JP2017179330A - Energy sensitive composition, cured article and manufacturing method of cured article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy sensitive composition excellent in heat weight stability, a cured article by curing the same and a manufacturing method of the cured article.SOLUTION: There is provided an energy sensitive composition containing (P) at least one polymerizable or crosslinkable compound component and (Q) a sulfonium salt represented by the formula (a1).SELECTED DRAWING: None

Description

  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 an encapsulant for organic EL display elements 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 outgas which causes deterioration of an organic EL display element has an epoxy group or an oxetanyl group, and an ether other than an epoxy group or an oxetanyl group. An energy sensitive resin composition free of bonds and ester bonds has been proposed. Patent Document 2 discloses an alicyclic epoxy compound having a specific structure, two or more glycidyl groups in the molecule as an energy-sensitive resin that is suppressed in yellowing even in a high-temperature environment and is excellent in transparency and curability. An energy-sensitive resin composition containing a siloxane compound having a curing agent and a curing agent has been proposed.

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

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

  An object of this invention is to provide the energy sensitive composition excellent in thermogravimetric stability, the hardened | cured material which hardened this composition, and the manufacturing method of this hardened | cured material.

  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.

  The first aspect of the present invention comprises (P1) a cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound, and (P2) a compound that increases its solubility in a developer under the action of an acid. And (Px) at least one compound component (P) selected from the group consisting of radically polymerizable or crosslinkable compounds and (Q) a sulfonium salt represented by the 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。）

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

（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。）

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, acyloxy group, alkylthio group which may be substituted with a halogen atom. , Thienyl group, thienylcarbonyl group, furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy (poly) alkyleneoxy group, 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 R ⁵ 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 group Hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom substituted also represents a group represented by an alkylene group or the following formula (a5), R ⁶ is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Ali Ruthiocarbonyl 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, an alkyl group optionally substituted with a halogen atom, or a group represented by the following formula (a6), A ² represents a single bond, S, O And 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 A group, 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 a group represented by the formula (a2), ^{R 9} and R ⁰ may form a ring with the sulfur atom bonded to each other, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, X ^- are as defined above, n2 Represents 0 or 1, provided that R ⁹ and R ¹⁰ are not simultaneously an alkyl group which may be 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 Z ² represents an aromatic hydrocarbon ring, and R ¹¹ represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl group which may be substituted with a halogen atom. 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 ( A poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents 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。）

(In the formula, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl group which may be substituted with a halogen atom. 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 represents an integer of 0 or more.)

  The 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.

  3rd aspect of this invention is a manufacturing method of hardened | cured material including superposing | polymerizing and / or bridge | crosslinking the energy sensitive composition of 1st aspect of this invention.

  ADVANTAGE OF THE INVENTION According to this invention, the energy sensitive composition excellent in thermogravimetric stability, the hardened | cured material which hardened 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. 10 is a TG / DSC curve showing the thermogravimetric change of Comparative Example 7. 10 is a TG / DSC curve showing the thermogravimetric change of Comparative Example 8. 10 is a TG / DSC curve showing the thermogravimetric change of Comparative Example 9. It is a TG / DSC curve which shows the thermogravimetric change of a reference example.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. .
In the present specification, description such as “A and / or B”, “A and / or B”, “A and / or B”, and the like, for example, “cationically and / or acid-catalyzed” “At least one selected from the group consisting of A and B”. Here, A and B are arbitrary terms.

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

  The energy-sensitive composition according to the present invention includes a sulfonium salt represented by the above formula (a1) (hereinafter also referred to as “sulfonium salt (Q)”), whereby the compound component (P) and the sulfonium salt (Q ), The proton concentration increases as the temperature rises, so that the sequential polymerization in the compound component (P) proceeds continuously, the polymerization is promoted, and it is presumed that there are few monomers decomposed by heat. Thereby, it is estimated that the energy sensitive composition which concerns on this invention improves the weight stability with respect to a heat | fever. 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 extracting hydrogen from the components in the system.

[(P1) Cationic and / or Acid Catalytically Polymerizable and / or Crosslinkable Compound]
A cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound (hereinafter also referred to as “compound (P1)”) can be cationically polymerized, for example, with an alkyl group or aryl group-containing cation, or with a proton. Contains compounds. Examples thereof include cyclic ethers, especially epoxy compounds and oxetane compounds, 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 having an epoxy group and / or oxetanyl group (epoxy / oxetanyl group-containing / vinyl group-containing compound), In the case of P1) and other compounds (epoxy / oxetanyl group-free / vinyl group-containing compound), the compound (Px) is used. In this specification, unless otherwise specified, “epoxy” generally includes not only oxiranyl but also oxetanyl and alicyclic epoxy.

  Further examples include amino plastics or phenolic resole resins. These are in particular melamine resins, urea resins, epoxy resins, phenol resins, acrylic resins, polyester resins and alkyd resins, but in particular mixtures of acrylic resins, polyester resins or alkyd resins with melamine resins. These include modified surface coating resins (for example, acrylic modified polyester resins and acrylic modified alkyd resins). The term surface coating resin preferably includes an amino resin. Examples thereof include etherified and non-etherified melamine resins, urea resins, guanidine resins, biuret resins. Acid catalysts for curing surface coatings comprising etherified amino resins (eg methylated melamine resins or butylated melamine resins (N-methoxymethyl-melamine or N-butoxymethyl-melamine) or methylated / butylated glycoluril) Of particular importance.

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

  Specific examples of the aliphatic epoxy compound having an alicyclic epoxy group include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4 -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 modification 3 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxy) Cyclohexanecarboxylate), epoxycyclohexahydrophthalic acid dioctyl, epoxycyclohexahydrophthalic acid di-2-ethylhexyl, epoxy resin having tricyclodecene oxide group, and the following formulas (P1-1) to (P1-5) The compound represented by these is mentioned. Among the specific examples of these aliphatic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (P1-1) to (P1-4) are the following in that sequential polymerization proceeds and polymerization is promoted. Preferably, alicyclic epoxy compounds represented by the following formulas (P1-1) to (P1-2) are more preferable. 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 outgas, the alicyclic epoxy compound represented by the formula (P1-1) and the formula (P1-2) are represented. It is preferable to include at least one of the group consisting of the alicyclic epoxy compound and the alicyclic epoxy compound represented by the formula (P1-8), and the ratio of the compound component (P) to the compound (P1) is 1 It may be -99 mass%, and is 10-90 mass%, 20-80 mass%, 30-70 mass%, 40-60 mass%, etc. Moreover, 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 the viscosity of the outgas reduction and energy sensitive composition). It is preferable at the point made. When using together the alicyclic epoxy compound represented by Formula (P1-1) and the alicyclic epoxy compound represented by Formula (P1-2), the alicyclic represented by Formula (P1-1) The content of the alicyclic epoxy compound represented by the formula (P1-1) relative to the total amount of the epoxy compound and the alicyclic epoxy compound represented by the formula (P1-2) is not particularly limited. 1-99 mass% may be sufficient, 10-90 mass%, 20-80 mass%, 30-70 mass%, 40-60 mass% etc. may be sufficient.

（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 group. A group selected from the group consisting of groups, for example, a hydrogen atom, a halogen atom, or a hydrocarbon group that may contain an oxygen atom or a halogen atom, which may be the same or different, respectively. May be good.)

Examples of the linking group Z include a divalent hydrocarbon group, —O—, —O—CO—, —S—, —SO—, —SO ₂ —, —CBr ₂ —, —C (CBr ₃ ) _2. And a divalent group selected from the group consisting of —, —C (CF ₃ ) ₂ —, and —R ^a19 —O—CO—, and a group in which a plurality of these groups are bonded.

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

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

  As the compound represented by the formula (P1-1), a compound which is difficult to take a conjugated structure (particularly, a π-electron conjugated structure) by dehydrogenation is a cured product having excellent transparency in addition to thermogravimetric stability. It is preferable in that it can be obtained, and in particular, an alicyclic epoxy compound, specifically, two alicyclic epoxy groups in one molecule are connected via a linking group containing a quaternary carbon and / or a hetero atom. Bound compounds are preferred.

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

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

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

  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. And a group consisting of an oxygen atom and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1-20 are preferable, as for the carbon atom number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 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 Chain alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl, 2-n-butenyl, and 3-n-butenyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl And a cycloalkyl group such as 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, phenanthryl group and other aryl groups; benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group And aralkyl groups such as

  Specific examples of the halogenated hydrocarbon group 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, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And 4-bu Halogenated cycloalkyl group such as mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6 -Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4- Halogenated aryl groups such as fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2 -Fluorophenylmethyl group, 3-fluorophenyl Methyl group, a halogenated aralkyl group such as 4-fluorophenyl methyl group.

  Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxy chain groups such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl groups; halogenated cycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl groups; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3 -Hydroxyaryl groups such as dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group ; 2-hydroxyphenylmethyl group, 3-hydroxy A hydroxyaralkyl group such as an phenylmethyl group and a 4-hydroxyphenylmethyl group; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a 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-tri Decyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, etc. Chain alkoxy group; vinyloxy group, 1-propenylo Chain-like alkenyloxy groups such as 2- group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; phenoxy group, o-tolyloxy Group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, And aryloxy groups such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, β-naphthylethyloxy group, etc. Aralkyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethyl group 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl group, Alkoxymethoxy groups such as 4-methoxy-n-butyl group, 4-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- Alkoxyalkoxy such as methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group Groups; alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group and 4-methoxyphenyl group; alkoxyaryloxy groups such as 2-methoxyphenoxy group, 3-methoxyphenoxy group and 4-methoxyphenoxy group An aliphatic acyl group such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyl group; benzoyl group, α-naphthoyl group, and β-naphthoyl An aromatic acyl group such as a group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n -Octyloxy Chain alkyloxycarbonyl groups such as sulfonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl, α-naphthoxycarbonyl, and β-naphthoxycarbonyl Aliphatic groups such as formyloxy, acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy An acyloxy group; an aromatic acyloxy group such as a benzoyloxy group, an α-naphthoyloxy group, and a β-naphthoyloxy group;

R ^{a1 to} R ^a18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. It is more preferable that R ^{a1 to} R ^a18 are all hydrogen atoms from the viewpoint that the cured product obtained using the sensitive composition is excellent in mechanical properties.

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

  Specific examples of suitable compounds among the alicyclic epoxy compounds represented by the formula (P1-1) include alicyclic rings represented by the following formulas (P1-1a) (P1-1b) (P1-1c). An epoxy compound of the formula, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane [= 2,2-bis (3,4-epoxycyclohexyl) propane], and the like can be given.

  Specific examples of suitable compounds among the alicyclic epoxy compounds represented by the formula (P1-2) include bicyclononadiene diepoxides or dicyclononadiene diepoxides represented by the following formula (P1-2a). Etc.

Among the alicyclic epoxy compounds represented by the 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.

  Specific examples of suitable compounds among the alicyclic epoxy compounds represented by the formula (P1-4) include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4- (3- And methyloxiran-2-yl) -7-oxabicyclo [4.1.0] heptane.

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

In addition to the aliphatic epoxy compound having an alicyclic epoxy group described above, examples of non-polymer having an epoxy group that can be used as the compound (P1) include glycidyl (meth) acrylate, 2-methylglycidyl (meta ) Epoxyalkyl (meth) acrylates such as acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n- Epoxyalkyloxyalkyl such as propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate (Meth) acrylate; bi Bifunctional epoxy resins such as phenol 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 resin, brominated phenol Novolac epoxy resins such as novolac epoxy resins, orthocresol novolac epoxy resins, bisphenol A novolac epoxy resins, and bisphenol AD novolac epoxy resins; cycloaliphatic epoxy resins such as epoxidized products of dicyclopentadiene phenol resins; Aromatic epoxy resins such as epoxidized products of naphthalene type phenol resins; 9,9-bis [4- (glycidyloxy) phenyl] -9H-fluorene, 9,9-bis [ -[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-glycidyloxy) Naphthalen-2-yl) -9H-fluorene, 9,9-bis (6-glycidyloxynaphthalen-1-yl) -9H-fluorene, 9,9-bis (5-glycidyloxynaphthalen-1-yl) -9H -9,9-bis (glycidyloxynaphthyl) fluorenes such as fluorene; 9,9-bis [6- (2-glycidyloxyethoxy) naphthalene- 2-yl] -9H-fluorene, 9,9-bis [6- (2-glycidyloxypropoxy) naphthalen-2-yl] fluorene, 9,9-bis [5- (2-glycidyloxyethoxy) naphthalene-1 9,9-bis (glycidyloxyalkoxynaphthyl) fluorenes such as -yl] fluorene, 9,9-bis [5- (2-glycidyloxypropoxy) naphthalen-1-yl] fluorene; 9,9-bis {6 -[2- (2-glycidyloxyethoxy) ethoxy] naphthalen-2-yl} -9H-fluorene, 9,9-bis {6- [2- (2-glycidyloxypropoxy) propoxy] naphthalen-2-yl} -9H-fluorene, 9,9-bis {5- [2- (2-glycidyloxyethoxy) ethoxy] naphthalen-1-yl} -9H 9,9-bis (glycidyloxydialkoxynaphthyl) fluorenes such as fluorene, 9,9-bis {5- [2- (2-glycidyloxypropoxy) propoxy] naphthalen-1-yl} -9H-fluorene; Epoxy group-containing fluorene compounds; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmetaxylylenediamine, and tetraglycidyl bisaminomethyl Glycidylamine type epoxy resins such as cyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ester Ter, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3- Epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2 , 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, etc .; tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, And tetrafunctional epoxy resins such as tetraglycidoxybiphenyl, and 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel).
Further, 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl oxetane, 3-ethyl-3-hydroxymethyl oxetanyl methacrylate, bis-1-ethyl-3-oxetanyl methyl ether, 1,4-bis-3-ethyl oxetane Monofunctional or bifunctional or higher functional oxetane compounds such as -3-ylmethoxymethylbenzene, 3-ethyl-3--2-ethylhexyloxymethyl oxetane, and 3-ethyl-3-phenoxymethyl oxetane are also preferably exemplified.

  Among the non-polymers having an epoxy group that can be used as the compound (P1) other than the aliphatic epoxy compound having an alicyclic epoxy group, an epoxy group-containing fluorene compound is preferable in terms 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 represents a condensed polycyclic aromatic hydrocarbon ring, R ^P35 and R ^P36 represent a substituent, R ^P37 represents a hydrogen atom or a methyl group, and k1 represents 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 is a condensed bicyclic hydrocarbon ring (for example, a C8-C20 condensed dicyclic ring such as an indene ring or a naphthalene ring). A condensed bicyclic hydrocarbon ring such as a cyclic hydrocarbon ring, preferably a C10-C16 condensed bicyclic hydrocarbon ring), a condensed tricyclic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.), etc. Can be mentioned. Preferred examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable. In addition, the two rings Z ⁴ substituted at the 9-position of fluorene may be the same or different rings, and may usually be the same rings.

In addition, the substitution position of the ring Z ⁴ substituted at the 9th position of fluorene is not particularly limited. For example, the naphthyl group substituted at the 9th position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like. In particular, a 2-naphthyl group is preferable.

In the above formula (P1-8), examples of the substituent represented by R ^P35 include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, Non-reactive substituents such as an aryl group (C6-C10 aryl group such as a phenyl group) and the like are mentioned, and in particular, a halogen atom, a cyano group or an alkyl group (particularly an alkyl group) is often used. Examples of the alkyl group include C1-C6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C1-C4 alkyl group, particularly a methyl group). In addition, when k1 is plural (two or more), R ^P35 may be different from each other or the same. Also, R ^P35 substituting the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or may be different. Further, the bonding position (substitution position) of R ^P35 to the benzene ring constituting the fluorene is not particularly limited. Preferred k1 is 0 to 1, particularly 0. In the two benzene rings constituting fluorene, k1 may be the same or different from each other.

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

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. ^Rp36 is preferably a hydrocarbon group [eg, alkyl group (eg, C1-C6 alkyl group)], alkoxy group (C1-C4 alkoxy group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom). Etc.).

In the same ring Z ⁴ , when k2 is plural (two or more), ^RP36 may be different from each other or the same. In the two rings Z ⁴ , R ^P36 may be the same or different. The preferable k2 may be 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably 0 to 4, particularly 0 to 2 (for example, 0 to 1). Incidentally, in the two rings Z ^4, k2 may be the same or different from each other.

In the above formula (P1-8), R ^P37 is a hydrogen atom or a methyl group, and preferred R ^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. Note that 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 of ring Z ⁴ . In particular, the epoxy group-containing group is at least substituted in a condensed polycyclic hydrocarbon ring with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene (eg, the 5-position, 6-position, etc. of the naphthalene ring). There are many cases.

  Specific examples of the compound represented by the formula (P1-8) include 9,9-bis (glycidyloxynaphthyl) fluorene [for example, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene. , 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene and the like], and the like, and the like, and the like.

(Polymer having epoxy group)
The polymer having an epoxy group may be a polymer obtained by polymerizing a monomer mixture containing an epoxy group-containing monomer or an epoxy group-containing monomer, and includes a hydroxyl group, a carboxy group, and an amino group. For example, an epoxy group may be introduced into a polymer having a functional group having reactivity such as an epoxy group such as epichlorohydrin. A partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain such as 1,2-polybutadiene can also be suitably used as the polymer having an epoxy group. Such a partial oxide includes an epoxy group generated by oxidation of an unsaturated bond contained in the side chain.

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

(Polymer of a monomer mixture containing a monomer having an epoxy group or a monomer having an epoxy group)
Among the polymers having an epoxy group, it is easy to prepare, or is a homopolymer of an (meth) acrylic acid ester having an epoxy group, from the viewpoint of applicability of the energy sensitive composition to a substrate, A copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is preferred.

  The (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Moreover, the (meth) acrylic acid ester which has an epoxy group may contain the aromatic group. Among the (meth) acrylic acid ester having an epoxy group, an aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group or the like from the viewpoint of transparency of a cured product formed using an energy sensitive composition An aliphatic (meth) acrylic acid ester having an alicyclic epoxy group is preferable, and an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group is more preferable.

  Examples of (meth) acrylic acid ester 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, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.

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

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

  Specific examples of the aliphatic (meth) acrylic acid ester 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 aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents a divalent having 1 to 10 carbon atoms. A hydrocarbon group is shown, t shows the integer of 0-10. R ^a21 is preferably 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, or a hexamethylene group. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, and a cyclohexylene group are preferable.

  As the polymer having an epoxy group, any of a homopolymer of (meth) acrylic acid ester having an epoxy group and a copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is used. However, the content of the unit derived from the (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 has an unsaturated carboxylic acid or an epoxy group. Examples thereof include (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 alkali and the like, (meth) acrylic acid ester having an epoxy group and other monomers And the copolymer preferably contains no unit derived from an unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and 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. Linear or branched alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (Meth) acrylate, furfuryl (meth) acrylate; (meth) acrylic acid ester having a group having an alicyclic skeleton. Among (meth) acrylic acid esters having no epoxy group, (meth) acrylic acid ester having a group having an alicyclic skeleton is used from the viewpoint of transparency of a cured product formed using an 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. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl 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 preferable, and compounds represented by the following formula (a3-3) or (a3-4) are more preferable.

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^a24 is preferably a single bond or 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, or 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, and 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 acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Etc.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl 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- Dichlorov And the like; vinyl ether, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Examples include phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

  Examples of styrenes include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene. Alkyl styrene such as ethoxymethyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Methylstyrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

(Partial oxide of polymer having unsaturated aliphatic hydrocarbon group in side chain)
The polymer having an unsaturated aliphatic hydrocarbon in the side chain is not particularly limited, but 1,2-polybutadiene having a vinyl group in the side chain is preferred because it is easily available and synthesized. By partially oxidizing 1,2-polybutadiene, an epoxidized polybutadiene having an oxiranyl group and a vinyl group in the side chain is obtained. The ratio of the oxiranyl group in such epoxidized polybutadiene is preferably 10 to 70 mol%, more preferably 10 to 50 mol%, and more preferably 10 to 40 mol% with respect to the total number of moles of the oxiranyl group and the vinyl group. preferable. As the epoxidized polybutadiene, JP-100 and JP-200 commercially available from Nippon Soda Co., Ltd. can be suitably used.

  The molecular weight of the polymer having an epoxy group described above is not particularly limited as long as the object of the present invention is not impaired, but the polystyrene-equivalent mass average molecular weight is preferably 3,000 to 30,000, preferably 5,000 to 5,000. 15,000 is more preferable.

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

（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 represent a linear, branched or cyclic alkylene group, an arylene group, —O—, —C (═O) —, —NH—, and these 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. And at least one substituent selected from the group consisting of a group, a thiol group, a carboxy group, a hydroxyl group and a succinic anhydride group, 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 group represented by R ^P31 and E ¹ , R ^P32 and E ² , and R ^P33 and E ³ is a group represented by the following formula (P1-6a), for example. It is preferable that at least two are groups represented by the following formula (P1-6a), and each is a group represented by the following formula (P1-6a). More preferably. The groups represented by formula (P1-6a) bonded to one compound are preferably the same group.
-LC (P1-6a)
(In the formula (P1-6a), L is a group consisting of a linear, branched or cyclic alkylene group, an arylene group, —O—, —C (═O) —, —NH—, and a combination thereof. And C is at least one selected from the group consisting of an epoxy group and an oxetanyl group, and 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 as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is a carbon atom. The arylene group of several 5-10 is preferable. In the formula (P1-6a), L represents a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, —O—, —C (═O) —, —NH—, and a combination thereof. It is preferable that at least one of a linear alkylene group having 1 to 3 carbon atoms such as a methylene group and a phenylene group, or these, and -O-, -C (= O)-, and NH-. A group consisting of a combination with at least one of these 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). When forming the structure which has an epoxy group, the organic group represented by the following formula (P1-6b) or (P1-6c) is 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 represents a hydrogen atom or a methyl group.)

  Hereinafter, examples of the epoxy compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, and an alicyclic epoxy group are shown as examples of the compound represented by the formula (P1-6). 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 prevention property (= heat resistant transparency) when exposed to a high temperature environment for a long time to the obtained cured product, and two or more glycidyl groups in the molecule. And a compound having a siloxane skeleton composed of siloxane bonds (Si—O—Si). Examples of the siloxane skeleton in the siloxane compound (B) include a cyclic siloxane skeleton and a polysiloxane skeleton (for example, a linear or branched silicone (linear or branched polysiloxane), a cage type or a ladder type). And polysilsesquioxane, etc.).

  As the siloxane compound (B), among them, a compound having a cyclic siloxane skeleton represented by the following formula (B-1) (hereinafter, referred to as the following formula (B-1) is excellent in curability and the cured product obtained is particularly excellent in heat-resistant transparency. (It may be referred to as “cyclic siloxane”).

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 represent a monovalent group or an alkyl group containing a glycidyl group. However, at least two of the n R ^B1 and n R ^{B2 in} the compound represented by the formula (B-1) are monovalent groups containing a glycidyl group. N in the formula (B-1) represents an integer of 3 or more. In addition, R ^B1 and R ^B2 in the compound represented by the formula (B-1) may be the same or different. Moreover, several R ^<B1> may be the same and may differ. The plurality of R ^B2 may be the same or different.

The monovalent group containing the glycidyl group is preferably a glycidyl ether group represented by -D-O-R ^B3 [D represents an alkylene group, and R ^B3 represents a glycidyl group]. Examples of D (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. be able to.

  Examples of the 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 a methyl group, an ethyl group, a propyl group, and an isopropyl group. And a branched alkyl group.

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

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

  The epoxy equivalent (based on JlS K7236) of the siloxane compound (B) is preferably from 100 to 350, particularly preferably from 150 to 300, most preferably 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 this embodiment includes other siloxane compounds (for example, alicyclic epoxy group-containing cyclic siloxane, and 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, and the like.

  More specifically, examples of the siloxane compound (B) include cyclic siloxanes having two or more glycidyl groups in the molecule represented by the following formula. Examples of the siloxane compound (B) include trade names “X-40-2701”, “X-40-2728”, “X-40-2738”, “X-40-2740” (hereinafter, Shin-Etsu Chemical). Commercial products such as those manufactured by Kogyo Co., Ltd. can be used.

[(P2) Compound that increases its solubility in a developer under the action of an acid]
Examples of compounds that increase their solubility in a developer under the action of an acid (hereinafter also referred to as “compound (P2)”) include, for example, oligomers and polymers that can be obtained by copolymerization of the monomers listed below. And copolymers.

  Acyclic or cyclic secondary and tertiary alkyl (meth) acrylates [eg tert-butyl acrylate, tert-butyl methacrylate, 3-oxocyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2-methyl- 2-adamantyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl methacrylate, 5-norbornene-2-tert-butyl ester, 8-ethyl-8-tricyclodecanyl (meth) acrylate , (2-tetrahydropyranyl) oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl) oxymethyltricyclododecane methanol methacrylate, trimethylsilylmethyl (meth) acrylate (2-tetrahydropyranyl) oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl) oxymethyltricyclododecane methanol methacrylate, trimethylsilylmethyl (meth) acrylate], o- / m- / p- (3-oxocyclohexyl Oxy) 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 [eg o- / m- / p-tert-butoxycarbonylstyrene, o − / M− / p− (3-oxocyclohexyloxycal Nyl) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonyl) styrene, o- / m- / p-tetrahydropyranyloxycarbonylstyrene, o- / m- / p-adamantyloxy Carbonyl styrene, o- / m- / p-cyclohexyloxycarbonyl styrene, o- / m- / p-norbornyloxycarbonyl styrene], acyclic or cyclic alkoxycarbonyloxy styrene [eg 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 alkoxycarbonylalkoxystyrene [e.g. o- / m- / p-butoxycarbonylmethoxystyrene, p-tert-butoxycarbonylmethoxystyrene, o- / m- / p- (3-oxocyclohexyloxycarbonylmethoxy) styrene, o- / m- / p- ( 1-methyl-1-phenylethoxycarbonylmethoxy) styrene, o- / m- / p-tetrahydropyranyloxycarbonylmethoxystyrene, o- / m- / p-adamantyloxycarbonylmethoxystyrene, o- / m- / p -Cyclohexyloxycar Nylmethoxystyrene, o- / m- / p-norbornyloxycarbonylmethoxystyrene, trimethylsiloxystyrene, dimethyl (butyl) siloxystyrene], unsaturated alkyl acetates (eg isopropenyl acetate, derivatives thereof), 5-norbornenyl- 2-tert-butyl ester

  Monomers carrying acid labile groups with low activation energy [eg p- or m- (1-methoxy-1-methylethoxy) styrene, p- or m- (1-methoxy-1-methylethoxy)- Methylstyrene, p- or m- (1-methoxy-1-methylpropoxy) styrene, p- or m- (1-methoxy-1-methylpropoxy) 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-isoprop Xyl-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-methylethoxy) styrene, p- or m- (1-n-butoxyethoxy) styrene, p- or m- ( 1-isobutoxy-1-methyl-ethoxy) -styrene, p- or m- (1-tert-butoxy-1-methylethoxy) styrene, p- or m- (1-n-pentyloxy-1-methylethoxy) Styrene, p- or m- (1-isoamyloxy-1-methylethoxy) styrene, p- or m- (1-n-hexyloxy-1-methyl- Ethoxy) styrene, p- or m- (1-cyclohexyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy) -1-methylethoxy) -methylstyrene, p- or m- (1-benzyloxy-1-methylethoxy) styrene, p- or m- (1-benzyloxy-1-methylethoxy) methylstyrene, p- or m- (1-methoxy-1-methylethoxy) styrene, p- or m- (1-methoxy-1-methylethoxy) -methylstyrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy)- Styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) methylstyrene]

  The compound (P2) may be a polymer having an alkoxyalkyl ester acid labile group. Examples of polymers with alkoxyalkyl ester acid labile groups can be found in US 5225316 and EP 829766. Examples of polymers with acetal protecting groups are described, for example, in US 5670299, EP 780732, US 5627006, US 5558976, US 5558971, US 5468589, EP 704762, EP 762206, EP 342498, EP 553737, and ACS Symp. Ser. 614, Microelectronics Technology, pp. 35-55 (1995), J. MoI. Photopolymer Sci. Technol. Vol. 10, no. 4 (1997), pp. 571-578, J.A. Photopolymer Sci. Technol. Vol. 12, no. 4 (1999) p. 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, suitable polymers for the composition according to this embodiment are not limited thereto.

  In addition, monomers having acid labile groups, where appropriate, other free radical polymerizable monomers that do not carry acid labile groups [eg, styrene, acrylonitrile, methyl, to establish specific solubility and adhesion. (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 a targeted manner prior to such polymer-like reactions, for example by partial hydrogenation, partial alkylation, partial acetylation. That is, a polymer having an acid labile group need not be synthesized from the monomer by copolymerization in all cases.

  For example, H.M. -T. Schacht, P.A. Falcigno, N .; Muenzel, R.M. Schulz and A.M. Medina, ACS Symp. Ser. 706 (Micro- and Nanopatterning Polymers), pp. 78-94, 1997; -T. Schacht, N .; Muenzel, P.M. Falcigno, H .; Holzwarth and J.H. Schneider, J. et al. Photopolymer Science and Technology, Vol. 9, (1996), 573-586, it is also possible to introduce acid labile bridges. Such an acid crosslinking system is preferred from the viewpoint of thermal stability. Such acid labile crosslinking can also be obtained by reaction of a phenolic group-containing polymer (eg, 4-hydroxystyrene copolymer) with bi- and polyfunctional vinyl ethers.

  Another example of the compound (P2) is a monomer compound (for example, a carboxylic acid and a phenol group-containing compound) in which each of a carboxylic acid group or a phenolic OH group is blocked by an acid labile protecting group. Such acid labile blocking is, for example, tert-butyl ester group, 2-methyl-2-adamantyl ester group, 8-ethyl-8-tricyclodecanyl ester group, tetrahydropyranyl ester group or some other acid cleavage. Can be carried out by conversion of a carboxy group to a functional ester group. The phenolic OH groups can be blocked according to known methods, for example by conversion to acid-cleavable tert-butyl carbonate groups, silyl ethers, acetal groups and ketal groups.

  The compound (P2) is selected from the group consisting of an alicyclic copolymer, a 4-hydroxy-phenyl group-containing copolymer, a maleic anhydride-containing copolymer, an acrylic acid-containing copolymer, an acrylate ester-containing copolymer, and a methacrylate ester-containing copolymer. At least one compound, wherein the copolymers carry functional groups that increase the solubility of the polymer in an alkaline developer after reaction with the acid.

[(Px) radical polymerizable or crosslinkable compound]
Examples of the radically polymerizable or crosslinkable compound (also referred to herein as “compound (Px)”) include acrylates having a reactive functional group. The reactive functional group can be selected from the group consisting of, for example, a hydroxyl group, a thiol group, an isocyanate group, an anhydride group, a carboxy group, an amino group, and a blocked amino group. Examples of the OH group-containing unsaturated acrylate include hydroxyethyl acrylate and hydroxybutyl acrylate. Compound (Px) may also be of any desired structure (eg, it may contain units such as polyesters, polyacrylates, polyethers, etc.), which contain ethylenically unsaturated double bonds and Furthermore, it contains a free OH group, COOH group, NH ₂ group or NCO group.

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

であって、ＣＨ_２＝ＣＨＣＯＯＨと

との反応により得られるものである。

Where CH ₂ = CHCOOH and

It is obtained by the reaction with.

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

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

（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 represent a linear, branched or cyclic alkylene group, an arylene group, —O—, —C (═O) —, —NH—, and these A group consisting of a combination, which may be the same or different, and each of E ^{4 to} E ⁶ is between the compound (P1) and the compound represented by the formula (Px-1); A functional group or a hydrogen atom that can be radically polymerized or cross-linked between the compounds represented by the formula (Px-1), provided that at least one of E ^{4 to} E ⁶ is the functional group. .)

In the 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 are groups represented by the following formula (Px-1a), and each of them is a group represented by the following formula (Px-1a). More preferably. The groups represented by the formula (Px-1a) bonded to one compound are preferably the same group.
-L'-C '(Px-1a)
(In the formula (Px-1a), L ′ represents a linear, branched or cyclic alkylene group, an arylene group, —O—, —C (═O) —, —NH—, and a combination thereof. 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. And 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 as L ′ is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is carbon. An arylene group having 5 to 10 atoms is preferred. In the formula (Px-1a), L ′ is composed of a linear alkylene group having 1 to 6 carbon atoms, a phenylene group, —O—, —C (═O) —, —NH—, and combinations thereof. Group, preferably a linear alkylene group having 1 to 6 carbon atoms such as a methylene group and a phenylene group, or these, -O-, -C (= O)-and NH A group consisting of a combination of at least one of-is preferred. When the branched alkylene group and the succinic anhydride group are bonded to form a cyclic structure, specifically, cyclohexane-1,2-dicarboxylic anhydride can be mentioned.

  In the energy-sensitive composition of the present 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 preferable that it is 90-99.99 mass%, and it is still more preferable that it is 92 mass%-99.9 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), a compound selected from the group consisting of the compound (P1), the compound (P2), and the compound (Px) can be used alone or in combination of two or more. When using in combination of 2 or more types, it is preferable that a compound (P1) is included. In this case, the content of the compound (P1) is preferably 10% by mass or more, more preferably 30% by mass or more, and still 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 thermogravimetric stability is particularly great. Moreover, when using an energy sensitive composition for 3D printing, you may combine a compound (Px) with a compound (P1), and it is preferable to use photopolymerization initiators, such as a radical photoinitiator, in that case.

[(Q) Sulfonium salt represented by the above formula (a1)]
The sulfonium salt represented by the above formula (a1) (hereinafter also referred to as “sulfonium salt (Q)”) is ortho-positioned to the carbon atom to which A ¹ is bonded in the benzene ring in the above formula (a1). A methyl group is bonded to the carbon atom. Since the sulfonium salt (Q) has a methyl group at the above-mentioned position, it is more prone to generate protons and has higher sensitivity to active energy rays such as ultraviolet rays as compared with conventional sulfonium salts.

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

In the above formula (a2), R ⁴ represents an alkyl group which may be substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group or an optionally substituted amino group. It is preferably a group or a nitro group, more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group optionally substituted with a halogen atom.
In the above formula (a2), m1 may be selected depending on the species of the ring ^{Z 1,} for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably be an integer of 0 to 2 .

In the above formula (a3), R ⁵ is an alkylene group; a hydroxyl group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or a group represented by the above formula (a5). Preferably, it is a group represented by the above formula (a5).
In the above formula (a3), R ⁶ is an alkyl group; a hydroxy group, an optionally substituted amino group, or an alkyl group substituted with a nitro group; or a group represented by the above formula (a6). A group represented by the above formula (a6) is more preferable.
In the above formula (a3), A ² is preferably S or O, and more preferably S.
In the above formula (a3), n1 is preferably 0.

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

In the formula (a5), R ¹¹ is preferably an alkyl group optionally substituted with a halogen atom, a hydroxy group, an optionally substituted amino group, or a nitro group, and is substituted with a halogen atom. It is more preferable that it is a good alkyl group.
In the above formula (a5), m @ 2 may be selected depending on the species of the ring ^{Z 2,} for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably be an integer of 0 to 2 .

In the above formula (a6), R ¹² represents an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, or an optionally substituted amino group. It is preferably a group or a nitro group, more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group optionally substituted with a halogen atom.
In the above formula (a6), m3 can be selected according to the type of the 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 active energy (heat, visible light, ultraviolet light, electron beam, X-ray, etc.). Is a valent anion. When the sulfonium salt (Q) is used as an acid generator, preferred examples of X ⁻ include monovalent polyatomic anions, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY ₄₋ An anion 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 ⁻ is more preferable. X ⁻ may be a halogen anion, and examples thereof include fluoride ion, chloride ion, bromide ion, and iodide ion.

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

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

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

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

  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 the fluoroalkyl group are linear or branched. The alkyl group, the fluoroalkyl group, or the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxy group, an optionally substituted amino group (for example, those exemplified in the following description of the above formulas (a2) to (a6)), a nitro group, and the like. It is done.
Further, the carbon chain in the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 may have a hetero atom such as an oxygen atom, a nitrogen atom 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 (eg, ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonylamide). A bond, a sulfonylimide bond, a urethane bond, etc.).
When the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 has the above substituent, heteroatom, or functional group, the number of the substituent, heteroatom, or functional group may be one. Two or more may be sufficient.

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

Examples of the anion represented by MY _a ⁻ include an anion represented by SbF ₆ ⁻ , PF ₆ ^— or BF ₄ ^— .

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

The anion represented by R ^x1 _c BY _4-c ^— is preferably R ^x1 _c BY _4-c ^—.
(In the formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms are substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4.)
For example, (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF _{^{2 -, C 6 F 5 BF}} 3 - or _{(C 6 H 3 F 2)} 4 B - anion, and the like represented. Of _{these, (C 6 F 5) 4} B - , or _{((CF 3) 2 C 6} H 3) 4 B - anion represented by are preferred.

Examples of the anion represented by R ^x1 _c GaY _4-c ^— include (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , and (CF ₃ C ₆ H ₄ ) _4. Examples include an anion represented by Ga ⁻ , (C ₆ F ₅ ) ₂ GaF ₂ ⁻ , C ₆ F ₅ GaF ₃ ^— or (C ₆ H ₃ F ₂ ) ₄ Ga ⁻ . Of _{these, (C 6 F 5) 4} Ga - or _{((CF 3) 2 C 6} H 3) 4 Ga - anion represented by are preferred.

^{Examples of the} anion represented by R ^x2 SO ₃ ^— include a trifluoromethanesulfonic acid anion, a pentafluoroethanesulfonic acid anion, a heptafluoropropanesulfonic acid anion, a nonafluorobutanesulfonic acid anion, a pentafluorophenylsulfonic acid anion, and p-toluene. Examples include a sulfonate anion, a benzenesulfonate anion, a camphorsulfonate anion, a methanesulfonate anion, an ethanesulfonate anion, a propanesulfonate anion, and a butanesulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion are preferred.

The anion represented ^{_{by, (CF 3 SO 2) 3}} C - - (R x2 SO 2) 3 C, (C 2 F 5 SO 2) 3 C -, (C 3 F 7 SO 2) 3 C - or _{(C 4 F 9 SO 2)} 3 C - anion such as represented and the like.

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

As monovalent polyatomic anions, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4-c ⁻ , R ^x1 _c GaY _4-c ⁻ , R ^x2 SO ₃ ⁻ , (R ^x2 SO _{2) 3} C ^- or ^{_{(R x2 SO 2) 2 N}} - besides the anion represented by the perhalogenated acid ion _{^(ClO 4} ^-, BrO 4 -, etc.), halogenated sulfonic acid ion ^_(FSO 3 -, ClSO ₃ ^- and the like), sulfate ion ^{_{(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.), hexafluoro bismuthate ions (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.), an aryl boronic acid ions ^{_{(B (C 6 H 5)}} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.), Thiocyanate ion (SCN ⁻ ), nitrate ion (NO ₃ ⁻ ) and the like can be used.

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

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

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

In the above formulas (a1) to (a6), as the alkyl group, 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.), a branched alkyl group having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, neopentyl, tert) -Pentyl, isohexyl, isooctadecyl, etc.), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, etc.) and the like. In particular, in the above formulas (a1), (a2), and (a4) to (a6), the alkyl group which may be substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. . Examples of the alkyl group substituted with a halogen atom include groups in which at least one hydrogen atom in the above linear alkyl group, branched alkyl group, or cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, trimethyl). Fluoromethyl and the like). Of the alkyl groups that may be substituted with a halogen atom, 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), as the alkoxy group, 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.).

  In the above formulas (a2) to (a6), as the alkyl group in the alkylcarbonyl group, the above-mentioned linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or 3 carbon atoms. -18 cycloalkyl group, and as the alkylcarbonyl group, a linear, branched or cyclic alkylcarbonyl group 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.).

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

  In the above formulas (a2) to (a6), as the alkoxycarbonyl group, 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.).

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

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

  In the above formulas (a2) to (a6), as the acyloxy group, 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 and the like.

  In the above formulas (a3) to (a6), the arylthio group is 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- (Fe Ruthio) 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 and the like.

  In the above formulas (a2) to (a6), the alkylthio group may be 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, isooctadecylthio and the like.

  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, and the like).

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

  In the above formulas (a3) to (a6), examples of the heterocyclic hydrocarbon group include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl). , Pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromonyl, xanthonyl And dibenzofuranyl etc.).

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

  In the above formulas (a2) to (a6), as the alkylsulfinyl group, 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, isooctadecylsulfinyl, etc.).

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

  In the above formulas (a2) to (a6), as the alkylsulfonyl group, a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, 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.) and the like.

In the above formulas (a2) to (a6), as the hydroxy (poly) alkyleneoxy group, HO (AO) _q- (wherein AO independently represents an ethyleneoxy group and / or a propyleneoxy group, q is 1 A hydroxy (poly) alkyleneoxy group represented by -5).

In the above formulas (a2) to (a6), the amino group which may be substituted 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.).

  In the above formulas (a3) and (a4), as the alkylene group, 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, undeca -1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, and hexadecane-1,16 -Diyl group and the like).

The sulfonium salt (Q) can be synthesized, for example, according to the following scheme. Specifically, 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) is reacted with a compound represented by the following formula (b2) in the presence of a base such as potassium hydroxide. Thus, a nitro compound represented by the following formula (b3) is obtained, and then reduction is performed in the presence of reduced iron to obtain an amine compound represented by the following formula (b4). A diazo compound is obtained by reacting this amine compound with MaNO ₂ (wherein Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom) represented by a nitrite (for example, sodium nitrite). Next, a cuprous halide represented by this diazo compound and CuX ′ (wherein X ′ represents a halogen atom such as a bromine atom, the same shall apply hereinafter) and a hydrogen halide represented by HX ′. Mixing is allowed to proceed to obtain a halide represented by the following formula (b5). A Grignard reagent is prepared from this halide and magnesium, and then this Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) in the presence of chlorotrimethylsilane to represent the following formula (b7). Can be obtained. Further, this sulfonium salt is converted into Mb ⁺ X ″ ⁻ (wherein Mb ⁺ represents a metal cation, for example, an alkali metal cation such as potassium ion, and X ″ ⁻ represents a monovalent anion represented by X ⁻ (wherein The sulfonium salt represented by the following formula (b8) can be obtained by performing salt exchange by reacting with the salt represented by the formula (b8). In the following formulas (b2) to (b8), R ^{1 to} R ³ and A ¹ are the same as the above formula (a1).

<Scheme>

Specific examples of the cation moiety of the sulfonium salt (Q) represented by the above formula (a1) include the following. Specific examples of the anion moiety of the sulfonium salt (Q) represented by the above formula (a1), the X ^- like those described for, can be mentioned those known in the art. The sulfonium salt (Q) represented by the above formula (a1) can be synthesized according to the above scheme, and the cation moiety can be combined with the desired anion moiety by further salt exchange if necessary. ^x1 _c BY _4-c ⁻ (wherein R ^x1 represents a phenyl group in which at least a part of the hydrogen atom is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents 1 to 4) A combination with an anion represented by an integer is preferred.
The

  In the energy sensitive composition of the present 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), More preferably, it is 0.01-10 mass%, and it is still more preferable that it is 0.1-8 mass%. When the content of the sulfonium salt (Q) is within the above range, the thermogravimetric stability tends to be good. In particular, when the viscosity of the energy-sensitive composition is adjusted to a low viscosity such as 1000 mPa · s (1000 cP) or less, which will be described later, the content of the sulfonium salt (Q) is the entire composition (however, excluding the solvent). ) May be within the above range, but may be 0.001 to 1% by mass, 0.005 to 0.1% by mass, or 0.008 to 0.05%. It may be 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 the onium salt include an onium salt composed of a monovalent anion represented by X ⁻ in the formula (a1) and an onium ion different from a cation other than X ⁻ in the formula (a1). And a sulfonium salt (also referred to herein as “sulfonium salt (Q ′)”) is preferable. As the monovalent anion represented by X ⁻ , the above-described R ^x1 _c BY _4-c ^— is preferable.

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

（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 above formula (a1 ′) include the following.

The sulfonium salt (Q ′) is also represented by the above formula (a1) (wherein R ¹ and R ² independently represent a group represented by the following formula (a2 ′)). A sulfonium salt is 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。）

(In the formula, rings Z ¹ and m 1 are as described above, and R ^{4 ′} represents an aryl group.)

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

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

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

  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, ethyl heptanoate; cyclopentyl acetate, cyclohexyl acetate, cyclooctyl acetate, methyl cyclohexyl acetate, ethyl cyclohexyl acetate, propyl cyclohexyl acetate, Isopropyl cyclohexyl acetate, butyl cyclohexyl acetate, isobutyl cyclohexyl acetate, s-butyl cyclohexyl acetate, t-butyl cyclohexyl acetate Cyclic alkyl esters such as pentylcyclohexyl acetate: ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone, etc .; β-ketoester compounds (methyl acetoacetate, ethyl acetoacetate, Acetoacetate-n-propyl, isopropyl acetoacetate, acetoacetate-n-butyl, α-acetyl-γ-butyrolactone, etc.); β-diketone compounds (acetylacetone, 2,4-hexanedione, 2,4-heptanedione, etc.) Ether (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, triethylene glycol die Ether 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.) Two or more types can be used.

In addition, a conventionally known ketone solvent, alcohol solvent, amide solvent, or hydrocarbon solvent may be used. Further, a solvent known as a protic solvent and / or a basic solvent may be used.
Examples of protic solvents include alcohols such as monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, diethylene glycol monomethyl ether, and polyhydric alcohols such as ethylene glycol and glycerine; 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; phenol; Examples thereof include phenols such as p-butylphenol; active methylene compounds such as acetylacetone and diethyl malonate.
Examples of the basic solvent include, in addition to the examples of the above amines and the above nitrogen-containing amides, pyridine, triethylamine, N, N-dimethylacetamide, hexamethylphosphoric triamide, 1,3-dimethyl-2- Examples include imidazolidinone, N, N, N ′, N′-tetramethylurea, N, N, 2-trimethylpropionamide and the like.

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

(Alkali-soluble resin)
The energy-sensitive composition according to this embodiment may contain an alkali-soluble resin (A) as necessary.
In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and 2.38% by mass. When immersed in an aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute, it means a film that dissolves in a thickness of 0.01 μm or more.

Examples of the alkali-soluble resin include (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, for a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. And (b) an alkali-soluble group such as an alkali-soluble resin (A1), a carboxy group, a phenol hydroxyl group, or a sulfo group (—SO ₃ H) obtained by reacting tetracarboxylic acid or its acid dianhydride. And a conventionally known resin (A2). In this specification, Preferably, alkali-soluble resin (A2) represents alkali-soluble resins other than alkali-soluble resin (A1). These alkali-soluble resins are also preferred when it is desirable 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.

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

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

  Among these, a resin represented by the following formula (f-1) is preferable. The resin represented by the formula (f-1) itself is preferable in terms of high photocurability.

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

In the general formula (f-2), R ^f1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and 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 the general formula (f-1), Y ^f represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above general formula ^(f-1), Z f represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in the said general formula (f-1), m shows the integer of 0-20.

Moreover, as an alkali-soluble resin having an ethylenically unsaturated group, a polyester obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or a polybasic acid. (Meth) acrylate; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin Bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine Epoxy resins, and epoxy resins such as dihydroxybenzene type epoxy resin, can also be used (meth) epoxy obtained by reacting acrylic acid (meth) acrylate resin.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth) acrylate” means both acrylate and methacrylate.

  On the other hand, as an alkali-soluble resin having no ethylenically unsaturated group, an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic group-containing unsaturated compound are at least copolymerized. It is possible to use a resin obtained by the above process.

  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; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl ( (Meth) acrylic acid epoxy alkyl esters such as (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 4-oxatetracyclo- [6.2.1.02,703,5] undecanyl (meth) acrylate Α-alkyl acrylate epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl; o-Vinylbenzylglycidyl ether, m-vinylbenzyl Glycidyl ether, glycidyl ethers such as p- vinylbenzyl glycidyl ether; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoints of copolymerization reactivity, strength of cured resin, 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. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulae.

In the above general formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or 1 to carbon atoms. 5 represents an alkyl group. R ^a4 is preferably a single bond or 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 or a hexamethylene group. As R ^a5 , for example, a methyl group and an ethyl group are preferable.

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

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

Further, 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. The linking group is, for example, an alkylene group, a cycloalkylene group, which may be a straight chain or branched chain having 1 to 10 carbon atoms, or An arylene group or a divalent group obtained by combining these groups.
The linking group may have an ether bond, an amino bond, an amide bond, or a vinyl bond, and preferably has an amide bond. Examples of R ^r1 include, but are not limited to, the following. In addition, * in the following formula | equation means the terminal of the bond hand of ^Rr1 couple ^| bonded with Si in a formula (A2-1).

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

  When the alkali-soluble resin is contained, the content of the alkali-soluble resin is, for example, 60% by mass or less and 30% by mass or less with respect to the entire energy-sensitive composition (excluding the solvent). Preferably, it is more preferably 20% by mass or less, and further preferably 15% by mass or less. If it is 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 and 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 may contain a surfactant as necessary. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

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

In addition, the energy-sensitive composition according to the present embodiment may include known additives (radical photopolymerization initiators, sensitizers, pigments, dispersants, fillers, antistatic agents, flame retardants, flame retardants, and the like as necessary. Foaming agent, flow control agent, light stabilizer, antioxidant, adhesion-imparting agent, ion scavenger, anti-coloring agent, solvent, non-reactive resin and radical polymerizable compound).
In particular, by combining a radical photopolymerization initiator and the like, the balance between thermal reactivity and photoreactivity of the energy-sensitive composition according to this embodiment can be appropriately adjusted.

[Characteristic]
In the thermosensitive measurement (TG) in which the energy-sensitive composition according to this embodiment is heated to 230 ° C. at 10 ° C./min in an air stream, the weight reduction rate from the peak value is preferably 10% or less. .

  As described above, the inclusion of the sulfonium salt (Q) increases the proton concentration in the system containing the compound component (P) and the sulfonium salt (Q), and the sequential polymerization in the compound component (P) is continued. It is speculated that the polymerization is promoted. Thus, the energy sensitive composition according to this embodiment has a small weight loss rate of preferably 10% or less even when the temperature is increased to 230 ° C.

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

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

  In general, in order to lower the viscosity of the composition, a compound (P1) having a low molecular weight, such as an epoxy monomer, is used. On the other hand, the heat resistance decreases as the compound having a low molecular weight is blended. It is easy to generate outgas. However, it was confirmed that the energy-sensitive composition according to the present embodiment includes the sulfonium salt (Q), so that it has excellent heat resistance and can reduce outgassing even when the viscosity is low. Surprisingly, even if the addition amount of the sulfonium salt (Q) is small compared to the addition amount of a general cationic polymerization initiator or the like, the viscosity of the energy sensitive composition is reduced and the heat resistance is improved. It was confirmed by an experiment described later that the effect of improvement and reduction of outgas generation can be obtained.

  The energy-sensitive composition according to this embodiment is preferably used in ink jet printing that requires a low-viscosity ink because it has a low viscosity but is excellent in heat resistance and can reduce the generation of outgas. Ink jet ink is preferably used for a display body such as a touch panel when applied to a relatively large area in terms of productivity and the like, and is preferably used for applications such as a sealing material for organic EL display elements.

<Method for manufacturing wafer level lens>
The wafer level lens can be manufactured by subjecting the above-described energy-sensitive composition to molding (for example, casting molding method or injection molding method). The wafer level lens mold may be made of metal, glass, or plastic.

  Casting molding methods include simultaneous molding methods and individual piece molding methods, each having the following steps.

(Simultaneous molding method)
Step 1: The energy-sensitive composition is poured into a wafer level lens mold having a shape in which a plurality of lens molds are aligned in a certain direction, and is cured by heating and / or light irradiation. Step 2: Wafer level lens mold Is removed, and annealing treatment is performed to obtain a cured product having a shape in which a plurality of wafer level lenses are coupled. Step 3: A cured product having a shape in which a plurality of wafer level lenses are coupled is singulated to obtain a wafer level lens.

(Single piece molding method)
Step 1: Pour the energy-sensitive composition into a wafer level lens mold having a single lens mold and cure it by heating and / or light irradiation Step 2: Remove the wafer level lens mold and perform an annealing treatment Get a wafer level lens

(Injection molding method)
Step 1: Pour the energy sensitive composition into a wafer level lens mold for injection molding and cure it by heating and / or light irradiation. Step 2: Remove the wafer level lens mold and perform an annealing process to remove burrs. And get a wafer level lens

  The heat treatment in the above-described process may be performed at a temperature of, for example, about 100 to 200 ° C. (preferably 120 to 160 ° C.) for a short 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, or laser light can be used as the light source. Moreover, after light irradiation, you may heat-process at the temperature of about 50-180 degreeC, for example, and may advance hardening reaction.

  The 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, for example.

  In the above simultaneous molding method, it is preferable that the energy-sensitive composition has a low viscosity and excellent fluidity from the viewpoint of excellent filling property in a mold. The viscosity at 25 ° C. and a shear rate of 20 (1 / s) of the energy sensitive composition used in the co-molding method is, for example, about 0.05 to 5 Pa · s, preferably 0.1 to 2 Pa · s. An energy-sensitive composition having a viscosity in the above range is excellent in fluidity, hardly causes bubbles to remain, and can be filled into a mold while suppressing an increase in injection pressure. That is, it is excellent in application property and filling property, and is excellent in workability over the entire molding operation.

  The cured product of the energy sensitive composition has excellent heat resistance even in a high temperature environment of about 100 to 250 ° C. Therefore, a wafer level lens having excellent lens center position accuracy can be efficiently manufactured even if annealing is performed after removing from the mold. Therefore, in step 3 of the above simultaneous molding method, by stacking a plurality of cured products having a shape in which a plurality of wafer level lenses are combined, by determining the position of the cutting line based on the cured product at the top, and cutting, The wafer level lens can be separated without being damaged, and the wafer level lens or a laminate thereof can be efficiently manufactured at low cost.

  The wafer level lens obtained by the energy sensitive composition of this embodiment can prevent yellowing even when exposed to a high temperature environment for a long period of time, and can maintain high transparency. Therefore, for example, an imaging lens, a spectacle lens, a light beam condensing lens, a light diffusion lens of a camera (camera such as an in-vehicle camera, a digital camera, a PC camera, a camera for a mobile phone, a camera such as a surveillance camera, particularly a wafer level camera). For example, it can be suitably used as a wafer level lens for an in-vehicle camera that is particularly required to have heat resistance.

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

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

<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 compound (P1), the compound (P2), and the compound (Px), and the sulfonium salt (Q). Polymerizing and / or crosslinking an energy sensitive composition comprising: Since the energy-sensitive composition has energy sensitivity, it can be cured by polymerization and / or crosslinking by applying active energy. The activation energy to be applied may be any energy as long as it has an energy that induces the 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 measured at 25 ° C. using an E-type viscometer, for example, 5000 mPa · s (5000 cP) or less, preferably 100 mPa · s (100 cP) or less. When prepared low, it can be preferably used as an inkjet ink. As long as the viscosity of the energy sensitive composition of this embodiment used as an inkjet ink is within the above range, it may be, for example, 1 mPa · s (1 cP) or more, or 10 mPa · s (10 cP) or more. The energy-sensitive composition used as an ink-jet ink preferably has a sulfonium salt (Q) content when prepared to have the low viscosity described above.

  EXAMPLES Hereinafter, examples of the present invention will be shown and the present invention will be described in more detail. However, the present invention is not limited to the following examples.

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

<Material>
[Compound (P1)]
-Compound represented by the following formula (P1-1a)

-Compound represented by the following formula (P1-1c)

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

[Sulphonium salt]
-A sulfonium salt represented by the following formula (Q1)

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

-Sulfone compound represented by the following formula (z2)

  ・ Triphenylsulfonium tetrakis- (pentafluorophenyl) borate

[Evaluation 1]
The liquid mixture obtained in Examples 1 to 3 and Comparative Examples 1 to 9 was heated at a rate of 10 ° C. in an air stream using a differential heat / thermogravimetry apparatus (TG / DTA-6200, manufactured by Seiko Instruments Inc.). The temperature was raised from 20 ° C. to 250 ° C. under the conditions of / min, and a TG / DSC curve was obtained. In the obtained TG curve, the weight reduction rate from the peak value was calculated. The results are shown in Table 1. The weight reduction rate is evaluated according to 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. FIG. 5 shows a TG / DSC curve as a reference example when the temperature of the compound (P1) represented by the formula (P1-2a) is raised under the same conditions.

[Discussion]
As shown in Table 1 and the TG curves shown in FIGS. 1 to 4, in Examples 1 to 3 using the compound (P1) and the sulfonium salt (Q), the weight reduction rate was 10% or less, and Comparative Example 1 The high heat resistance was better than that of ~ 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 the compound (P1) is ring-opened and the successive polymerization is proceeding, and it is surmised that the polymerization is proceeding from a low temperature around 110 ° C. On the other hand, a sharp peak was 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 reduction rate. It is guessed. For example, as shown in FIG. 2, in Comparative Example 7, the weight is reduced by about 65% around 170 ° C. As shown in FIG. 3, in Comparative Example 8, the weight is reduced by about 30% around 150 ° C. As shown in FIG. 4, in Comparative Example 9, the weight is reduced by about 50% at around 170 ° C. From the results of FIG. 5, the compound (P1) represented by the formula (P1-2a) alone shows a sharp peak at 50 ° C. or less in the DSC curve, and is represented by the formula (P1-2a) at 50 ° C. or less. It was confirmed that the compound (P1) started to decompose, the weight started to decrease from around 100 ° C., and decreased by about 80% at around 165 ° C.

[Evaluation 2]
A mixture obtained by changing the mass ratio of the mixture obtained in Example 1 to the compound of the formula (P1-1a): the sulfonium salt of the formula (Q1) = 99: 1 is applied on a glass substrate with a spin coater. The film having a thickness of 20 μm was irradiated with ghi rays at an exposure amount of 1000 mJ / cm ² using HMW-532D (manufactured by ORC), and then the transmittance of the film at a wavelength of 400 nm was determined as MCPD-3000 (Otsuka Measured by using an electronic company). The transmittance was 99.6%.

[Discussion]
From this result, in Examples 6 to 9 to be described later, the permeation of the hard coat formed by applying a coating liquid containing the same compound (P1) and sulfonium salt (Q) as in Example 1 on the polyimide film is also permeated. It is suggested that the rate will not be adversely affected.

<< Examples 4 and 5 >>
Bis-1-ethyl-3-oxetanyl methyl ether which is an alicyclic epoxy compound represented by the above formula (P1-1a) or an oxetane compound represented by the following formula (P1-7a) as the compound (P1), and The sulfonium salt represented by the above formula (Q1) is mixed at the blending ratio shown in Table 2, and the obtained mixture is exposed to an exposure amount of 100 mJ / cm ² (broadband) using an ultraviolet curing machine, Example 4 was post-baked at 150 ° C. for 2 minutes, and Example 5 was cured under the curing condition that no post-bake was performed. As a result, none of the mixtures of Examples 4 and 5 produced tack. Cured. In Table 2, the unit of the compounding ratio is part by mass.

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

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

[Method for producing polyimide film 1]
The reactor was filled with 832 g of N, N-dimethylacetamide (DMAc) while passing nitrogen through a 1 L reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and condenser, After the temperature was adjusted to 25 ° C., 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was dissolved in the solvent in the reaction vessel, and this solution was maintained at 25 ° C. Then, 2.09 g (0.07 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 8.83 g of biphenyltetracarboxylic dianhydride (BPDA) (0 0.03 mol) was added, and the mixture was stirred and dissolved and reacted within a certain period of time. At this time, the temperature of the solution was maintained at 25 ° C. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid concentration of 13% by weight. The polyamic acid solution was charged with 25.6 g of pyridine and 33.1 g of acetic anhydride, stirred at 25 ° C. for 30 minutes, further stirred at 70 ° C. for 1 hour, cooled to room temperature, precipitated in 20 L of methanol, The precipitated solid content was filtered and pulverized, and then dried in vacuum at 100 ° C. for 6 hours to obtain 111 g of a solid powdery polyimide.

  0.03 g (0.03 wt%) of amorphous silica particles having OH groups bonded to the surface was added to N, N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, After sonication, 100 g of the solid powdery 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, and then the film was peeled off from the stainless steel plate and fixed to the frame with pins. The frame on which the film was fixed was placed in a vacuum oven and gradually heated from 100 ° C. to 300 ° C. within 2 hours, then gradually cooled and separated from the frame to obtain a polyimide film. Thereafter, as a final heat treatment step, heat treatment was further performed at 300 ° C. for 30 minutes. The obtained polyimide film 1 had a thickness of 50 μm, a total light transmittance of 88%, and a yellowness (YI) of 2.5.

[Production method of polyimide film 2]
After applying a solution of polysilazane having a weight average molecular weight of 2000 g / mol (MOPS-1800, manufactured by Az Materials) in dibutyl ether (DBE) at 2 wt% on one surface of the polyimide film 1, about 80 ° C. A polysilazane film having a thickness of 300 nm was formed by drying at a temperature. Then, after standing at room temperature for about 5 minutes, the polysilazane film is thermally cured at a temperature of about 250 ° C. to form a silicon oxide layer, and a polyimide film 2 having a colorless transparent polyimide film / silicon oxide layer structure is manufactured. did. The resulting polyimide film 2 had a thickness of 50 μm, a total light transmittance of 92%, and a yellowness (YI) of 1.0.

[Production Method of Polyimide Film 3]
While introducing nitrogen gas, 1000 g of N-methylpyrrolidone (NMP) was added to a 3 L separable flask equipped with an oil bath and equipped with a stirring rod, and 232.4 g of 3,3- (diaminodiphenyl) sulfone (referred to as diamine 1) was added. While 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 both terminal amine-modified methyl phenyl 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 raising the temperature 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 resulting polyamic acid had a weight average molecular weight (Mw) of 84000.

  The varnish is coated on 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 curing oven (manufactured by Koyo Lindberg, model name VF-2000B). And heated at 140 ° C. for 60 minutes, and further heated at 350 ° C. for 60 minutes under a nitrogen atmosphere (oxygen concentration 100 ppm), allowed to stand at room temperature for 24 hours, and the resin film was peeled from the glass to produce a polyimide film. did. The obtained polyimide film 3 had a thickness of 20 μm, a total light transmittance of 88%, and a yellowness (YI) of 7.0.

[Method for producing polyimide film 4]
(Synthesis of imidazole compound (d))
First, 30 g of cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to the methanol. The methanol solution was then stirred at 40 ° C. Methanol was distilled off and the residue was suspended in 200 g of water. To the obtained suspension, 200 g of tetrahydrofuran was mixed and stirred, and the aqueous phase was separated. 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 collected. The target 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 method described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, tetracarboxylic dianhydride represented by the following formula (norbornane-2-spiro-α-cyclopentanone) -Α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride) was prepared.

(Preparation of polyamic acid)
First, a 30 ml three-necked flask was heated with a heat gun and sufficiently dried. Next, the atmosphere gas in the three-necked flask was replaced with nitrogen, and the inside of the three-necked flask was changed to a nitrogen atmosphere. After adding 0.2045 g (0.90 mmol: Nippon Pure Chemicals: DABAN) of 4,4′-diaminobenzanilide into the three-necked flask, N, N, N ′, N′-tetramethylurea (TMU) Of 3.12 g was added. The contents of the three-necked flask were stirred to obtain a slurry liquid in which aromatic diamine (DABAN) was dispersed in TMU.
Next, after adding 0.3459 g (0.90 mmol) of the tetracarboxylic dianhydride of the above formula into the three-necked flask, the reaction was conducted by stirring the contents of the flask for 12 hours at room temperature (25 ° C.) in a nitrogen atmosphere. A liquid was obtained. In this way, a reaction solution in which the polyamic acid was 15% by mass (TMU solvent: 85 parts by mass) was formed in the reaction solution.

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

(Preparation of polyimide film)
A polyimide precursor composition obtained as described above is heated on a glass substrate (large slide glass, trade name “S9213” manufactured by Matsunami Glass Industrial Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm). The coating film was formed by spin coating so that the thickness of the cured coating film was 13 μm. Next, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ° C. and allowed to stand for 2 hours, and the solvent was removed from the coating film by evaporation.
After removing the solvent, the glass substrate on which the coating film was formed was put into an inert oven in which nitrogen was flowing at a flow rate of 3 L / min. After standing in an inert oven for 0.5 hours under a temperature condition of 25 ° C. in a nitrogen atmosphere (oxygen concentration of 100 ppm), the mixture is heated for 0.5 hours under a temperature condition of 135 ° C., and further a temperature condition of 300 ° C. (final The coating film was cured by heating at a heating temperature for 1 hour to obtain a polyimide-coated glass in which a thin film (polyimide film) made of polyimide was coated on the glass substrate.

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

In order to identify the molecular structure of the resin that is the material of the obtained polyimide film, the IR spectrum of the sample of the polyimide film was measured using an IR measuring machine (trade name: FT / IR-4100, manufactured by JASCO Corporation). did. As a result of the measurement, it was found that the C═O stretching vibration of imidecarbonyl was observed at 1696.2 cm ⁻¹ in the IR spectrum of the resin that is 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 made of a polyimide resin.

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

  In addition, the value (unit:%) of the total light transmittance of a film, and yellowness (YI) are JIS K7361 using the brand name "Hazemeter NDH-5000" by Nippon Denshoku Industries Co., Ltd. as a measuring apparatus. 1 (issued in 1997).

[Preparation of coating solution]
An energy photosensitive composition containing the compound (P1) represented by the above formula (P1-1a) and the sulfonium salt represented by the above formula (Q1) in a mass ratio of 99: 1 is used as a solvent (propylene glycol monomethyl ether). A coating solution 1 having a solvent ratio of 80% by mass was prepared by dissolving in acetate (PGMEA).

[Preparation of coating solution for comparison]
A photosensitive composition containing an acrylic monomer (dipentaerythritol hexaacrylate) and a polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone) in a mass ratio of 99: 1 is dissolved in a solvent (PGMEA) to dissolve the solvent. A comparative coating solution 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, using a UV curing machine with a wavelength of 365 nm, the coating layer was irradiated at 100 mJ / cm ² to obtain each polyimide film having a hard coat (cured film) formed on one surface. Each obtained polyimide film was peeled from the wafer, and the appearance was visually observed.

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

[Evaluation 4]
In evaluation 3, the surface resistance value of each hard coat formed on the polyimide films 1 to 4 was measured with a Hiresta MCP-HT450 (manufactured by Mitsubishi Analytech), a probe UR-100, and a measurement voltage of 1,000V. The surface resistance values were all over 1 × 10 ¹⁵ Ω.
From this result, it was confirmed that the coating liquid 1 which concerns on a present Example can form a hard coat with high surface resistance.

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

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

[Sulphonium salt etc. (z3)]

[Evaluation 5]
The viscosities of the mixed liquids obtained in Examples 10 to 14 and Comparative Examples 14 to 15 were measured using an E-type viscometer at 25 ° C. and 1 to 100 rpm. The results are shown in Table 1. The viscosity of the compound (P1-1a) is about 60 mPa · s (60 cP), the viscosity of the compound (P1-2a) is about 20 mPa · s (20 cP), and the viscosity of the compound (P1-6d) is 200 mPa · s (200 cP). )

0.3 g of the liquid mixture obtained in Examples 10 to 14 and Comparative Examples 14 to 15 was precisely weighed and sealed in a glass vial, and the exposure amount was 1500 mJ / cm using an ultraviolet irradiator (HMW-532D, manufactured by ORC). After exposure according to ^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), heated at 100 ° C. for 30 minutes, and then measured for outgas using a gas chromatograph mass spectrometer (Claras580, manufactured by Perkins Elmer). . The results are shown in Table 3. In addition, in the table | surface, it showed by the relative value which set the measured value (area%) of the comparative example 14 to 100.

[Discussion]
As shown in Table 3, Example 10 using the compound (P1-1a) and the sulfonium salt (Q1) was outgassed while having the same viscosity as that of Comparative Example 14 not using the sulfonium salt (Q1). It was 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 the same viscosity as that of the comparative example 15 not using the sulfonium salt (Q1). However, 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 when the amount of the sulfonium salt (Q1) is very small, the effect of reducing the viscosity of the mixed solution (energy sensitive composition) and reducing the outgas is obtained. It was confirmed that there was. Similarly, as can be seen from the results of Examples 12 and 13, even when the amount of the sulfonium salt (Q1) is extremely small, the effect of reducing the viscosity of the mixed solution (energy-sensitive composition) and reducing outgas. It was confirmed that there is.

  From the results of Examples 11 and 12, when the total content of the compound component (P) to the compound (P1) is the same, as the compound component (P) to the compound (P1), from the compound (P1-1a) alone In addition, it was confirmed that the combined use of the compound (P1-1a) and the compound (P1-2a) has an effect of reducing the viscosity of the mixed solution (energy-sensitive composition) and reducing outgas. From this, as compound component (P) thru | or compound (P1), the alicyclic epoxy compound represented by the above-mentioned 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.

<< Examples 15 to 24 >>
[Preparation of high refractive index energy sensitive composition]
In Examples 15 to 24, the following cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound (P1) and a sulfonium salt were mixed at a blending ratio shown in Table 4 to obtain an energy sensitive composition. A product was made. In Table 4, the unit of the mixing ratio is part by mass, and the mixing ratio of the solvent is the mass ratio. In Example 23, 10 parts by mass of cerium oxide (average particle size: 50 nm) was further added to 100 parts by mass of the sum of the components (P1) and (Q1) in Example 15 and prepared. In Example 24, 100 parts by mass of titanium oxide (average particle size: 5 to 10 nm) was further added to 100 parts by mass of the sum of the component (P1) and (Q1) in Example 15 and prepared. In Examples 15 to 23, the amount of the solvent was adjusted so that the concentration of the component 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 would be 10% by mass.

<Material>
[Compound (P)] (Compound (P1))
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, in a 500 ml four-necked flask, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate 0.34 mol, acrylic acid 0.68 mol, propylene glycol monomethyl ether acetate 139.0 g and 2.15 g of tetraethylammonium bromide (TEAB) were charged and reacted at 100 to 105 ° C. with stirring for 20 hours under heating. Next, 0.13 mol of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 0.27 mol of 1,2,3,6-tetrahydrophthalic anhydride are charged into the flask, and the temperature is 120 to 125 ° C. And stirred for 8 hours under heating. Furthermore, 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 obtained alkali-soluble resin (A1a) had a solid content concentration of 57.0 wt%, an acid value (converted to a solid content) of 82 mgKOH / g, and Mw of 3500 by GPC analysis.

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

Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain an alkali-soluble resin (A2a) having a cardo structure. It was. The disappearance of the acid anhydride group 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 Big Chemie Japan Co., Ltd.]

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

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

[Evaluation 6]
Each of the energy sensitive compositions of Examples 15 to 24 was applied to a glass substrate using a spin coater, pre-baked at 100 ° C. for 120 seconds, and exposed (broadband) with an exposure amount of 100 mJ / cm ² using an ultraviolet curing machine. Thereafter, post-baking treatment was performed at 150 ° C. for 20 minutes (in Example 24, 230 ° C. for 20 minutes). The film thicknesses of the cured films of Examples 15 to 23 were 500 nm, and 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 the compositions had a high refractive index of 1.7 or more. In particular, the cured film of Example 23 to which cerium oxide as metal oxide particles was added had a refractive index of 1.75 or higher, and Example 24 had a refractive index of 1.8 or higher. I was able to plan.

Claims (7)

(P1) a cationically and / or acid-catalyzed 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;
(Q) An energy sensitive composition comprising a sulfonium salt represented by the following formula (a1).

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

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

Wherein R ⁵ 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 group Hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom substituted also represents a group represented by an alkylene group or the following formula (a5), R ⁶ is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Ali Ruthiocarbonyl 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, an alkyl group optionally substituted with a halogen atom, or a group represented by the following formula (a6), A ² represents a single bond, S, O And 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 A group, 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 a group represented by the formula (a2), ^{R 9} and R ⁰ may form a ring with the sulfur atom bonded to each other, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, X ^- are as defined above, n2 Represents 0 or 1, provided that R ⁹ and R ¹⁰ are not simultaneously an alkyl group which may be substituted with a halogen atom.

(In the formula, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl group which may be substituted with a halogen atom. 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 ( A poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more.)

(In the formula, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl group which may be substituted with a halogen atom. 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 represents an integer of 0 or more.) The compound component (P) is the compound (P1),
The energy-sensitive composition according to claim 1, wherein the (P1) compound is an epoxy compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, and an alicyclic epoxy group. 3. The energy sensitive composition according to claim 1, wherein the sulfonium salt is a boron-containing anion in which the monovalent anion represented by X ⁻ is represented by the following general formula.
R ^x1 _c BY _4-c ⁻
(In the formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms are substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4.)   4. The weight reduction rate from the peak value in thermogravimetry (TG) in which the temperature is raised to 230 ° C. at a heating rate of 10 ° C./min in an air stream is 10% or less. Energy sensitive composition.   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.   Hardened | cured material which hardened | cured the energy sensitive composition of any one of Claims 1-5.   The manufacturing method of hardened | cured material including superposing | polymerizing and / or bridge | crosslinking the energy sensitive composition of any one of Claims 1-5.

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