin that suppresses yellowing even in a high-temperature environment and has excellent transparency and curability. and an energy-sensitive resin composition containing a curing agent.

WO2015/064410 WO2015/129503

However, conventional energy-sensitive compositions are required to have weight stability in high-temperature environments.

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.

The present inventors have found that thermogravimetric stability is improved by using a sulfonium salt having a specific structure, and have completed the present invention.

A first aspect of the present invention comprises (P1) a cationically and/or acid-catalysically 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 containing a sulfonium salt represented by the following formula (a1) It is a thing.

（式中、Ｒ^１及びＲ^２は独立に、ハロゲン原子で置換されていてもよいアルキル基又は下記式（ａ２）で表される基を示し、Ｒ^１及びＲ^２は相互に結合して式中の硫黄原子と共に環を形成してもよく、Ｒ^３は下記式（ａ３）で表される基又は下記式（ａ４）で表される基を示し、Ａ^１はＳ、Ｏ、又はＳｅを示し、Ｘ^－は１価のアニオンを示し、但し、Ｒ^１及びＲ^２は、同時に、ハロゲン原子で置換されていてもよいアルキル基ではない。）

(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 mutually bonded to form A ring may be formed with the sulfur atom in R ³ is a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ is S, O, or Se and X ^- represents a monovalent anion, provided that R ¹ and R ² are not alkyl groups optionally substituted with halogen atoms at the same time.)

（式中、環Ｚ^１は芳香族炭化水素環を示し、Ｒ^４はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アルコキシカルボニル基、アシロキシ基、アルキルチオ基、チエニル基、チエニルカルボニル基、フラニル基、フラニルカルボニル基、セレノフェニル基、セレノフェニルカルボニル基、複素環式脂肪族炭化水素基、アルキルスルフィニル基、アルキルスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ１は０以上の整数を示す。）

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

（式中、Ｒ^５はヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキレン基又は下記式（ａ５）で表される基を示し、Ｒ^６はヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキル基又は下記式（ａ６）で表される基を示し、Ａ^２は単結合、Ｓ、Ｏ、スルフィニル基、又はカルボニル基を示し、ｎ１は０又は１を示す。）

(Wherein ^R5 is a hydroxy 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 a 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 alkylene group or a group represented by the following formula (a5), wherein R ⁶ is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthio carbonyl group, 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, represents an optionally substituted amino group, a cyano group, a nitro group, or an optionally halogen-substituted alkyl group or a group represented by the following formula (a6), wherein A ² is a single bond, S, O, represents a sulfinyl group or a carbonyl group, and n1 represents 0 or 1.)

（式中、Ｒ^７及びＲ^８は独立に、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキレン基又は下記式（ａ５）で表される基を示し、Ｒ^９及びＲ^１０は独立に、ハロゲン原子で置換されていてもよいアルキル基又は上記式（ａ２）で表される基を示し、Ｒ^９及びＲ^１０は相互に結合して式中の硫黄原子と共に環を形成してもよく、Ａ^３は単結合、Ｓ、Ｏ、スルフィニル基、又はカルボニル基を示し、Ｘ^－は前記のとおりであり、ｎ２は０又は１を示し、但し、Ｒ^９及びＲ^１０は、同時に、ハロゲン原子で置換されていてもよいアルキル基ではない。）

(wherein R ⁷ and R ⁸ are independently a hydroxy 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, 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 or an alkylene group optionally substituted with a halogen atom or a group represented by the following formula (a5), wherein R ⁹ and R ¹⁰ are independently an alkyl group optionally substituted with a halogen atom or the above represents a group represented by 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 is a single bond, S, O, a sulfinyl group, or a carbonyl group, X ^- is as described above, n2 is 0 or 1, provided that R ⁹ and R ¹⁰ are not simultaneously an alkyl group optionally substituted with a halogen atom.)

（式中、環Ｚ^２は芳香族炭化水素環を示し、Ｒ^１１はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ２は０以上の整数を示す。）

(In the formula, ring ^Z2 represents an aromatic hydrocarbon ring, and ^R11 represents an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryl oxycarbonyl group, arylthiocarbonyl group, 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, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 is an integer of 0 or more.)

（式中、環Ｚ^３は芳香族炭化水素環を示し、Ｒ^１２はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、チエニルカルボニル基、フラニルカルボニル基、セレノフェニルカルボニル基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ３は０以上の整数を示す。）

(Wherein, ring Z ³ represents an aromatic hydrocarbon ring, R ¹² represents an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryl oxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, 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, and m3 is an integer of 0 or greater.)

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 cross-linking 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 which hardened|cured this composition, and the manufacturing method of this hardened|cured material can be provided.

4 is a TG/DSC curve showing the thermogravimetric change of Example 3. FIG. 10 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 7. FIG. 4 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 8. FIG. 10 is a TG/DSC curve showing the thermogravimetric change of Comparative Example 9. FIG. It is a TG/DSC curve which shows the thermogravimetric change of a reference example.

Embodiments of the present invention will be described in detail below, but the present invention is by no means limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. .
In this specification, descriptions such as "A and/or B", "A and/or B", "A and/or B", such as "cationically and/or acid-catalyzed", mean " at least one selected from the group consisting of A and B". where A and B are arbitrary terms.

<Energy Sensitive Composition>
The energy-sensitive composition according to the present invention comprises (P1) a cationically and/or acid-catalyzed polymerizable and/or crosslinkable compound, (P2) increasing its solubility in a developer under the action of an acid compound, (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 formula (a1) above.

The energy-sensitive composition according to the present invention contains the sulfonium salt represented by the formula (a1) (hereinafter also referred to as "sulfonium salt (Q)"), whereby the compound component (P) and the sulfonium salt (Q ), the concentration of protons increases as the temperature rises, so the sequential polymerization in the compound component (P) proceeds continuously and polymerization is promoted, and it is presumed that the amount of thermally decomposed monomers is small. As a result, the energy-sensitive composition according to the present invention is presumed to have improved weight stability against heat. 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 a mode in which protons are generated by abstracting hydrogen from components in the system.

[(P1) Cationic and/or acid catalytically polymerizable and/or crosslinkable compound]
The cationically and/or acid-catalyzed polymerizable and/or crosslinkable compound (hereinafter also referred to as "compound (P1)") can be cationically polymerized by, for example, an alkyl group- or aryl group-containing cation or by protons. Contains compounds. Examples thereof include cyclic ethers, especially epoxy and oxetane compounds, as well as vinyl ether compounds and hydroxy-containing compounds. Lactone compounds and cyclic thioether compounds and vinyl thioether compounds can also be used. However, in this specification, when the compound having an ethylenically unsaturated group (vinyl group) is a compound also having an epoxy group and/or an oxetanyl group (epoxy-oxetanyl group-containing/vinyl group-containing compound), the compound ( P1), and other compounds (epoxy/oxetanyl group-free/vinyl group-containing compounds) are referred to as compounds (Px). In this specification, "epoxy" generally includes not only oxiranyl but also oxetanyl and cycloaliphatic epoxies, unless otherwise specified.

Further examples include aminoplastics or phenolic resole resins. These are especially melamine, urea, epoxy, phenolic, acrylic, polyester and alkyd resins, but especially mixtures of acrylic, polyester or alkyd resins with melamine resins. These also include modified surface coating resins (eg, acrylic-modified polyester resins, acrylic-modified alkyd resins, etc.). The term surface coating resin preferably includes amino resins. Examples thereof include etherified and non-etherified melamine resins, urea resins, guanidine resins, biuret resins. Acid catalysts for the curing of surface coatings containing etherified amino resins (e.g., methylated or butylated melamine resins (N-methoxymethyl-melamine or N-butoxymethyl-melamine) and methylated/butylated glycoluril) especially important.

When the compound (P1) is an epoxy compound, it is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, preferably a compound having at least two epoxy groups in the molecule. The epoxy compound can be selected from various compounds having an epoxy group that are conventionally blended in curable compositions. The epoxy compound may be a low-molecular-weight compound having an epoxy group, which is a non-polymer, or a polymer having an epoxy group, but is preferably a non-polymer. As the non-polymer having an epoxy group, an aliphatic epoxy compound containing no aromatic group is preferable because the cured product formed using the energy-sensitive composition has excellent thermogravimetric stability. Among the aliphatic epoxy compounds, an aliphatic epoxy compound having an alicyclic epoxy group is preferable because ring-opening polymerization promotes sequential polymerization and promotes polymerization.

Specific examples of aliphatic epoxy compounds having an alicyclic epoxy group include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4 -epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, β-methyl-δ - Valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, methylenebis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, and di-2-ethylhexyl epoxycyclohexahydrophthalate, an epoxy resin having a tricyclodecene oxide group, and the following formula (P1-1) and compounds represented by (P1-5). Among specific examples of these aliphatic epoxy compounds, alicyclic epoxy compounds represented by the following formulas (P1-1) to (P1-4) are preferred in that sequential polymerization proceeds and polymerization is promoted. Alicyclic epoxy compounds represented by the following formulas (P1-1) and (P1-2) are preferred, and more preferred. These alicyclic epoxy compounds may be used alone or in combination of two or more. As the compound component (P) to the compound (P1), particularly when it is desirable to reduce outgassing, an alicyclic epoxy compound represented by the formula (P1-1) or the compound represented by the formula (P1-2) It preferably contains at least one of the group consisting of an alicyclic epoxy compound and an alicyclic epoxy compound represented by the formula (P1-8), and the proportion of the total compound component (P) to compound (P1) is 1. ~99 wt%, such as 10-90 wt%, 20-80 wt%, 30-70 wt%, 40-60 wt%. 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) reduces outgassing and reduces the viscosity of the energy-sensitive composition). It is preferable in that it allows When the alicyclic epoxy compound represented by formula (P1-1) and the alicyclic epoxy compound represented by formula (P1-2) are used in combination, the alicyclic epoxy compound represented by formula (P1-1) The content of the alicyclic epoxy compound represented by the formula (P1-1) with respect to the total amount of the epoxy compound and the alicyclic epoxy compound represented by the formula (P1-2) is not particularly limited. It may be 1 to 99% by mass, 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, 40 to 60% by mass, and the like.

（式（Ｐ１－１）中、Ｚは単結合又は連結基（１以上の原子を有する二価の基）を示す。Ｒ^ａ１～Ｒ^ａ１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基であり、例えば、水素原子、ハロゲン原子、又は酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。）

(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 each independently represent a hydrogen atom, a halogen atom, and an organic is a group selected from the group consisting of, for example, a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an oxygen atom or a halogen atom, each of which may be the same or different; is also good.)

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

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

R ^a19 is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.

As the compound represented by the formula (P1-1), a compound that does not easily form a conjugated structure (especially a π-electron conjugated structure) by dehydrogenation produces a cured product that has excellent transparency in addition to thermogravimetric stability. In particular, an alicyclic epoxy compound, specifically, two alicyclic epoxy groups in one molecule via a linking group containing a quaternary carbon and/or a hetero atom Bonding compounds are preferred.

Further, the compound (P1) includes alicyclic epoxy compounds represented by the following formulas (P1-2) to (P1-5).

（式（Ｐ１－２）中、Ｒ^ａ１～Ｒ^ａ１２は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基であり、例えば、水素原子、ハロゲン原子、又は酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｒ^ａ２及びＲ^ａ１０は、互いに結合してもよい。）

(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 is a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different, and R ^a2 and R ^a10 may be bonded to each other.)

（式（Ｐ１－３）中、Ｒ^ａ１～Ｒ^ａ１０は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基であり、例えば、水素原子、ハロゲン原子、又は酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｒ^ａ２及びＲ^ａ８は、互いに結合してもよい。）

(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 a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different, and R ^a2 and R ^a8 may be bonded to each other.)

（式（Ｐ１－４）中、Ｒ^ａ１～Ｒ^ａ１２は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基であり、例えば、水素原子、ハロゲン原子、又は酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｒ^ａ２及びＲ^ａ１０は、互いに結合してもよい。）

(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 is a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different, and R ^a2 and R ^a10 may be bonded to each other.)

（式（Ｐ１－５）中、Ｒ^ａ１～Ｒ^ａ１２は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基であり、例えば、水素原子、ハロゲン原子、又は酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。）

(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 It is a hydrocarbon group that may contain an atom or a halogen atom, and may be the same or different.)

In formula (P1-1), when R ^a1 to R ^a12 are organic groups, the organic groups are not particularly limited as long as they do not hinder the object of the present invention. or a group containing hetero atoms such as halogen atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms in addition to carbon atoms and hydrogen atoms. Examples of halogen atoms include chlorine, bromine, iodine, and fluorine atoms.

The organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom, and a halogen atom, a carbon atom, and a hydrogen atom. , an oxygen atom and a halogen atom are preferred. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms in the organic group is preferably 1-20, more preferably 1-10, and particularly preferably 1-5.

Specific examples of hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and 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-hexadecyl group , n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and chain alkyl groups such as n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n -chain alkenyl groups such as butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and 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, and aryl groups such as 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 halogenated hydrocarbon groups include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl groups such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , and halogenated cycloalkyl groups such as 4-bromocyclohexyl 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, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl Halogenated aryl groups such as group, 4-fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl halogenated aralkyl groups such as a methyl group, a 2-fluorophenylmethyl group, a 3-fluorophenylmethyl group and a 4-fluorophenylmethyl group;

Specific examples of groups consisting of carbon atoms, hydrogen atoms, and oxygen atoms include hydroxy chain groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group. Alkyl group; Halogenated cycloalkyl group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 -hydroxyaryl groups such as a dihydroxyphenyl group, a 2,4-dihydroxyphenyl group, a 2,5-dihydroxyphenyl group, a 2,6-dihydroxyphenyl group, a 3,4-dihydroxyphenyl group, and a 3,5-dihydroxyphenyl group hydroxyaralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 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, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, Chain alkoxy groups such as n-nonadecyloxy group and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group and chain alkenyloxy groups such as 3-n-butenyloxy; phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, α-naphthyloxy, β-naphthyloxy, biphenyl-4 -yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and aryloxy group such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, Aralkyloxy groups such as β-naphthylmethyloxy, α-naphthylethyloxy, and β-naphthylethyloxy; methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxy ethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4 Alkoxyalkyl groups such as -ethoxy-n-butyl group and 4-n-propoxy-n-butyl group; methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy 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 Alkoxyalkoxy groups such as -n-butyloxy group and 4-n-propoxy-n-butyloxy group; Alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group and 4-methoxyphenyl group; 2-methoxy Alkoxyaryloxy groups such as phenoxy, 3-methoxyphenoxy, and 4-methoxyphenoxy; formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, and aliphatic acyl groups such as decanoyl; aromatic acyl groups such as benzoyl, α-naphthoyl, and β-naphthoyl; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butyloxycarbonyl, Chain alkyloxycarbonyl groups such as n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group; Aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group, and β-naphthoxycarbonyl group; formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy aliphatic acyloxy groups such as heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy groups; aromatic acyloxy groups such as benzoyloxy, α-naphthoyloxy, and β-naphthoyloxy groups; is the base.

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, particularly energy All of R ^a1 to R ^a18 are more preferably hydrogen atoms from the viewpoint that the cured product obtained using the sensitive composition has excellent mechanical properties.

In formulas (P1-2) to (P1-5), R ^a1 to R ^a12 are the same as R ^a1 to R ^a12 in formula (P1-1). In formulas (P1-2) and (P1-4), examples of the divalent group formed when R ^a2 and R ^a10 are bonded to each other include —CH ₂ — and —C(CH ₃ ) _2- . In formula (P1-3), examples of the divalent group formed when R ^a2 and R ^a8 are bonded together include —CH ₂ — and —C(CH ₃ ) ₂ —.

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

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

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

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

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

In addition to the aliphatic epoxy compounds having an alicyclic epoxy group described above, examples of non-polymers having an epoxy group that can be used as the compound (P1) 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- Epoxyalkyloxyalkyls such as propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate and 6-glycidyloxy-n-hexyl (meth)acrylate (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; phenol novolac type epoxy Novolak epoxy resins such as resins, brominated phenol novolak type epoxy resins, ortho-cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, and bisphenol AD novolak type epoxy resins; Aliphatic epoxy resins; aromatic epoxy resins such as epoxides of naphthalene-type phenolic resins; 9,9-bis[4-(glycidyloxy)phenyl]-9H-fluorene, 9,9-bis[4-[2-( glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3 -methylphenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, and 9,9-bis(6-glycidyloxynaphthalen-2-yl )-9H-fluorene, 9,9-bis(6-glycidyloxynaphthalen-1-yl)-9H-fluorene, 9,9-bis(5-glycidyloxynaphthalene-1-yl)-9H-fluorene, etc. ,9-bis(glycidyloxynaphthyl)fluorenes; 9,9-bis[6-(2-glycidyloxyethoxy)naphthalen-2-yl]-9H-fluorene, 9,9-bis[6-(2-glycidyl Oxypropoxy)naphthalen-2-yl]fluorene, 9,9-bis[5-(2-glycidyloxyethoxy)naphthalen-1-yl]fluorene, 9,9-bis[5-(2-glycidyloxypropoxy)naphthalene 9,9-bis(glycidyloxyalkoxynaphthyl)fluorenes such as -1-yl]fluorene; 9,9-bis{6-[2-(2-glycidyloxyethoxy)ethoxy]naphthalen-2-yl}-9H -fluorene, 9,9-bis{6-[2-(2-glycidyloxypropoxy)propoxy]naphthalen-2-yl}-9H-fluorene, 9,9-bis{5-[2-(2-glycidyloxy) 9,9 such as ethoxy)ethoxy]naphthalen-1-yl}-9H-fluorene, 9,9-bis{5-[2-(2-glycidyloxypropoxy)propoxy]naphthalen-1-yl}-9H-fluorene -epoxy group-containing fluorene compounds such as bis(glycidyloxydialkoxynaphthyl) fluorenes; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; Glycidylamine type epoxy resins such as tetraglycidyl metaxylylenediamine and tetraglycidylbisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; Phenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl ]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxy Trifunctional epoxy resins such as propoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether and tetraglycides Examples include tetrafunctional epoxy resins such as xibiphenyl, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-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).
3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3-hydroxymethyloxetanyl methacrylate, bis-1-ethyl-3-oxetanylmethyl ether, 1,4-bis-3-ethyloxetane -3-ylmethoxymethylbenzene, 3-ethyl-3-2-ethylhexyloxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane and other monofunctional or bifunctional oxetane compounds are also suitable.

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

（式（Ｐ１－８）中、環Ｚ^４は縮合多環式芳香族炭化水素環、Ｒ^Ｐ３５及びＲ^Ｐ３６は置換基、Ｒ^Ｐ３７は水素原子又はメチル基を示し、ｋ１は０～４の整数、ｋ２は０以上の整数、ｋ３は１以上の整数である。）

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

In the above formula (P1-8), the condensed polycyclic aromatic hydrocarbon ring represented by ring Z ⁴ includes condensed bicyclic hydrocarbon rings (e.g., C8-C20 condensed dicyclic rings such as indene ring and naphthalene ring). condensed bi- to tetracyclic hydrocarbon rings such as cyclic hydrocarbon rings, preferably C10-C16 condensed bicyclic hydrocarbon rings), condensed tricyclic hydrocarbon rings (e.g., anthracene ring, phenanthrene ring, etc.), etc. mentioned. Preferred condensed polycyclic aromatic hydrocarbon rings include naphthalene ring, anthracene ring and the like, with naphthalene ring being particularly preferred. The two rings Z ⁴ substituted at the 9-position of fluorene may be the same or different rings, and usually may be the same rings.

The substitution position of the ring Z ⁴ substituted at the 9-position of fluorene is not particularly limited. For example, the naphthyl group substituted at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like. , and particularly preferably a 2-naphthyl group.

In the above formula (P1-8), the substituent represented by R ^P35 includes, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [e.g., an alkyl group, aryl group (C6-C10 aryl group such as phenyl group), etc.], and in particular, halogen atoms, cyano groups or alkyl groups (especially alkyl groups) are often used. Examples of the alkyl group include C1-C6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (eg, C1-C4 alkyl group, particularly methyl group). When k1 is plural (2 or more), R ^P35 may be different from each other or may be the same. In addition, the R ³⁵ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Also, the bonding position (substitution position) of R ^P35 with respect to the benzene ring constituting fluorene is not particularly limited. Preferred k1 is 0 to 1, especially 0. In two benzene rings constituting fluorene, k1 may be the same or different.

R ^P36 substituted on ring Z ⁴ is, for example, an alkyl group (e.g., C1-C12 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, preferably C1-C8 alkyl group, more preferably is a C1-C6 alkyl group, etc.), a cycloalkyl group (e.g., a C5-C8 cycloalkyl group such as a cyclohexyl group, preferably a C5-C6 cycloalkyl group, etc.), an aryl group (e.g., a phenyl group, a tolyl group, C6-C14 aryl groups such as xylyl groups, preferably C6-C10 aryl groups, more preferably C6-C8 aryl groups, etc.), aralkyl groups (e.g., benzyl groups, C6-C10 aryl groups such as phenethyl groups, and C1-C4 aralkyl group formed by bonding with an alkyl group, etc.); cycloalkyloxy group, etc.), aryloxy group (C6-C10 aryloxy group, etc.), etc. —OR ^P38 [In the formula, R ^P38 represents a hydrocarbon group (such as the hydrocarbon group exemplified above). ]; Alkylthio groups (e.g., C1-C8 alkylthio groups such as methylthio groups, preferably C1-C6 alkylthio groups, etc.) and other groups -SR ^P38 (wherein R ^P38 is the same as described above); acyl groups (e.g., C1-C6 acyl group such as acetyl group, etc.); alkoxycarbonyl group (for example, alkoxycarbonyl group in which C1-C4 alkoxy group such as methoxycarbonyl group and carbonyl group are bonded); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); hydroxyl group; nitro group; cyano group;

Among these, R ^P36 is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, etc., particularly , Preferred R ^P36 are hydrocarbon groups [e.g., alkyl groups (e.g., C1-C6 alkyl groups)], alkoxy groups (C1-C4 alkoxy groups, etc.), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms etc.).

In the same ring ^Z4 , when k2 is plural (2 or more), R ^P36 may be different from each other or may be the same. In two rings Z ⁴ , R ^P36 may be the same or different. Also, k2 may be preferably 0 to 8, preferably 0 to 6 (eg, 1 to 5), more preferably 0 to 4, particularly 0 to 2 (eg, 0 to 1). In the two rings ^Z4 , k2 may be the same or different.

In the above formula (P1-8), R ^{2 P37} is a hydrogen atom or a methyl group, preferably R ^{2 P37} is a hydrogen atom.

In the above formula (P1-8), k3 may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. In addition, k3 may be the same or different in each ring Z, and is usually the same in many cases. The substitution position of the epoxy group-containing group is not particularly limited as long as it is substituted at an appropriate substitution position on the ring ^Z4 . In particular, the epoxy group-containing group is substituted at least on a hydrocarbon ring other than the hydrocarbon ring bonded to the 9-position of the fluorene (e.g., the 5-position, 6-position, etc. of the naphthalene ring) in the condensed polycyclic hydrocarbon ring. often have.

Specific compounds represented by the above formula (P1-8) include, for example, 9,9-bis(glycidyloxynaphthyl)fluorene [e.g., 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene , 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene, etc.] and compounds in which k3 is 1 in the above formula (P1-8).

(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 may be a polymer having a hydroxyl group, a carboxyl group, or an amino group. For example, epoxy groups may be introduced into polymers having reactive functional groups such as epichlorohydrin using compounds having epoxy groups. Partial oxides of polymers having unsaturated aliphatic hydrocarbon groups in side chains, such as 1,2-polybutadiene, can also be suitably used as polymers having epoxy groups. Such partial oxides contain epoxy groups generated by oxidation of unsaturated bonds contained in side chains.

Since it is easy to obtain, prepare, and adjust the amount of epoxy groups in the polymer, the polymer having an epoxy group is a monomer having an epoxy group or a monomer containing a monomer having an epoxy group. A polymer obtained by polymerizing a mixture of organic compounds and a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in a side chain are preferred.

(Polymer of a monomer mixture containing a monomer having an epoxy group or a monomer having an epoxy group)
Among polymers having an epoxy group, from the viewpoints of ease of preparation and applicability of the energy-sensitive composition to a substrate, a homopolymer of a (meth)acrylic acid ester having an epoxy group, Copolymers of (meth)acrylic acid esters having epoxy groups and other monomers are preferred.

The (meth)acrylic acid ester having an epoxy group may be a (meth)acrylic acid ester having a chain aliphatic epoxy group, or a (meth)acrylic acid ester having an alicyclic epoxy group as described later. There may be. Moreover, the (meth)acrylic acid ester having an epoxy group may contain an aromatic group. From the viewpoint of the transparency of the cured product formed using the energy-sensitive composition, among the (meth)acrylic acid esters having an epoxy group, aliphatic (meth)acrylic acid esters having a chain aliphatic epoxy group, , an aliphatic (meth)acrylic acid ester having an alicyclic epoxy group is preferred, and an aliphatic (meth)acrylic acid ester having an alicyclic epoxy group is more preferred.

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

Examples of aliphatic (meth)acrylic acid esters having a chain aliphatic epoxy group include ester groups (-O-CO- ) in which a chain aliphatic epoxy group is bonded to the oxy group (--O--). A chain aliphatic epoxy group possessed by such a (meth)acrylic acid ester may contain one or more oxy groups (--O--) in the chain. The number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but is preferably 3-20, more preferably 3-15, and particularly preferably 3-10.

Specific examples of aliphatic (meth)acrylic acid esters having a chain aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6, Epoxy alkyl (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-glycidyloxy-n-hexyl (meth)acrylate, 6-glycidyloxy-n-hexyl (meth)acrylate and other epoxyalkyloxyalkyl (meth)acrylates.

Specific examples of aliphatic (meth)acrylic acid esters having an alicyclic epoxy group include compounds represented by the following formulas (a2-1) to (a2-15). 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 above 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, and R ^a22 represents a divalent divalent hydrocarbon group having 1 to 10 carbon atoms. represents a hydrocarbon group, and t represents an integer of 0-10. R ^a21 is preferably a linear or branched alkylene group such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group and hexamethylene group. R ^a22 is preferably, 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 and a cyclohexylene group.

As the polymer having an epoxy group, either a homopolymer of a (meth)acrylic acid ester having an epoxy group or a copolymer of a (meth)acrylic acid ester having an epoxy group and another monomer is used. However, the content of units derived from a (meth)acrylic acid ester having an epoxy group in the polymer having an epoxy group is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. % or more is particularly preferable, and 100% by mass is most preferable.

When the polymer having an epoxy group is a copolymer of a (meth)acrylic acid ester having an epoxy group and another monomer, the other monomer may be an unsaturated carboxylic acid or an epoxy group-having polymer. (Meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more. From the viewpoint of the storage stability of the energy-sensitive composition and the chemical resistance of the cured product formed using the energy-sensitive composition to alkalis, etc., it is necessary to use a (meth)acrylic acid ester having an epoxy group and other monomers. The copolymer with preferably does not contain a unit derived from an unsaturated carboxylic acid.

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

Examples of (meth)acrylic acid esters having no epoxy group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, t-octyl (meth)acrylate and the like. Chain 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; and (meth)acrylic acid ester having a group having an alicyclic skeleton. Among (meth)acrylic acid esters having no epoxy group, (meth)acrylic acid esters having a group having an alicyclic skeleton are preferred from the viewpoint of the transparency of the cured product formed using the energy-sensitive composition. 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. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group etc. are mentioned as a polycyclic alicyclic group.

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, compounds represented by the following formulas (a3-3) to (a3-8) are preferred, and compounds represented by the following formulas (a3-3) or (a3-4) are more preferred.

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or 1 carbon atom. -5 alkyl groups. R ^a24 is preferably a single bond, a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group and a hexamethylene group. 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 and the like.

Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc.

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, hydroxy Alkyl vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4- vinyl aryl ethers such as dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether;

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenylacetate, vinylacetoacetate, vinyllactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

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

(Partial Oxides of Polymers Having Unsaturated Aliphatic Hydrocarbon Groups in Side Chains)
Although the polymer having an unsaturated aliphatic hydrocarbon in its side chain is not particularly limited, 1,2-polybutadiene having a vinyl group in its side chain is preferred because of its availability and ease of synthesis. By partially oxidizing 1,2-polybutadiene, epoxidized polybutadiene having oxiranyl and vinyl groups in the side chains is obtained. The ratio of oxiranyl groups in such epoxidized polybutadiene is preferably 10 to 70 mol%, more preferably 10 to 50 mol%, more preferably 10 to 40 mol% with respect to the total number of moles of oxiranyl groups and vinyl groups. preferable. As the epoxidized polybutadiene, JP-100 and JP-200 commercially available from Nippon Soda Co., Ltd. can be preferably used.

The molecular weight of the epoxy group-containing polymer described above is not particularly limited as long as it does not hinder the object of the present invention. 15,000 is more preferred.

Further, the compound (P1) includes compounds represented by the following formula (P1-6).

（式（Ｐ１－６）中、Ｒ^Ｐ３１～Ｒ^Ｐ３３は、直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－ＮＨ－及びこれらの組み合わせからなる基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｅ^１～Ｅ^３は、エポキシ基、オキセタニル基、エチレン性不飽和基、アルコキシシリル基、イソシアネート基、ブロックイソシアネート基、チオール基、カルボキシ基、水酸基及びコハク酸無水物基からなる群より選択される少なくとも１種の置換基又は水素原子である。但し、Ｅ^１～Ｅ^３のうち少なくとも１つは、エポキシ基及びオキセタニル基からなる群より選択される少なくとも１種である。）

(In formula (P1-6), R ^P31 to R ^P33 are linear, branched or cyclic alkylene groups, arylene groups, —O—, —C(═O)—, —NH— and these It is a combination of groups, each of which may be the same or different, and E ¹ to E ³ are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate. at least one substituent selected from the group consisting of a group consisting of a group consisting of a thiol group, a carboxy group, a hydroxyl group and a succinic anhydride group, or a hydrogen atom, provided that at least one of E ¹ to E ³ is an epoxy group and at least one selected from the group consisting of oxetanyl groups.)

In formula (P1-6), at least one of the groups represented by R ^{1 P31} and E ¹ , R ^{1 P32} and E ² , and R ^{1 P33} and E ³ is a group represented by the following formula (P1-6a). more preferably, at least two are each a group represented by the following formula (P1-6a), and each is a group represented by the following formula (P1-6a) is more preferred. The groups represented by formula (P1-6a) that bind to one compound are preferably the same group.
-LC (P1-6a)
(In the formula (P1-6a), L is a linear, branched or cyclic alkylene group, arylene 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 epoxy group and an oxetanyl group.In formula (P1-6a), L and C may combine to form a cyclic structure.)

In formula (P1-6a), the linear, branched or cyclic alkylene group for L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group for L is a carbon atom. Arylene groups of numbers 5 to 10 are preferred. In formula (P1-6a), L is a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH- and a group consisting of a combination thereof. Preferably, at least one of a straight-chain alkylene group having 1 to 3 carbon atoms such as a methylene group and a phenylene group, or these together with -O-, -C (= O) - and NH- A group consisting of a combination with at least one of 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 (alicyclic structure structure having an epoxy group), an organic group represented by the following formula (P1-6b) or (P1-6c) can be mentioned.

（式（Ｐ１－６ｂ）中、Ｒ^Ｐ３４は、水素原子又はメチル基である。）

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

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

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

The siloxane compound (B) can impart yellowing resistance (= heat-resistant transparency) to the obtained cured product when exposed to a high-temperature environment for a long period of time, and has two or more glycidyl groups in the molecule. and further has a siloxane skeleton composed of siloxane bonds (Si—O—Si). The siloxane skeleton in the siloxane compound (B) includes, for example, a cyclic siloxane skeleton and a polysiloxane skeleton (e.g., linear or branched silicone (linear or branched polysiloxane), cage type or ladder type polysilsesquioxane, etc.).

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

式（Ｂ－１）中、Ｒ^Ｂ１、Ｒ^Ｂ２は、グリシジル基を含有する一価の基又はアルキル基を示す。但し、式（Ｂ－１）で表される化合物におけるｎ個のＲ^Ｂ１及びｎ個のＲ^Ｂ２のうち、少なくとも２個はグリシジル基を含有する一価の基である。また、式（Ｂ－１）中のｎは３以上の整数を示す。尚、式（Ｂ－１）で表される化合物におけるＲ^Ｂ１、Ｒ^Ｂ２は同一であってもよいし、異なっていてもよい。また、複数のＲ^Ｂ１は同一であってもよいし、異なっていてもよい。複数のＲ^Ｂ２も同一であってもよいし、異なっていてもよい。

In formula (B-1), R ^B1 and R ^B2 each represent a monovalent group or alkyl group containing a glycidyl group. At least two of n R ^{1 B1} and n R ^{1 B2} in the compound represented by formula (B-1) are monovalent groups containing a glycidyl group. Further, n in formula (B-1) represents an integer of 3 or more. R ^B1 and R ^B2 in the compound represented by formula (B-1) may be the same or different. Moreover, a plurality of R ^B1 may be the same or different. A plurality of R ^B2 may be the same or different.

As the monovalent group containing a 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 D (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms such as methylene group, methylmethylene group, dimethylmethylene group, dimethylene group and trimethylene group. be able to.

Examples of the above-mentioned alkyl group include linear chains having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as methyl group, ethyl group, propyl group, and isopropyl group. Mention may be made of linear or branched alkyl groups.

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

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

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

In addition to the siloxane compound (B), the energy-sensitive composition of the present embodiment includes other siloxane compounds (e.g., cycloaliphatic epoxy group-containing cyclic siloxanes, alicyclic epoxy groups described in JP-A-2008-248169). containing silicone resin, organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422, etc.).

More specifically, the siloxane compound (B) includes cyclic siloxanes having two or more glycidyl groups in the molecule represented by the following formula. Further, as the siloxane compound (B), for example, trade names "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" (Shin-Etsu Chemical (manufactured by Kogyo Co., Ltd.) can be used.

[(P2) a compound that increases its solubility in a developer under the action of acid]
Examples of compounds that increase the solubility in a developer under the action of an acid (hereinafter also referred to as "compound (P2)") include oligomers and polymers obtainable by copolymerization of the following monomers: , copolymers.

Acyclic or cyclic secondary and tertiary alkyl (meth)acrylates [e.g. 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)oxymethyltricyclododecanemethanol methacrylate, trimethylsilylmethyl (meth)acrylate, (2-tetrahydropyranyl)oxynorbornyl alcohol acrylate , (2-tetrahydropyranyl)oxymethyltricyclododecanemethanol methacrylate, trimethylsilylmethyl (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-norbornyloxystyrene, acyclic or cyclic alkoxycarbonylstyrene [e.g. o-/m-/p-tert-butoxycarbonylstyrene, o-/m-/p-(3-oxocyclohexyloxy carbonyl)styrene, o-/m-/p-(1-methyl-1-phenylethoxycarbonyl)styrene, o-/m-/p-tetrahydropyranyloxycarbonylstyrene, o-/m-/p-adamantyloxy carbonylstyrene, 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-adamantyloxycarbonyloxystyrene, o-/m-/p-cyclohexyloxycarbonyloxystyrene, o-/m-/p -norbornyloxycarbonyloxystyrene], acyclic or cyclic alkoxycarbonylalkoxystyrenes [e.g. o-/m-/p-butoxycarbonylmethoxystyrene, p-tert-butoxycarbonylmethoxystyrene, o-/m-/p- (3-oxocyclohexyloxycarbonylmethoxy)styrene, o-/m-/p-(1-methyl-1-phenylethoxycarbonylmethoxy)styrene, o-/m-/p-tetrahydropyranyloxycarbonylmethoxystyrene, o -/m-/p-adamantyloxycarbonylmethoxystyrene, o-/m-/p-cyclohexyloxycarbonylmethoxystyrene, o-/m-/p-norbornyloxycarbonylmethoxystyrene, trimethylsiloxystyrene, dimethyl(butyl ) siloxystyrene], unsaturated alkyl acetates (eg isopropenyl acetate, derivatives thereof), 5-norbornenyl-2-tert-butyl ester

Monomers bearing acid labile groups with low activation energy [e.g. p- or m-(1-methoxy-1-methylethoxy)styrene, p- or m-(1-methoxy-1-methylethoxy)- methylstyrene, p- or m-(1-methoxy-1-methylpropoxy)styrene, p- or m-(1-methoxy-1-methylpropoxy)methylstyrene, p- or m-(1-methoxyethoxy)styrene , p- or m-(1-methoxyethoxy)-methylstyrene, p- or m-(1-ethoxy-1-methylethoxy)styrene, p- or m-(1-ethoxy-1-methyl-ethoxy)methyl styrene, p- or m-(1-ethoxy-1-methylpropoxy)styrene, p- or m-(1-ethoxy-1-methylpropoxy)methylstyrene, p- or m-(1-ethoxyethoxy)styrene, p- or m-(1-ethoxyethoxy)-methylstyrene, p-(1-ethoxyphenylethoxy)styrene, p- or m-(1-n-propoxy-1-methylethoxy)-styrene, p- or m -(1-n-propoxy-1-methylethoxy)methylstyrene, p- or m-(1-n-propoxyethoxy)-styrene, p- or m-(1-n-propoxyethoxy)methylstyrene, p- or m-(1-isopropoxy-1-methylethoxy)-styrene, p- or m-(1-isopropoxy-1-methylethoxy)methylstyrene, p- or m-(1-isopropoxyethoxy)-styrene , p- or m-(1-isopropoxyethoxy)methylstyrene, p- or m-(1-isopropoxy-1-methylpropoxy)styrene, p- or m-(1-isopropoxy-1-methylpropoxy) -methylstyrene, p- or m-(1-iso-propoxypropoxy)styrene, p- or m-(1-isopropoxypropoxy)-methylstyrene, p- or m-(1-n-butoxy-1-methyl ethoxy)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 alkoxyalkyl ester acid labile group. Examples of polymers with alkoxyalkyl ester acid labile groups can be found in US5225316 and EP829766. Examples of polymers with acetal protecting groups are described, for example, in US5670299, EP780732, US5627006, US5558976, US5558971, US5468589, EP704762, EP762206, EP342498, EP553737 and ACS Symp. Ser. 614, Microelectronics Technology, pp. 35-55 (1995), J.P. 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 compositions according to this embodiment are not limited thereto.

Monomers with acid-labile groups may also, where appropriate, be combined with other free radically polymerizable monomers [e.g., styrene, acrylonitrile, methyl (meth)acrylate, (meth)acrylic acid, 4-hydroxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-vinylcyclohexanol, norbornene, ethylnorbornene, maleic anhydride]. Alternatively, acid-labile groups can only be introduced subsequently in a polymer-analogous reaction. It is also known to those skilled in the art that prepolymers can be modified in targeted ways prior to such polymer-analogous reactions, for example by partial hydrogenation, partial alkylation, partial acetylation. That is, the polymer with acid-labile groups need not be synthesized from monomers 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; -T. Schacht, N.; Muenzel, P.; Falcigno, H.; Holzwarth andJ. Schneider, J.; Photopolymer Science and Technology, Vol. 9, (1996), 573-586, it is also possible to introduce acid-labile crosslinks. Such an acid-crosslinked system is preferred from the viewpoint of thermal stability. Such acid-labile crosslinks can also be obtained by reaction of phenol group-containing polymers (eg 4-hydroxystyrene copolymers) with di- and polyfunctional vinyl ethers.

Other examples of compounds (P2) are monomeric compounds (eg compounds containing carboxylic acid and phenolic groups) in which the carboxylic acid group or the phenolic OH group, respectively, is blocked by an acid-labile protecting group. Such acid-labile blocking can be, for example, a tert-butyl ester group, a 2-methyl-2-adamantyl ester group, an 8-ethyl-8-tricyclodecanyl ester group, a tetrahydropyranyl ester group or some other acid-cleavage. conversion of the carboxy group to a functional ester group. Phenolic OH groups can be blocked according to known methods, for example by converting them into acid-cleavable tert-butyl carbonate groups, silyl ethers, acetal groups and ketal groups.

Compound (P2) is also selected from the group consisting of cycloaliphatic copolymers, 4-hydroxy-phenyl group-containing copolymers, maleic anhydride-containing copolymers, acrylic acid-containing copolymers, acrylic acid ester-containing copolymers and methacrylic acid ester-containing copolymers. wherein a copolymer thereof carries a functional group that increases the solubility of the polymer in an alkaline developer after reaction with an acid.

[(Px) radically polymerizable or crosslinkable compound]
Radically polymerizable or crosslinkable compounds (also referred to herein as “compound (Px)”) include, for example, acrylates having reactive functional groups. Reactive functional groups may be selected, for example, from the group consisting of hydroxyl groups, thiol groups, isocyanate groups, anhydride groups, carboxy groups, amino groups and blocked amino groups. OH group-containing unsaturated acrylates include hydroxyethyl acrylate and hydroxybutyl acrylate. Compound (Px) may also be of any desired structure (for example, it may contain units of polyesters, polyacrylates, polyethers, etc.), but it may contain ethylenically unsaturated double bonds and In addition they contain free OH, COOH, _NH2 or NCO groups.

Compounds (Px) can also be obtained, for example, by reacting acrylic or methacrylic acid with epoxy-functional oligomers. Typical examples of OH-functional oligomers with vinylic double bonds are

であって、ＣＨ_２＝ＣＨＣＯＯＨと

との反応により得られるものである。

and CH ₂ =CHCOOH and

It is obtained by the reaction with

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

Further, the compound (Px) includes a compound represented by the following formula (Px-1).

（式（Ｐｘ－１）中、Ｒ^Ｐ３１～Ｒ^Ｐ３３は、直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－ＮＨ－及びこれらの組み合わせからなる基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｅ^４～Ｅ^６は、化合物（Ｐ１）と式（Ｐｘ－１）で表される化合物との間、若しくは式（Ｐｘ－１）で表される化合物同士の間でラジカル的に重合又は架橋し得る官能基或いは水素原子である。但し、Ｅ^４～Ｅ^６のうち少なくとも１つは、該官能基である。）

(In formula (Px-1), R ^P31 to R ^P33 are linear, branched or cyclic alkylene groups, arylene groups, —O—, —C(═O)—, —NH— and these A group consisting of a combination, each of which may be the same or different, and E ⁴ to E ⁶ are between the compound (P1) and the compound represented by the formula (Px-1), or A functional group or hydrogen atom capable of radically polymerizing or cross-linking between compounds represented by the formula (Px-1), provided that at least one of E ⁴ to E ⁶ is the functional group .)

In formula (Px-1), 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 a group represented by the following formula (Px-1a). It is preferable that at least two of them are groups represented by the following formula (Px-1a), and each of them is a group represented by the following formula (Px-1a). is more preferred. The groups represented by formula (Px-1a) that bind 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 arylene group, -O-, -C(=O)-, -NH- and a group consisting of a combination thereof and C' is an ethylenically unsaturated group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a thiol group, a carboxy group, a hydroxyl group, a pyrazolyl group, an alkoxy group, a ketone group, a lactone ring and a succinic anhydride group. is at least one substituent selected from the group consisting of: In formula (Px-1a), L' and C' may combine to form a cyclic structure.)

In formula (P1-6a), the linear, branched or cyclic alkylene group for L′ is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group for L is carbon Arylene groups having 5 to 10 atoms are preferred. In formula (Px-1a), L' is a linear alkylene group having 1 to 6 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH- and combinations thereof. is preferably a group, and at least one of a linear C 1-6 alkylene group such as a methylene group and a phenylene group, or these together with -O-, -C(=O)- and NH A group consisting of a combination with at least one of - is preferred. When a branched alkylene group and a succinic anhydride group are combined to form a cyclic structure, specific examples thereof include cyclohexane-1,2-dicarboxylic anhydride.

In addition, in the energy-sensitive composition of this embodiment, the content of the compound component (P) is preferably 80 to 99.999% by mass with respect to the entire composition (excluding the solvent), It is more preferably 90 to 99.99% by mass, even more preferably 92 to 99.9% by mass. When the content of the compound component (P) is within the above range, the thermogravimetric stability tends to be good.

As the compound component (P), compounds selected from the group consisting of compounds (P1), (P2), and compounds (Px) can be used singly or in combination of two or more. When used in combination of two or more, it preferably contains compound (P1). In this case, the content of the compound (P1) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more in the compound component (P). When the content of the compound (P1) is within the above range, the effect of improving the thermogravimetric stability is particularly large. Further, when the energy-sensitive composition is used for 3D printing, the compound (P1) may be combined with the compound (Px), in which case a photopolymerization initiator such as a radical photopolymerization initiator is preferably used in combination.

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

In formula (a1) above, both R ¹ and R ² are preferably groups represented by formula (a2) above. R ¹ and R ² may be the same or different.
In the above formula (a1), when R ¹ and R ² are mutually bonded to form a ring together with the sulfur atom in the formula, the formed ring is preferably a 3- to 10-membered ring including the sulfur atom. Preferably, it is more preferably a 5- to 7-membered ring. The ring to be formed may be polycyclic, and is preferably a condensed 5- to 7-membered ring.
In formula (a1) above, R ³ is preferably a group represented by formula (a3) above.
In formula (a1) above, A ¹ is preferably S or O, more preferably S.

In the above formula (a2), R ⁴ is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an optionally substituted amino or a nitro group, more preferably an alkyl group optionally substituted with a halogen atom, an alkylcarbonyl group, or a thienylcarbonyl group.
In the above formula (a2), m1 can be selected depending on the type of ring Z ¹ , and may be, 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 above formula (a3), R ⁵ is an alkylene group; a hydroxy group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or a group represented by the above formula (a5). A group represented by the above formula (a5) is preferred, and more preferred.
In the above formula (a3), R ⁶ is an alkyl group; an alkyl group substituted with a hydroxy group, an optionally substituted amino group, or a nitro group; or a group represented by the above formula (a6). A group represented by the above formula (a6) is preferred, and more preferred.
In the above formula (a3), ^A2 is preferably S or O, more preferably S.
In the above formula (a3), n1 is preferably 0.

In the above formula (a4), R ⁷ and R ⁸ are independently represented by an alkylene group; a hydroxy group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or the above formula (a5). is preferably a group, more preferably a group represented by the above formula (a5). R ⁷ and R ⁸ may be the same or different.
In formula (a4) above, both R ⁹ and R ¹⁰ are preferably groups represented by formula (a2) above. R ⁹ and R ¹⁰ may be the same or different.
In the above formula (a4), when R ⁹ and R ¹⁰ are mutually bonded to form a ring together with the sulfur atom in the formula, the formed ring is preferably a 3- to 10-membered ring including the sulfur atom. Preferably, it is more preferably a 5- to 7-membered ring. The ring to be formed may be polycyclic, and is preferably a condensed 5- to 7-membered ring.
In the above formula (a4), ^A3 is preferably S or O, more preferably S.
In the above formula (a4), n2 is preferably 0.

In the above formula (a5), R ¹¹ is preferably an alkyl group optionally substituted with a halogen atom, a hydroxy group, an amino group optionally substituted, or a nitro group, and is substituted with a halogen atom. is more preferably an alkyl group having a
In the above formula (a5), m2 can be selected depending on the type of ring Z ² , and may be, 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 above formula (a6), R ¹² is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an optionally substituted amino or a nitro group, more preferably an alkyl group optionally substituted with a halogen atom, an alkylcarbonyl group, or a thienylcarbonyl group.
In the above formula (a6), m3 can be selected according to the type of ring Z ³ , and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2. .

In the above formula (a1), X ^- corresponds to an acid (HX) generated by irradiating the sulfonium salt (Q) with activation energy (heat, visible light, ultraviolet rays, electron beams, X-rays, etc.) 1 is a valent anion. When the sulfonium salt (Q) is used as an acid generator, X ⁻ is preferably a monovalent polyatomic anion such as MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4- Anions represented by _c ⁻ , R ^x1 _c GaY _4-c ⁻ , R ^x2 SO ₃ ⁻ , (R ^x2 SO ₂ ) ₃ C ⁻ , or (R ^x2 SO ₂ ) ₂ N ⁻ are more preferable. X ^{1 −} may also be a halogen anion such as fluoride ion, chloride ion, bromide ion, iodide ion and the like.

M represents a phosphorus atom, a boron atom, or an antimony atom.
Y represents a halogen atom (preferably a fluorine atom).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol % or more of the hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be Rf by fluorine substitution include straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched-chain alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.) and cyclo Alkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like are included. The ratio of hydrogen atoms of these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90 mol%, based on the number of moles of hydrogen atoms in the original alkyl group. % or more, particularly preferably 100%. When the substitution ratio with fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt (Q) is further improved. Particularly preferred examples of Rf include CF ₃ −, CF ₃ CF ₂ ⁻ , (CF ₃ ) ₂ CF ⁻ , CF ₃ CF ₂ CF ₂ ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ ⁻ and (CF ₃ ) ₂ CFCF ₂ ⁻ , CF ₃ CF ₂ (CF ₃ )CF ^— and (CF ₃ ) ₃ C ^— . The b Rf's are independent of each other and therefore may be the same or different.

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

R ^x1 represents a phenyl group in which a portion of hydrogen atoms are substituted with at least one element or electron-withdrawing group. Examples of such single elements include halogen atoms and include fluorine, chlorine and bromine atoms, and the like. Electron-withdrawing groups include trifluoromethyl, nitro and cyano groups. Among these, a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferred. The c R ^x1 are independent of each other, and therefore may be the same or different.

B represents a boron atom and 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 fluoroalkyl group are linear or branched. It may be either linear or cyclic, and the alkyl group, fluoroalkyl group, or aryl group may be unsubstituted or substituted. Examples of the substituent include a hydroxy group, an optionally substituted amino group (for example, those exemplified in the description below regarding the above formulas (a2) to (a6)), a nitro group, and the like. be done.
In addition, the carbon chain in the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 may have a heteroatom such as an oxygen atom, a nitrogen atom or a sulfur atom. In particular, the carbon chain in the alkyl group or fluoroalkyl group represented by R ^x2 is a divalent functional group (e.g., ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonylamide bond, sulfonylimide bond, urethane bond, etc.).
When the alkyl group, fluoroalkyl group, or aryl group represented by R ^x2 has the substituent, heteroatom, or functional group, the number of the substituent, heteroatom, or functional group may be one. It may be two or more.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.
a represents an integer of 4 to 6;
b is preferably an integer of 1-5, more preferably an integer of 2-4, particularly preferably 2 or 3.
c is preferably an integer of 1 to 4, more preferably 4.

Examples of anions represented by MY _a ^- include anions represented by SbF ₆ ^- , PF ₆ ^- and BF ₄ ^- .

Examples of anions represented by (Rf) _b PF _6-b ^- include (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 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 ⁻ Anions such as 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 Anions represented by PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- are preferred.

The anion represented by R ^x1 _c BY _4-c ^- is preferably R ^x1 _c BY _4-c ^-
(Wherein, R ^x1 represents a phenyl group in which at least part of the hydrogen atoms are substituted with halogen atoms or electron-withdrawing groups, 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 BF ₂ ⁻ , C ₆ F ₅ BF ₃ ⁻ or (C ₆ H ₃ F ₂ ) ₄ B ⁻ and the like. Among these, the anion represented by (C ₆ F ₅ ) ₄ ^B- or ((CF ₃ ) ₂ C ₆ H ₃ ⁾ ₄ B- is preferred.

Examples of anions represented by R ^x1 _c GaY _4-c ^- include (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , (CF ₃ C ₆ H ₄ ) ₄ Anions such as Ga ⁻ , (C ₆ F ₅ ) ₂ GaF ₂ ⁻ , C ₆ F ₅ GaF ₃ ⁻ and (C ₆ H ₃ F ₂ ) ₄ Ga ⁻ are included. Among these, anions represented by (C ₆ F ₅ ) ₄ Ga ^— or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^— are preferred.

Anions represented by R ^x2 SO ₃ ^- include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorophenylsulfonate anion, and p-toluene. Examples include sulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion. Among these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion and p-toluenesulfonate anion are preferable.

Anions represented by (R ^x2 SO ₂ ) ₃ C ^- include (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₃ F ₇ SO ₂ ) ₃ C ^- or an anion represented by (C ₄ F ₉ SO ₂ ) ₃ ^C- .

Anions 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 an anion represented by (C ₄ F ₉ SO ₂ ) ₂ ^N- .

The monovalent polyatomic anions 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 In addition to the anions represented by SO ₂ ) ₃ C ^- or (R ^x2 SO ₂ ) ₂ N ^- , perhalate ions (ClO ₄ ^- , BrO ₄ ^- etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^- etc.), sulfate ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^- etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^- etc.), aluminate ions (AlCl ₄ ^- , AlF _4- ^etc. ), hexafluorobismuthate ion (BiF ₆ ⁻ ), carboxylate ion (CH ₃ COO ⁻ , CF ₃ COO ⁻ , C ₆ H ₅ COO ⁻ , CH ₃ C ₆ H ₄ COO ⁻ , C ₆ F ₅ COO ⁻ , CF ₃ C ₆ H ₄ COO ⁻ etc.), arylborate ions (B(C ₆ H ₅ ) ₄ ⁻ , CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ⁻ etc.), thiocyanic acid Ions (SCN ⁻ ) and nitrate ions (NO ₃ ⁻ ) can be used.

Among these X ⁻ , MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4-c ⁻ , R ^x1 _c GaY _4-c ⁻ and (R ^x2 SO ₂ ⁾ Anions ^{represented by} _3C- are preferred, such _{as SbF6-} ^, _PF6- , ( _CF3CF2 ) _{3PF3- ,} ( _{C6F5 ) 4B-} ^, ₍ ( _CF3 ) _2C6 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 preferred, and R ^x1 _c BY _{4 -c-} ^is more preferred.

In the above formulas (a2), (a5), and (a6), the aromatic hydrocarbon ring includes a benzene ring, condensed polycyclic aromatic hydrocarbon ring [e.g., condensed bicyclic hydrocarbon ring (e.g., naphthalene C _8-20 condensed bicyclic hydrocarbon ring, preferably C _10-16 condensed bicyclic hydrocarbon ring such as ring), condensed tricyclic aromatic hydrocarbon ring (e.g., anthracene ring, phenanthrene ring, etc.), etc. condensed 2- to 4-ring aromatic hydrocarbon ring] and the like. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.

In the above formulas (a1) to (a6), the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

In the above formulas (a1) to (a6), the alkyl group includes a linear 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.), branched alkyl groups having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert -pentyl, isohexyl and isootadecyl, etc.), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, etc.). In particular, in the above 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 alkyl groups substituted with halogen atoms include groups in which at least one hydrogen atom in the straight-chain alkyl group, branched-chain alkyl group or cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, trifluoromethyl, fluoromethyl, etc.). Among the alkyl groups optionally substituted with halogen atoms, R ¹ , R ² , R ⁹ or R ¹⁰ is particularly preferably a trifluoromethyl group, and R ⁴ , R ⁶ , R ¹¹ or R ¹² is particularly preferably a methyl group.

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

In the above formulas (a2) to (a6), the alkyl group in the alkylcarbonyl group includes the straight-chain alkyl group having 1 to 18 carbon atoms, the branched-chain alkyl group having 3 to 18 carbon atoms, or 3 carbon atoms. to 18 cycloalkyl groups, and the alkylcarbonyl group includes linear, branched or cyclic alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl group, cyclohexanoyl group, etc.) and the like.

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

In the above formulas (a2) to (a6), the alkoxycarbonyl group includes a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, iso butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.) and the like.

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

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

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

In the above formulas (a3) to (a6), the arylthio group includes an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio , 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxy phenylthio, 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-benzoylphenylthio, 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, 4-(p-tert-butylbenzoyl)phenylthio, etc.).

In the above formulas (a2) to (a6), the alkylthio group includes 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, etc.).

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

In the above formula (a2), the heterocyclic aliphatic hydrocarbon group includes a heterocyclic hydrocarbon group having 2 to 20 (preferably 4 to 20) carbon atoms (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidinyl, tetrahydro pyranyl, tetrahydrothiopyranyl, morpholinyl, etc.) and the like.

In the above formulas (a3) to (a6), the heterocyclic hydrocarbon group includes a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl , pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl , and dibenzofuranyl, etc.).

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

In the above formulas (a2) to (a6), the alkylsulfinyl group includes a linear or branched 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.).

In the formulas (a3) to (a6), examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl, etc.).

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

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

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

In the above formulas (a2) to (a6), the optionally substituted amino group includes an amino group (—NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methyl ethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methyl phenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.) and the like.

In the above formulas (a3) and (a4), the alkylene group includes 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, 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, hexadecane-1,16-diyl group, etc.).

A 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. to obtain a nitro compound represented by the following formula (b3), which is then reduced in the presence of reduced iron to obtain an amine compound represented by the following formula (b4). This amine compound is reacted with a nitrite (e.g., sodium nitrite) represented by MaNO ₂ (wherein Ma represents a metal atom, e.g., an alkali metal atom such as a sodium atom) to obtain a diazo compound. Then, this diazo compound and CuX' (wherein X' represents a halogen atom such as a bromine atom; hereinafter the same) and a hydrogen halide represented by HX' are combined. By mixing and allowing the reaction to proceed, a halide represented by the following formula (b5) is obtained. A Grignard reagent is prepared from this halide and magnesium, and then, in the presence of chlorotrimethylsilane, this Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) to obtain a compound represented by the following formula (b7). sulfonium salts can be obtained. Furthermore, this sulfonium salt is Mb ⁺ X″ ⁻ (wherein Mb ⁺ represents a metal cation, for example, an alkali metal cation such as potassium ion, and X″ ⁻ represents a monovalent anion represented by X ⁻ (provided that (excluding halogen anions)) to perform salt exchange to obtain a sulfonium salt represented by the following formula (b8). In formulas (b2) to (b8) below, R ¹ to R ³ and A ¹ are the same as in formula (a1) above.

<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 portion of the sulfonium salt (Q) represented by the formula (a1) include conventionally known ones such as those mentioned in the explanation of X ^{1 −} above. The sulfonium salt (Q) represented by the above formula (a1) can be synthesized according to the above scheme, and if necessary, by further salt-exchanging, the cation moiety can be combined with the desired anion moiety. ^x1 _c BY _4-c ⁻ (Wherein, R ^x1 represents a phenyl group in which at least part of the hydrogen atoms are substituted with halogen atoms or electron-withdrawing groups, Y represents a halogen atom, and c represents 1 to 4 represents an integer) is preferred.
be.

In addition, in the energy-sensitive composition of this embodiment, the content of the sulfonium salt (Q) is preferably 0.001 to 20% by mass with respect to the entire composition (excluding the solvent), It is more preferably 0.01 to 10% by mass, even more preferably 0.1 to 8% by 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 energy-sensitive composition is prepared to have a low viscosity, for example, 1000 mPa·s (1000 cP) or less, the content of the sulfonium salt (Q) is the total composition (excluding the solvent). ) may be within the above range, but may be 0.001 to 1% by mass, may be 0.005 to 0.1% by mass, and may be 0.008 to 0.05 % by 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).
Examples of such onium salts include onium salts composed of a monovalent anion represented by X ⁻ in the formula (a1) and an onium ion different from the cations other than X ⁻ in the formula (a1). and sulfonium salts (also referred to herein as “sulfonium salts (Q′)”) are preferred. As the monovalent anion represented by X ⁻ , R ^x1 _c BY _4-c ⁻ described above is preferable.

Examples of the sulfonium salt (Q') having a monovalent anion represented by R ^x1 _c BY _4-c ^- include sulfonium salts represented by the following formula (a1').

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ａ^１、Ｒ^ｘ１、Ｙ及びｃは上述のとおり。）

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

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

The sulfonium salt (Q') is also represented by the above formula (a1) (wherein R ¹ and R ² are independently groups represented by the following formula (a2')). Sulfonium salts are mentioned.

（式中、環Ｚ^１及びｍ１は上述のとおりであり、Ｒ^４’はアリール基を示す。）

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

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

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

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

Examples of solvents include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.); esters (ethyl acetate, methyl propionate, ethyl propionate, methyl butanoate, ethyl butanoate, pentanoic acid chain alkyl esters such as methyl, ethyl pentanoate, methyl hexanoate, ethyl hexanoate, methyl heptanoate, and ethyl heptanoate; Cyclic alkyl esters such as isopropylcyclohexyl acetate, butylcyclohexyl acetate, isobutylcyclohexyl acetate, s-butylcyclohexyl acetate, t-butylcyclohexyl acetate, pentylcyclohexyl acetate: ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.); β-ketoester compounds (methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, α-acetyl-γ-butyrolactone, etc. ); β-diketone compounds (acetylacetone, 2,4-hexanedione, 2,4-heptanedione, etc.); ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.), etc. and can be used singly or in combination of two or more.

In addition, conventionally known ketone-based solvents, alcohol-based solvents, amide-based solvents, and hydrocarbon-based solvents may be used. Solvents known as protic solvents and/or basic solvents may also be used.
Examples of protic solvents include alcohols such as monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol and diethylene glycol monomethyl ether, and polyhydric alcohols such as ethylene glycol and glycerin; acetic acid, formic acid, (meth) carboxylic acids such as 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 p-butylphenol; and active methylene compounds such as acetylacetone and diethyl malonate.
Examples of the basic solvent include, in addition to the above amines and nitrogen-containing amides, pyridine, triethylamine, N,N-dimethylacetamide, hexamethylphosphorictriamide, 1,3-dimethyl-2- imidazolidinone, N,N,N',N'-tetramethylurea, N,N,2-trimethylpropionamide and the like.

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

(alkali-soluble resin)
The energy-sensitive composition according to this embodiment can contain an alkali-soluble resin (A), if necessary.
In this specification, the alkali-soluble resin means a resin solution (solvent: propylene glycol monomethyl ether acetate) with a resin concentration of 20% by mass to form a resin film with a film thickness of 1 μm on the substrate. It is a material that dissolves to a film thickness of 0.01 μm or more when immersed in an aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute.

As the alkali-soluble resin, (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof is added to a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and an unsaturated group-containing monocarboxylic acid and (b) an alkali-soluble resin (A1) obtained by reacting a tetracarboxylic acid or its acid dianhydride, an alkali-soluble group such as a carboxy group, a phenolic hydroxyl group, or a sulfo group (--SO ₃ H). conventionally known resins (A2) having In this specification, the alkali-soluble resin (A2) preferably represents an alkali-soluble resin other than the alkali-soluble resin (A1). These alkali-soluble resins are also preferred when it is desired that the resulting cured product has heat resistance.

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

The alkali-soluble resin (A2) is not particularly limited, and conventionally known alkali-soluble resins can be used. This alkali-soluble resin may or may not have an ethylenically unsaturated group.

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

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

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

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

In general formula (f-1) above, Y ^f represents a residue obtained by removing the acid anhydride group (--CO--O--CO--) from the dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride. Examples include phthalic anhydride and glutaric anhydride.

In general formula (f-1) above, Z ^f represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride and the like.
Further, m represents an integer of 0 to 20 in the general formula (f-1).

Further, as an alkali-soluble resin having an ethylenically unsaturated group, a polyester obtained by reacting a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid with (meth)acrylic acid. (Meth)acrylate; Polyurethane (meth)acrylate obtained by reacting polyol with a compound having two isocyanate groups and then reacting (meth)acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin , bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy An epoxy (meth)acrylate resin obtained by reacting an epoxy resin such as a resin, a dihydroxybenzene-type epoxy resin, and (meth)acrylic acid, or the like can also be used.
In addition, in this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth)acrylate" means both acrylate and methacrylate.

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

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

Examples of epoxy group-containing unsaturated compounds having no alicyclic group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl ( (Meth)acrylic acid epoxyalkyl esters such as meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 4-oxatetracyclo-[6.2.1.02,7 03,5]undecanyl (meth)acrylate α-alkyl acrylate epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl acrylate, α-n-butyl acrylate glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl are preferred in terms of copolymerization reactivity, strength of the resin after curing, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether are preferred. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. Alicyclic groups may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Examples of polycyclic alicyclic groups include adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group and tetracyclododecyl group. Specifically, the alicyclic group-containing unsaturated compound includes, for example, compounds represented by the following formulas.

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

The proportion of structural units derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, more preferably 5 to 25% by mass. Also, the proportion of the constituent units derived from the epoxy group-containing unsaturated compound is preferably 71 to 95% by mass, more preferably 75 to 90% by mass. Further, the proportion of structural units derived from the alicyclic group-containing unsaturated compound is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and 5 to 15% by mass. is more preferred. By setting it as said range, the hardened|cured material obtained can have sufficient heat resistance, making alkali solubility of resin obtained moderate.

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

The carboxy group-containing resin in the alkali-soluble resin (A2) may be a silicon-containing resin, and examples thereof include siloxane resins containing the following structural units.
It may contain a structural unit represented by the following formula (A2-1).

In formula (A2-1), R ^r1 is an organic group having at least one carboxy group in its structure. The carboxy group is preferably bonded to the Si atom via a linking group, and the linking group is, for example, an alkylene group having 1 to 10 carbon atoms which may be linear or branched, a cycloalkylene group, or It is an arylene group or a divalent group combining these.
The linking group may have an ether bond, an amino bond, an amide bond, or a vinyl bond, and preferably has an amide bond. Examples of R ^r1 include, but are not limited to, the following. Note that * in the following formula means the terminal of the bond of R ^r1 that bonds to Si in formula (A2-1).

The ratio of the structural unit of formula (A2-1) in the silicon-containing resin is, for example, 1 to 90% by mass. The silicon-containing resin may have conventionally known constitutional units other than (A2-1).
The mass average molecular weight of the silicon-containing resin is, for example, 300-100,000, more preferably 500-70,000.

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

(Surfactant)
The energy-sensitive composition according to this embodiment can contain a surfactant, if necessary. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants.

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

In addition, the energy-sensitive composition according to the present embodiment may optionally contain known additives (radical photopolymerization initiators, sensitizers, pigments, dispersants, fillers, antistatic agents, flame retardants, A foaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion imparting agent, an ion scavenger, an anti-coloring agent, a solvent, a non-reactive resin, a radically polymerizable compound, etc.) can be contained.
In particular, by combining a radical photopolymerization initiator and the like, it is possible to appropriately adjust the balance between the thermal reactivity and the photoreactivity of the energy-sensitive composition according to this embodiment.

[Characteristic]
The energy-sensitive composition according to this embodiment has a weight loss rate of preferably 10% or less from the peak value in thermogravimetry (TG) in which the temperature is raised to 230°C at 10°C/min in an air current. .

As described above, by containing the sulfonium salt (Q), the concentration of protons increases in the system containing the compound component (P) and the sulfonium salt (Q), and the sequential polymerization in the compound component (P) continues. It is presumed that the polymerization is accelerated by progressing to As a result, the energy-sensitive composition according to this embodiment has a low weight loss rate of preferably 10% or less even when heated to 230°C.

The energy-sensitive composition according to this embodiment is preferably used as a sealing material for organic EL display elements or a curable composition for wafer-level lenses. The energy-sensitive composition according to the present embodiment has excellent weight stability even when exposed to high temperatures, and maintains its quality over a long period of time. preferred. Moreover, since it has both thermal reactivity and photoreactivity, it is preferably used in a composition for 3D printing.

In addition, the energy-sensitive composition according to the present embodiment is prepared, for example, as a coating liquid, and applied to an object to be coated such as a polyimide film using a spin coater, dip coater, bar coater, slit coater, or other coating device. A hard coat can be formed by post-curing. The coating liquid cures the coating liquid or hard coat even if the object to be coated is a thin film having a thickness of, for example, 10 mm or less, preferably 100 μm or less, for example, 50 μm or less, 30 μm or less, 20 μm or less, or even 15 μm or less. It is possible to suppress the degree of deformation such as curling of the object to be coated. The film thickness of the object to be coated may be, for example, 10 μm or more.

In general, a low-molecular-weight compound (P1), such as an epoxy monomer, is used to reduce the viscosity of the composition. and outgassing is likely to occur. However, it was confirmed that the energy-sensitive composition according to the present embodiment, which contains the sulfonium salt (Q), has excellent heat resistance and can reduce the generation of outgas even when the viscosity is low. Moreover, unexpectedly, even if the amount of the sulfonium salt (Q) added is smaller than that of a general cationic polymerization initiator, the viscosity of the energy-sensitive composition can be reduced and the heat resistance can be improved. It was confirmed by the experiment described later that the effect of improving and reducing the generation of outgas can be obtained.

The energy-sensitive composition according to the present embodiment has excellent heat resistance and can reduce outgassing while having a low viscosity, and is therefore preferably used in inkjet printing that requires a low-viscosity ink. From the point of view of productivity and the like, inkjet inks are preferably used for displays such as touch panels when applied to a relatively large area, and are also preferably used for applications such as sealing materials for organic EL display elements.

<Manufacturing method of wafer level lens>
Wafer-level lenses can be produced by subjecting the energy-sensitive composition described above to molding (eg, casting molding, injection molding). The wafer level lens mold may be made of metal, glass, or plastic.

The casting molding method includes a simultaneous molding method and an individual piece molding method, each of which has 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 fixed direction, and cured by heating and/or light irradiation. Step 2: 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 bonded Step 3: The cured product having a shape in which a plurality of wafer-level lenses are bonded is singulated to obtain wafer-level lenses

(Individual piece molding method)
Step 1: The energy-sensitive composition is poured into a wafer-level lens mold having one lens mold and cured by heating and/or light irradiation. Step 2: The wafer-level lens mold is removed and annealed. , to get a wafer level lens

(Injection molding method)
Step 1: The energy-sensitive composition is poured into a wafer-level lens mold for injection molding and cured by heating and/or light irradiation Step 2: The wafer-level lens mold is removed and annealed to remove burrs. to get the wafer level lens

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

Internal strain can be removed by annealing. The annealing treatment is preferably performed at a temperature of 100 to 200° C. for about 30 minutes to 1 hour.

In the simultaneous molding method, it is preferable that the energy-sensitive composition has a low viscosity and excellent fluidity from the viewpoint of excellent fillability into a mold. The viscosity of the energy-sensitive composition used in the simultaneous molding method at 25° C. and a shear rate of 20 (1/s) is, for example, about 0.05 to 5 Pa·s, preferably 0.1 to 2 Pa·s. An energy-sensitive composition having a viscosity within the above range has excellent fluidity, does not easily leave air bubbles, and can be filled into a mold while suppressing an increase in injection pressure. That is, it is excellent in applicability and filling property, and excellent in workability over the entire molding operation.

A cured product of the energy sensitive composition has excellent heat resistance even in a high temperature environment of about 100 to 250°C. Therefore, it is possible to efficiently manufacture a wafer level lens having excellent lens center position accuracy even if annealing treatment is performed after removal from the mold. 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 bonded are stacked, and the position of the cutting line is determined based on the uppermost cured product. The wafer level lens can be separated without being damaged, and the wafer level lens or its laminate can be efficiently manufactured at low cost.

A wafer-level lens obtained from the energy-sensitive composition of this embodiment can prevent yellowing and maintain high transparency even when exposed to a high-temperature environment for a long period of time. Therefore, for example, imaging lenses for cameras (vehicle cameras, digital cameras, PC cameras, mobile phone cameras, cameras such as surveillance cameras, especially wafer level cameras), spectacle lenses, light beam condensing lenses, and light diffusion lenses As such, it can be suitably used as a wafer-level lens for a vehicle-mounted camera, which particularly requires heat resistance.

Furthermore, since the wafer-level lens obtained from the energy-sensitive composition of this embodiment has excellent heat resistance, it can be mounted on a circuit board by soldering by reflow. Therefore, a camera equipped with such a wafer level lens can be directly mounted on a PCB (Printed Circuit Board) board by the same solder reflow process as surface mounting of other electronic components, which is extremely efficient. Product manufacturing becomes possible.

<Cured product>
The cured product according to the present invention contains at least one compound component (P) selected from the group consisting of the above-described compound (P1), compound (P2), and compound (Px), and a sulfonium salt (Q). It is a cured product obtained by curing the energy-sensitive composition. The cured product according to the present invention has excellent weight stability against heat, as described above. This is because the inclusion of the sulfonium salt (Q) in the energy-sensitive composition increases the concentration of protons in the system containing the compound component (P) and the sulfonium salt (Q). It is presumed that this is because the sequential polymerization proceeds continuously and the polymerization is promoted, and the amount of thermally decomposed monomers is small. The cured product is suitable as, for example, a sealing material for an organic EL display device, a wafer level lens, the above hard coat, and the like. It is also suitable for flexible devices.
The cured product of this embodiment can also be a cured product with a high refractive index by selecting the components of the energy-sensitive composition. Preferred components from the viewpoint of obtaining a cured product with a high refractive index include, for example, metal oxide particles, epoxy group-containing fluorene compounds as the compound (P1), and the like, and these can be used alone or in combination of two or more. It is preferable to use metal oxide particles from the viewpoint of increasing the refractive index. The refractive index of the resulting cured product is, for example, a high refractive index of 1.7 or more at a wavelength of 633 nm. A high refractive index is also possible. Although the upper limit of the refractive index at the wavelength of 633 nm is not particularly limited, it is, for example, 1.9 or less, 1.85 or less, and the like.

<Method for producing cured product>
The method for producing a cured product according to the present invention includes 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 cross-linking the energy sensitive composition comprising Since the energy-sensitive composition has energy sensitivity, it can be cured by polymerization and/or cross-linking by applying activation energy. Any activation energy can be applied as long as it has energy that induces 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 this embodiment has a viscosity of, for example, 5000 mPa s (5000 cP) or less, preferably 100 mPa s (100 cP) or less, as measured using an E-type viscometer at 25 ° C. When prepared to be low, it can be preferably used as an inkjet ink. Within the above range, 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 may be 10 mPa·s (10 cP) or more. The energy-sensitive composition used as an inkjet ink preferably has a sulfonium salt (Q) content for preparing the composition to have a low viscosity as described above.

EXAMPLES Hereinafter, the present invention will be described in more detail by showing examples of the present invention, but the present invention is not limited to the following examples.

<<Examples 1 to 3 and Comparative Examples 1 to 9>>
In Examples 1 to 3 and Comparative Examples 1 to 9, compound (P1) shown below and sulfonium salts and the like were mixed at the compounding ratios shown in Table 1 to prepare mixed solutions. In addition, in Table 1, the unit of the compounding ratio is parts by mass.

<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]
- a sulfonium salt represented by the following formula (Q1)

- a sulfonium salt represented by the following formula (z1)

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

・Triphenylsulfonium tetrakis-(pentafluorophenyl)borate

[Evaluation 1]
The mixed liquids obtained in Examples 1 to 3 and Comparative Examples 1 to 9 were measured in an air current at a temperature elevation rate of 10° C. using a differential thermal/thermogravimetry device (TG/DTA-6200, manufactured by Seiko Instruments Inc.). /min, the temperature was raised from 20°C to 250°C, and a TG/DSC curve was obtained. In the obtained TG curve, the weight loss rate from the peak value was calculated. Table 1 shows the results. The evaluation of the weight reduction rate is based on the following criteria.
○: Weight reduction rate is 10% or less △: Weight reduction rate is more than 10% and less than 40% ×: Weight reduction rate is 40% or more

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

[Discussion]
As shown in the TG curves shown in Table 1 and FIGS. It showed good high heat resistance as compared with ~9. In the DSC curve of Example 3 shown in FIG. 1, gentle peaks were observed at 110.6°C and 222.3°C. This is presumed to be a peak indicating that the epoxy group of compound (P1) is ring-opened and sequential polymerization is proceeding, and it is presumed that polymerization proceeds from a low temperature around 110°C. On the other hand, sharp peaks were observed in the DSC curves of the comparative examples shown in FIGS. This is presumed to be a peak indicating that the sulfonium salt represented by the above formula (z1) or the sulfone compound represented by the above formula (z2) is decomposed, thereby increasing the weight loss rate. It is speculated that For example, as shown in FIG. 2, in Comparative Example 7, the weight is reduced by about 65% at around 170.degree. As shown in FIG. 3, in Comparative Example 8, the weight decreased by about 30% at around 150.degree. As shown in FIG. 4, in Comparative Example 9, the weight decreased by about 50% at around 170.degree. From the results of FIG. 5, the compound (P1) represented by the formula (P1-2a) alone showed a sharp peak at 50° C. or lower in the DSC curve, and the compound (P1-2a) represented by the formula (P1-2a) at 50° C. or lower. It was confirmed that the decomposition of the compound (P1) started, the weight started to decrease from around 100°C, and decreased by about 80% at around 165°C.

[Evaluation 2]
The mass ratio of the mixture obtained in Example 1 was changed to the compound of formula (P1-1a):sulfonium salt of formula (Q1)=99:1, and the mixture was applied onto a glass substrate with a spin coater. A 20 μm thick coating film was irradiated with ghi rays at an exposure amount of 1000 mJ/cm ² using HMW-532D (manufactured by ORC). (manufactured by Denshi Co., Ltd.). The transmittance was 99.6%.

[Discussion]
From this result, in Examples 6 to 9 described later, a hard coat formed by applying a coating liquid containing the same compound (P1) and sulfonium salt (Q) as in Example 1 onto a polyimide film also showed permeation It is suggested that it would not adversely affect rates.

<<Examples 4 and 5>>
bis-1-ethyl-3-oxetanyl methyl ether, which is an alicyclic epoxy compound represented by the above formula (P1-1a) as the compound (P1) or an oxetane compound represented by the following formula (P1-7a), and , The sulfonium salt represented by the above formula (Q1) was mixed at the compounding ratio shown in Table 2, and the resulting mixture was exposed (broadband) with an exposure amount of 100 mJ / cm ² using an ultraviolet curing machine, Example 4 was post-baked at 150° C. for 2 minutes, and Example 5 was not post-baked. Cured. In addition, in Table 2, the unit of the compounding ratio is parts by mass.

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

<<Examples 6 to 9 and Comparative Examples 10 to 13>>
First, polyimide films 1 to 4 made of polyimide were prepared as follows.

[Method for producing polyimide film 1]
As a reactor, a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser was filled with 832 g of N,N-dimethylacetamide (DMAc) while passing nitrogen through it, and then the reactor was After the temperature was brought to 25°C, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was dissolved in the solvent in the reaction vessel and the solution was maintained at 25°C. Then, 31.09 g (0.07 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 8.83 g (0.07 mol) of biphenyltetracarboxylic dianhydride (BPDA) .03 mol) was added and stirred for a certain period of time to dissolve and react. At this time, the temperature of the solution was maintained at 25°C. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution with a solid concentration of 13% by weight. 25.6 g of pyridine and 33.1 g of acetic anhydride are added to the polyamic acid solution and stirred at 25° C. for 30 minutes, further stirred at 70° C. for 1 hour, cooled to room temperature, and precipitated in 20 L of methanol, The precipitated solids were filtered, pulverized, and dried at 100° C. under vacuum for 6 hours to obtain 111 g of solid powder polyimide.

0.03 g (0.03 wt%) of amorphous silica particles having OH groups bonded to their surfaces were added to N,N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, and the mixture was stirred until the solvent became clear. After sonication, 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 steel plate, cast to a thickness of 340 μm, dried with hot air at 130° C. for 30 minutes, peeled off from the stainless steel plate, and fixed to a frame with a pin. The frame fixed with the film was placed in a vacuum oven, gradually heated from 100° C. to 300° C. within 2 hours, cooled gradually, and separated from the frame to obtain a polyimide film. After that, as the final heat treatment step, heat treatment was further performed at 300° C. for 30 minutes. The obtained polyimide film 1 had a thickness of 50 μm, a total light transmittance of 88%, and a yellowness index (YI) of 2.5.

[Method for producing polyimide film 2]
A solution prepared by dissolving polysilazane (MOPS-1800, manufactured by Az Materials) having a weight average molecular weight of 2000 g/mol in dibutyl ether (DBE) at 2 wt % was applied to one surface of the polyimide film 1 with a wire. A polysilazane film having a thickness of 300 nm was formed by drying at high temperature. Then, after being left 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, thereby manufacturing a polyimide film 2 having a colorless transparent polyimide film/silicon oxide layer structure. bottom. The resulting polyimide film 2 had a thickness of 50 μm, a total light transmittance of 92%, and a yellowness index (YI) of 1.0.

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

The above varnish is applied to a non-alkali glass substrate (thickness 0.7 mm) with a bar coater, leveled at room temperature for 5 to 10 minutes, and a vertical cure oven (manufactured by Koyo Lindbergh, model name VF-2000B). Heat at 140 ° C. for 60 minutes, further heat at 350 ° C. for 60 minutes in a nitrogen atmosphere (oxygen concentration 100 ppm), leave at room temperature for 24 hours, peel the resin film from the glass, and prepare a polyimide film. bottom. The resulting polyimide film 3 had a thickness of 20 μm, a total light transmittance of 88%, and a yellowness index (YI) of 7.0.

[Method for producing polyimide film 4]
(Synthesis of imidazole compound (d))
First, after dissolving 30 g of a cinnamic acid derivative having the structure of the following formula in 200 g of methanol, 7 g of potassium hydroxide was added to the methanol. The methanol solution was then stirred at 40°C. Methanol was distilled off and the residue was suspended in 200 g of water. The resulting suspension was mixed with 200 g of tetrahydrofuran and stirred to separate the aqueous phase. Under ice-cooling, 4 g of hydrochloric acid was added and stirred, and then 100 g of ethyl acetate was mixed and stirred. After allowing the mixture to stand, the oil phase was separated. The desired product was crystallized from the oil phase, and the precipitate was recovered to obtain an imidazole compound (d) having the following structure.

(Preparation of tetracarboxylic dianhydride)
According to the methods described in Synthesis Example 1, Example 1 and Example 2 of WO 2011/099518, the tetracarboxylic dianhydride (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 gun to dry it sufficiently. Next, the atmospheric gas in the three-necked flask was replaced with nitrogen to create a nitrogen atmosphere in the three-necked flask. After adding 0.2045 g of 4,4'-diaminobenzanilide (0.90 mmol: manufactured by Nihon Junryo Yakuhin Co., Ltd.: DABAN) into a three-necked flask, N,N,N',N'-tetramethylurea (TMU) was added 3.12 g. The contents of the three-necked flask were stirred to obtain a slurry liquid in which the aromatic diamine (DABAN) was dispersed in the TMU.
Next, 0.3459 g (0.90 mmol) of the tetracarboxylic dianhydride of the above formula is added to the three-necked flask, and the contents of the flask are stirred at room temperature (25° C.) for 12 hours under a nitrogen atmosphere to react. I got the liquid. In this way, a reaction liquid containing 15% by mass of polyamic acid (TMU solvent: 85 parts by mass) was formed.

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

(Preparation of polyimide film)
The polyimide precursor composition obtained as described above was heated on a glass substrate (large slide glass, product name "S9213" manufactured by Matsunami Glass Industry Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm). A coating film was formed by spin coating so that the thickness of the coating film after curing was 13 μm. Then, the glass substrate with the coating film formed thereon was placed on a hot plate at 60° C. and allowed to stand still for 2 hours to evaporate and remove the solvent from the coating film.
After removing the solvent, the glass substrate with the coating film formed thereon 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), leave at 25°C for 0.5 hours, then heat at 135°C for 0.5 hours, then heat at 300°C (final heating temperature) for 1 hour to cure the coating film to obtain polyimide-coated glass in which a thin film of polyimide (polyimide film) is coated on the glass substrate.

The resulting polyimide-coated glass was immersed in hot water at 90° C. to separate the polyimide film from the glass substrate to obtain a polyimide film 4 (76 mm long, 52 mm wide, and 13 μm thick). .

In order to identify the molecular structure of the resin that is the material of the resulting polyimide film, an IR spectrometer (manufactured by JASCO Corporation, trade name: FT/IR-4100) was used to measure the IR spectrum of the polyimide film sample. bottom. As a result of the measurement, it was found that C═O stretching vibration of imidecarbonyl was observed at 1696.2 cm ⁻¹ in the IR spectrum of the resin that was the material of the polyimide film. From the molecular structure identified based on such results, it was confirmed that the obtained polyimide film was indeed composed of a polyimide resin.

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

The total light transmittance value (unit: %) and the yellowness index (YI) of the film are measured using a product name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. 1 (published in 1997).

[Preparation of coating liquid]
An energy-sensitive composition containing a compound (P1) represented by the above formula (P1-1a) and a sulfonium salt represented by the above formula (Q1) at a mass ratio of 99:1 was added to a solvent (propylene glycol monomethyl ether Acetate (PGMEA)) was dissolved to prepare a coating liquid 1 having a solvent ratio of 80% by mass.

[Preparation of coating liquid for comparison]
A photosensitive composition containing an acrylic monomer (dipentaerythritol hexaacrylate) and a polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone) at a mass ratio of 99:1 is dissolved in a solvent (PGMEA) to obtain a solvent. A comparative coating liquid 2 having a ratio of 80% by mass was prepared.

[Evaluation 3]
Each of the coating liquid 1 and the comparative coating liquid 2 was applied to one surface 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 coating film having a thickness of 4 μm. Thereafter, the coating layer was irradiated with 100 mJ/cm ² using an ultraviolet curing machine with a wavelength of 365 nm to obtain each polyimide film having a hard coat (cured film) formed on one surface. Each obtained polyimide film was peeled off from the wafer, and the appearance was visually observed.

[Results/Discussion]
In the polyimide films 1 to 4 (Examples 6 to 9) in which the hard coat was formed using the coating liquid 1 according to this example, the transparency of the film did not decrease, and the coating liquid or the hard coat cured. It was confirmed that the degree of curling of the film due to curing was small, and the cure shrinkage was small.
On the other hand, the polyimide films 1 to 3 (Comparative Examples 10 to 12) on which a hard coat was formed using the coating liquid 2 for comparison were slightly yellowed and curled significantly due to curing of the coating liquid or hard coat. The hard coat made of coating liquid 1 according to the present example is considered to have a smaller cure shrinkage rate than the hard coat made of coating liquid 2, and it was confirmed that the degree of deformation of the polyimide film to be coated can be suppressed. rice field.

[Evaluation 4]
In Evaluation 3, the surface resistance of each hard coat formed on polyimide films 1 to 4 was measured using Hiresta MCP-HT450 (manufactured by Mitsubishi Analytic Tech), probe UR-100, and measuring voltage of 1,000V. All the surface resistance values were over 1×10 ¹⁵ Ω.
From this result, it was confirmed that the coating liquid 1 according to this example can form a hard coat with high surface resistance.

<<Examples 10 to 14 and Comparative Examples 14 to 15>>
In Examples 10-13 and Comparative Examples 14-15, the compounds (P1-1a) and (P1-2a) used in Examples 1 and 3, the sulfonium salt (Q1), the compound (P1-6d) shown below, The sulfonium salt and the like (z3) were mixed at the compounding ratio shown in Table 1 to prepare a mixed solution. In addition, in Table 3, the unit of the compounding ratio is parts by mass.

<Material>
[Compound (p1-6d)]

[Sulfonium salt etc. (z3)]

[Evaluation 5]
The viscosities of the liquid mixtures obtained in Examples 10 to 14 and Comparative Examples 14 to 15 were measured using an E-type viscometer at 25° C. and 1 to 100 rpm. Table 1 shows the results. 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 mPa s (200 cP). ) was about.

0.3 g of the mixed solutions obtained in Examples 10 to 14 and Comparative Examples 14 to 15 were precisely weighed and sealed in glass vials, and exposed to an exposure amount of 1500 mJ/cm using an ultraviolet irradiation device (HMW-532D, manufactured by ORC). ² , post-baking was performed at 100° C. for 15 minutes and at 85° C. for 100 hours to prepare each sample.

Each sample was set in a headspace sampler (TurboMatrix ATD, manufactured by Perkins Elmer) and heated at 100° C. for 30 minutes, and outgassing was measured using a gas chromatograph mass spectrometer (Clarus 580, manufactured by Perkins Elmer). . Table 3 shows the results. In the table, the measured value (area %) of Comparative Example 14 is set to 100, and the values are shown as relative values.

[Discussion]
As shown in Table 3, Example 10 using the compound (P1-1a) and the sulfonium salt (Q1) has the same viscosity as Comparative Example 14 that does not use the sulfonium salt (Q1), but outgassing It was also confirmed that the amount of generated was small. Similarly, Example 14 using the compound (P1-1a), the compound (P1-6d), and the sulfonium salt (Q1) has an equivalent viscosity compared to Comparative Example 15 that does not use the sulfonium salt (Q1). Despite this, it was confirmed that the amount of outgas generated was small.

Further, as can be seen from the results of Examples 10 and 11, even if the amount of the sulfonium salt (Q1) is extremely small, it has the effect of reducing the viscosity of the mixed liquid (energy-sensitive composition) and reducing outgassing. One thing has been confirmed. Similarly, as can be seen from the results of Examples 12 and 13, even if the amount of the sulfonium salt (Q1) is extremely small, the effect of reducing the viscosity of the mixed liquid (energy-sensitive composition) and reducing outgassing It was confirmed that there is

From the results of Examples 11 and 12, when the total content of compound component (P) to compound (P1) is the same, as compound component (P) to compound (P1), compound (P1-1a) alone Also, it was confirmed that the combined use of the compound (P1-1a) and the compound (P1-2a) has the effect of lowering the viscosity of the mixed liquid (energy-sensitive composition) and reducing outgassing. Accordingly, as the compound component (P) to the compound (P1), the alicyclic epoxy compound represented by the above formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) It is suggested that it may be preferable to use together with.

<<Examples 15 to 24>>
[Preparation of energy-sensitive composition with high refractive index]
In Examples 15 to 24, the following cationically and/or acid catalytically polymerizable and/or crosslinkable compound (P1) and a sulfonium salt or the like were mixed at a compounding ratio shown in Table 4 to form an energy sensitive composition. made things. In Table 4, the unit of the compounding ratio is parts by mass, and the compounding ratio of the solvent is the mass ratio. Example 23 was prepared by further adding 10 parts by mass of cerium oxide (average particle size: 50 nm) to the sum of 100 parts by mass of the components (P1) and (Q1) in Example 15. Example 24 was prepared by further adding 100 parts by mass of titanium oxide (average particle size: 5 to 10 nm) to the sum of 100 parts by mass of components (P1) and (Q1) in Example 15. In Examples 15 to 23, the amount of solvent was adjusted so that the concentration of the components excluding the solvent was 20% by mass. In Example 24, the amount of solvent was adjusted so that the concentration of the components excluding the solvent was 10% by 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 reaction product of bisphenol A and epichlorohydrin)

[Alkali-soluble resin]
・Preparation of alkali-soluble resin (A1a) First, 0.34 mol of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, 0.68 mol of acrylic acid, and propylene glycol monomethyl ether acetate are placed in a 500 ml four-necked flask. 139.0 g of tetraethylammonium bromide (TEAB) and 2.15 g of tetraethylammonium bromide (TEAB) were charged and stirred for 20 hours under heating at 100 to 105° C. for reaction. Next, 0.12 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 0.27 mol of 1,2,3,6-tetrahydrophthalic anhydride were charged into the flask and heated to 120 to 125°C. The mixture was stirred for 8 hours under heating at , and reacted. Further, 0.28 mol of glycidyl methacrylate was charged and stirred for 8 hours while heating at 100 to 105° C. to obtain an alkali-soluble resin (A1a). The resulting alkali-soluble resin (A1a) had a solid content concentration of 57.0 wt %, an acid value (in terms of solid content) of 82 mgKOH/g, and an Mw of 3,500 by GPC analysis.

・Preparation of alkali-soluble resin (A2a) First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110 mg of tetramethylammonium chloride, 2,6-di-tert-butyl-4-methyl are placed in a 500 ml four-necked flask. 100 mg of phenol and 72.0 g of acrylic acid were charged and heated and dissolved at 90 to 100° C. while blowing air at a rate of 25 ml/min. Next, the solution was gradually heated to 120° C. while the solution was still cloudy and dissolved completely. At this time, the solution gradually became transparent and viscous, but the stirring was continued. During this time, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula (f-4).

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-obtained bisphenol fluorene type epoxy acrylate and dissolved, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. After mixing, the temperature was gradually increased to 110-115° C. for 4 hours to react. After confirming the disappearance of the acid anhydride groups, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain an alkali-soluble resin (A2a) having a cardo structure. rice field. Disappearance of acid anhydride groups was confirmed by IR spectrum.
The alkali-soluble resin (A2a) having a cardo structure corresponds to the compound represented by the above general formula (f-1).

[Additive]
・(Add-1)
Polyether-modified polydimethylsiloxane [BYK302 manufactured by BYK-Chemie Japan]

・(Add-2)
Perfluoroalkyl group-containing oligomer [F-477 manufactured by DIC]

[solvent]
・(S1) cyclohexyl acetate ・(S2) diethylene glycol monobutyl ether acetate ・(S3) propylene glycol monomethyl ether acetate ・(S4) diethylene glycol methyl ethyl ether ・(S5) N-methylpyrrolidone

[Evaluation 6]
Each 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 exposed (broadband) with an exposure dose of 100 mJ/cm ² using an ultraviolet curing machine. After that, a post-baking treatment was performed at 150° C. for 20 minutes (230° C. for 20 minutes in Example 24). The thickness of the cured films of Examples 15 to 23 was 500 nm, and that of Example 24 was 50 nm. Each cured film is heat resistant. The refractive index at a wavelength of 633 nm was measured for each cured film. It was confirmed that all compositions had a high refractive index of 1.7 or more. In particular, the cured film of Example 23, to which cerium oxide, which is a metal oxide particle, was added has a refractive index of 1.75 or more, and that of Example 24 has a refractive index of 1.8 or more, which indicates a high refractive index (transparency). I was able to plan.

Claims (7)

(P1) a cationically polymerizable compound;
(Q) a sulfonium salt represented by the following formula (a1);
and metal oxide particles.

(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 mutually bonded to form may form a ring together with the sulfur atom therein, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S or Se, X ^— represents a monovalent anion, provided that R ¹ and R ² are not both alkyl groups optionally substituted with halogen atoms.)

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

(Wherein ^R5 is a hydroxy 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 a 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 alkylene group or a group represented by the following formula (a5), wherein R ⁶ is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthio carbonyl group, 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, represents an optionally substituted amino group, a cyano group, a nitro group, or an optionally halogen-substituted alkyl group or a group represented by the following formula (a6), wherein A ² is a single bond, S, O, represents a sulfinyl group or a carbonyl group, and n1 represents 0 or 1.)

(wherein R ⁷ and R ⁸ are independently a hydroxy 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, 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 or an alkylene group optionally substituted with a halogen atom or a group represented by the following formula (a5), wherein R ⁹ and R ¹⁰ are independently an alkyl group optionally substituted with a halogen atom or the above represents a group represented by 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 is a single bond, S, O, a sulfinyl group, or a carbonyl group, X ^- is as described above, n2 is 0 or 1, provided that R ⁹ and R ¹⁰ are not simultaneously an alkyl group optionally substituted with a halogen atom.)

(In the formula, ring ^Z2 represents an aromatic hydrocarbon ring, and ^R11 represents an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryl oxycarbonyl group, arylthiocarbonyl group, 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, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 is an integer of 0 or more.)

(Wherein, ring Z ³ represents an aromatic hydrocarbon ring, R ¹² represents an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryl oxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, 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, and m3 is an integer of 0 or greater.) 2. The energy-sensitive composition according to claim 1, wherein the (P1) compound is a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, and an alicyclic epoxy group. 3. The energy-sensitive composition according to claim 1, wherein in said sulfonium salt, said monovalent anion represented by said X ^{1 -} 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 part of the hydrogen atoms are substituted with halogen atoms or electron-withdrawing groups, Y represents a halogen atom, and c represents an integer of 1 to 4.) 4. The weight loss rate from the peak value in thermogravimetric measurement (TG) in which the temperature is raised to 230° C. at a temperature elevation rate of 10° C./min in an air current is 10% or less, according to any one of claims 1 to 3. of energy sensitive compositions. 5. The energy-sensitive composition according to any one of claims 1 to 4, which is a sealing material for organic EL display elements or a curable composition for wafer-level lenses. A cured product obtained by curing the energy-sensitive composition according to any one of claims 1 to 5. A method for producing a cured product, comprising polymerizing and/or crosslinking the energy-sensitive composition according to any one of claims 1 to 5.

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