JP7012424B2 - Energy-sensitive compositions, cured products and methods for producing cured products - Google Patents

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 an organic EL display element or an energy sensitive composition for a wafer level lens. For example, Patent Document 1 has an epoxy group or an oxetanyl group as an energy-sensitive resin capable of suppressing the generation of outgas that causes deterioration of an organic EL display element, and ethers other than the epoxy group or the oxetanyl group. Energy sensitive resin compositions that do not contain bonds and ester bonds have been proposed. Further, Patent Document 2 describes an alicyclic epoxy compound having a specific structure as an energy-sensitive resin that suppresses yellowing even in a high temperature environment and has excellent transparency and curability, and two or more glycidyl groups in the molecule. An energy-sensitive resin composition containing a siloxane compound having a siloxane compound and a curing agent has been proposed.

International Publication No. 2015/0641410 International Publication No. 2015/129053

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

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

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

A first aspect of the invention is a (P1) cationic and / or acid-catalytically polymerizable and / or crosslinkable compound, (P2) a compound that increases its solubility in a developing solution under the action of an acid. , And (Px) an energy-sensitive composition comprising 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 indicate an alkyl group which may be 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 and the formula is expressed. A ring may be formed with the sulfur atom inside, 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. Shown, X ^- represents a monovalent anion, except that R ¹ and R ² are not alkyl groups that may be substituted with halogen atoms at the same time.)

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

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group or an 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, It indicates an amino group, a cyano group, a nitro group, or a halogen atom which may be substituted, and m1 indicates 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。）

(In the formula, 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, or a heterocyclic formula. A hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom. An alkylene group which may be substituted or a group represented by the following ^formula (a5) is shown, and R6 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an arylthio. Carbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, An amino group which may be substituted, a cyano group, a nitro group, or an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (a6) is shown, and A ² is a single bond, S, O, It indicates a sulfinyl group or a carbonyl group, and n1 indicates 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。）

(In the formula, R ⁷ and R ⁸ are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, Aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro An alkylene group which may be substituted with a group or a halogen atom or a group represented by the following formula (a5) is shown, and R ⁹ and R ¹⁰ are independently an alkyl group which may be substituted with a halogen atom or the above. Representing a group represented by the formula (a2), R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with the sulfur atom in the formula, and A ³ is a single bond, S, O, sulfinyl group. Alternatively, it indicates a carbonyl group, X ⁻ is as described above, n2 indicates 0 or 1, but R ⁹ and R ¹⁰ are not alkyl groups which may be substituted with a halogen atom at the same time.)

（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 is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl 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 ( Poly) Indicates an alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 indicates 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 is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl 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, It indicates 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 indicates 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.

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

According to the present invention, it is possible to provide an energy-sensitive composition having excellent thermogravimetric stability, a cured product obtained by curing the composition, and a method for producing the cured product.

It is a TG / DSC curve which shows the thermogravimetric change of Example 3. FIG. 6 is a TG / DSC curve showing a change in thermogravimetric analysis of Comparative Example 7. 6 is a TG / DSC curve showing a change in thermogravimetric analysis of Comparative Example 8. 6 is a TG / DSC curve showing a change in thermogravimetric analysis 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, but the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. ..
In the present specification, the description of "A and / or B", "A and / or B", "A and / or B", etc., such as "cationically and / or acid catalytically", is referred to as "A and / or B". It means "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 (P1) is a cationically and / or acid-catalystically polymerizable and / or crosslinkable compound, and (P2) increases its solubility in a developing solution under the action of an acid. It contains at least one compound component (P) selected from the group consisting of a compound and a (Px) radically polymerizable or crosslinkable compound, and (Q) a sulfonium salt represented by the above formula (a1).

The energy-sensitive composition according to the present invention contains the compound component (P) and the sulfonium salt (Q) by containing the sulfonium salt represented by the above formula (a1) (hereinafter, also referred to as “sulfonium salt (Q)”). ), Since the concentration of protons increases as the temperature rises, it is presumed that sequential polymerization of the compound component (P) is continuously promoted to promote polymerization, and that there are few monomers decomposed by heat. As a result, it is presumed that the energy-sensitive composition according to the present invention has improved weight stability with respect to heat. The mode in which the sulfonium salt (Q) generates a proton includes a mode in which a proton is generated by decomposing the sulfonium salt (Q) itself and a mode in which hydrogen is generated by extracting hydrogen from a component in the system.

[(P1) Catalytic and / or acid-catalytically polymerizable and / or crosslinkable compound]
Catalytic and / or acid-catalytically polymerizable and / or crosslinkable compounds (hereinafter, also referred to as “compound (P1)”) can be cationically polymerized, for example, by an alkyl group or aryl group-containing cation, or by a proton. Contains compounds. Examples thereof include cyclic ethers, particularly epoxy compounds and oxetane compounds, as well as vinyl ether compounds and hydroxy-containing compounds. In addition, lactone compounds, cyclic thioether compounds, and vinyl thioether compounds can also be used. However, in the present specification, when the compound having an ethylenically unsaturated group (vinyl group) is a compound having an epoxy group and / or an oxetanyl group (epoxy / oxetanyl group-containing / vinyl group-containing compound), the compound ( In the case of P1) and other compounds (epoxy / oxetanyl group-free / vinyl group-containing compound), the compound (Px) is used. As used herein, "epoxy" generally includes not only oxylanyl but also oxetanyl and alicyclic epoxies, unless otherwise stated.

Further examples include aminoplastics or phenolic resol resins. These are particularly melamine resin, urea resin, epoxy resin, phenol resin, acrylic resin, polyester resin and alkyd resin, and in particular, a mixture of acrylic resin, polyester resin or alkyd resin with melamine resin. Further, examples thereof include a modified surface coating resin (for example, an acrylic modified polyester resin, an acrylic modified alkyd resin, etc.). The term surface coating resin preferably comprises an amino resin. Examples thereof include etherified and non-etherified melamine resins, urea resins, guanidine resins and biuret resins. An acid catalyst for curing surface coatings containing etherified amino resins (eg, methylated melamine resin or butylated melamine resin (N-methoxymethyl-melamine or N-butoxymethyl-melamine) or methylated / butylated glycol uryl) Of particular importance.

When the compound (P1) is an epoxy compound, it is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, but it is preferably a compound having at least two epoxy groups in the molecule. The epoxy compound can be selected from various compounds having an epoxy group conventionally blended in the curable composition. The epoxy compound may be a low molecular weight compound having an epoxy group which is a non-polymer, or a polymer having an epoxy group, but a non-polymer is preferable. As the non-polymer having an epoxy group, an aliphatic epoxy compound containing no aromatic group is preferable because the cured product formed by using the energy-sensitive composition is excellent in thermal weight stability. Among the aliphatic epoxy compounds, the 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-meth-dioxane and bis (3,4). -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ -Valerolactone-modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-Epoxycyclohexanecarboxylate), Epoxycyclohexahydrophthalate dioctyl, Epoxycyclohexahydrophthalate di-2-ethylhexyl, Epoxy resin having a tricyclodeceneoxide group, and the following formula (P1-1). Examples thereof include compounds represented by (P1-5). Among the specific examples of these aliphatic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (P1-1) to (P1-4) are in that sequential polymerization proceeds and polymerization is promoted. Preferably, an alicyclic epoxy compound represented by the following formulas (P1-1) to (P1-2) is more preferable. These alicyclic epoxy compounds may be used alone or in combination of two or more. The compound component (P) to the compound (P1) is an alicyclic epoxy compound represented by the formula (P1-1) and represented by the formula (P1-2), particularly when it is desirable to reduce outgas. It is preferable to contain 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 whole compound (P1) is 1. It may be up to 99% by mass, 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, 40 to 60% by mass, and the like. Further, 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 outgas reduction and the viscosity of the energy-sensitive composition). It is preferable in that it can be made to. When the alicyclic epoxy compound represented by the formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) are used in combination, the alicyclic epoxy compound represented by the formula (P1-1) is used in combination. The content of the alicyclic epoxy compound represented by the formula (P1-1) with respect to the total amount of the epoxy compound and the alicyclic epoxy compound represented by the formula (P1-2) is not particularly limited, and is not particularly limited, for example. It may be 1 to 99% by mass, 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, 40 to 60% by mass, or the like.

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

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

Examples of the linking group Z include a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO _2- , -CBr _2- , and -C (CBr ₃ ) ₂ . Examples thereof include a divalent group selected from the group consisting of −, −C (CF ₃ ) _2- , and −R ^a19 −O—CO—, and a group to which a plurality of these 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, a divalent alicyclic hydrocarbon group and the like. .. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Examples thereof include a cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

^Ra19 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 that does not easily form a conjugated structure (particularly, a π-electron conjugated structure) by dehydrogenation is a cured product having excellent transparency in addition to thermal weight 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 via a linking group containing a quaternary carbon and / or a heteroatom. Bound compounds are preferred.

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

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

(In the formula ( ^P1-2 ), Ra1 to ^Ra12 are groups independently selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and are, for example, a hydrogen atom, a halogen atom, or oxygen. It is a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different from each other. Ra ² and ^{Ra 10} 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), Ra1 to ^Ra10 are groups independently ^selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and are, for example, a hydrogen atom, a halogen atom, or oxygen. It is a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different from each other. 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 ), Ra1 to ^Ra12 are groups independently selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and are, for example, a hydrogen atom, a halogen atom, or oxygen. It is a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different from each other. Ra ² and ^{Ra 10} 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 ), Ra1 to ^Ra12 are groups independently selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and are, for example, a hydrogen atom, a halogen atom, or oxygen. It is a hydrocarbon group which may contain an atom or a halogen atom, and may be the same or different from each other.)

In the formula (P1-1), when ^{Ra1 to Ra12 are} organic groups, the organic group is not particularly limited as long as it does not impair the object of the present invention, and even if it is a hydrocarbon group, a carbon atom and a halogen atom. It may be a group consisting of, or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom together with a carbon atom and a hydrogen atom. Examples of halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.

Organic groups include hydrocarbon groups, groups consisting of carbon atoms, hydrogen atoms, and oxygen atoms, halogenated hydrocarbon groups, groups consisting of carbon atoms, oxygen atoms, and halogen atoms, carbon atoms, and hydrogen atoms. , An oxygen atom, and a group consisting of a halogen atom are preferable. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

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

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 Halogen 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 cycloalkyl halides such as 4-bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group. , 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl Aryl halides such as groups and 4-fluorophenyl groups; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl It is a halogenated aralkyl group such as a methyl group, a 2-fluorophenylmethyl group, a 3-fluorophenylmethyl group and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom are hydroxy chains such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl group; Halogenized cycloalkyl group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 -Hydroxyaryl groups such as dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group. Hydroxyaralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy Group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy Group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, Chain alkoxy groups such as n-nonadesyloxy group and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group. Group and chain alkenyloxy group such as 3-n-butenyloxy group; phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4. -Aryloxy groups such as yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, Aralkyloxy groups such as β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethi Lu 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 Ekalkalkyl groups such as groups, 4-methoxy-n-butyl groups, 4-ethoxy-n-butyl groups, and 4-n-propoxy-n-butyl groups; methoxymethoxy groups, ethoxymethoxy groups, n-propoxymethoxy groups. , 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, Alkoxyalkoxy groups such as 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; 2-methoxyphenyl group, 3-methoxyphenyl group, and 4-. An alkoxyaryl group such as a methoxyphenyl group; an alkoxyaryloxy group such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, and a hexanoyl group. An aliphatic acyl group such as a group, a heptanoyle group, an octanoyl group, a nonanoyl group, and a decanoyle group; an aromatic acyl group such as a benzoyl group, an α-naphthoyl group, and a β-naphthoyl group; a methoxycarbonyl group, an ethoxycarbonyl group, n. -Propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyl Chain alkyloxycarbonyl groups such as oxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups, α-naphthoxycarbonyl groups, and β-naphthoxycarbonyl groups; formyloxy groups, acetyloxy groups, propionyloxy groups, pigs An aliphatic acyloxy group such as a noyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoiloxy group, an octanoyloxy group, a nonanoyloxy group, and a decanoyloxy group; a benzoyloxy group, an α-naphthoyloxy group, And aromatic acyloxy groups such as β-naphthoyloxy group.

R ^a1 to ^Ra18 are preferably groups independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and particularly energy. It is more preferable that all of ^{Ra1 to Ra18 are} hydrogen atoms because the cured product obtained by using the sensitive composition has excellent mechanical properties.

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

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

Among the alicyclic epoxy compounds represented by the formula (P1-2), specific examples of suitable compounds are bicyclononadeene epoxides represented by the following formula (P1-2a) or dicyclononanadiene epoxides. And so on.

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

Among the alicyclic epoxy compounds represented by the formula (P1-4), specific examples of suitable compounds include 4-vinylcyclohexenedioxide, dipentenedioxide, limonenedioxide, and 1-methyl-4- (3-). Methyloxylan-2-yl) -7-oxabicyclo [4.1.0] heptane and the like can be mentioned.

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

In addition to the aliphatic epoxy compound having an alicyclic epoxy group described above, examples of the non-polymer having an epoxy group that can be used as the compound (P1) include glycidyl (meth) acrylate and 2-methylglycidyl (meth). ) Epoxy alkyl (meth) acrylates such as acrylates, 3,4-epoxybutyl (meth) acrylates, 6,7-epoxyheptyl (meth) acrylates; 2-glycidyloxyethyl (meth) acrylates, 3-glycidyloxy-n- Epoxyalkyloxyalkyls such as propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate (Meta) acrylate; Bifunctional epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; phenol novolac type epoxy Novolak epoxy resin such as resin, brominated phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol AD novolak type epoxy resin; ring type such as epoxidized product of dicyclopentadiene type phenol resin. Aromatic epoxy resin such as epoxidized product of naphthalene type phenol resin; 9,9-bis [4- (glycidyloxy) phenyl] -9H-fluorene, 9,9-bis [4- [2- ( Glycidyloxy) ethoxy] phenyl] -9H-fluorene, 9,9-bis [4- [2- (glycidyloxy) ethyl] phenyl] -9H-fluoren, 9,9-bis [4- (glycidyloxy) -3 -Methylphenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3,5-dimethylphenyl] -9H-fluorene, and 9,9-bis (6-glycidyloxynaphthalen-2-yl) ) -9H-Fluoren, 9,9-Bis (6-glycidyloxynaphthalen-1-yl) -9H-Fluoren, 9,9-Bis (5-glycidyloxynaphthalen-1-yl) -9H-Fluoren, etc. , 9-Bis (glycidyloxynaphthyl) fluorene; 9,9-bis [6- (2-glycidyloxyethoxy) naphthalene- 2-yl] -9H-fluorene, 9,9-bis [6- (2-glycidyloxypropoxy) naphthalene-2-yl] fluorene, 9,9-bis [5- (2-glycidyloxyethoxy) naphthalene-1 -Il] fluorene, 9,9-bis [5- (2-glycidyloxypropoxy) naphthalene-1-yl] fluorene and other 9,9-bis (glycidyloxyalkoxynaphthyl) fluorene; 9,9-bis {6 -[2- (2-glycidyloxyethoxy) ethoxy] naphthalene-2-yl} -9H-fluorene, 9,9-bis {6- [2- (2-glycidyloxypropoxy) propoxy] naphthalene-2-yl} -9H-Fluorene, 9,9-bis {5- [2- (2-glycidyloxyethoxy) ethoxy] naphthalene-1-yl} -9H-fluorene, 9,9-bis {5- [2- (2- (2- (2- (2-) Glycidyloxypropoxy) Propoxy] Naphthalene-1-yl} -9H-Fluorene and other 9,9-bis (glycidyloxydialkoxynaphthyl) fluorenes; Epoxy group-containing fluorene compounds such as; dimer acid glycidyl ester and triglycidyl ester Glycidyl ester type epoxy resin such as: Tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethoxylylene diamine, and glycidylamine type epoxy resin such as tetraglycidylbisaminomethylcyclohexane; complex such as triglycidyl isocyanurate. Cyclic epoxy resin; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, fluorene 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] phenyl] propane. ) Fluorene] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and other trifunctional epoxy resins; tetra Tetrafunctional epoxy resins such as hydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresolsinol tetraglycidyl ether, and tetraglycidoxybiphenyl, and And 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. The 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel).
In addition, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3-hydroxymethyloxetanyl methacrylate, bis-1-ethyl-3-oxetanylmethyl ether, 1,4-bis-3-ethyloxetane. Monofunctional or bifunctional or higher oxetane compounds such as -3-ylmethoxymethylbenzene, 3-ethyl-3-2-ethylhexyloxymethyloxetane, and 3-ethyl-3-phenoxymethyloxetane are also preferably used.

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, the epoxy group-containing fluorene compound is preferable in terms of increasing the refractive index. , 9,9-Bis (glycidyloxynaphthyl) fluorene, the following formula (P1-8) 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 the formula (P1-8), ring Z ⁴ is a condensed polycyclic aromatic hydrocarbon ring, ^RP35 and ^RP36 are substituents, ^RP37 is a hydrogen atom or a methyl group, and k1 is an integer of 0 to 4. , K2 is an integer of 0 or more, and k3 is an integer of 1 or more.)

In the above formula (P1-8), the fused polycyclic aromatic hydrocarbon ring represented by ring Z ⁴ is a fused bicyclic hydrocarbon ring (for example, C8 to C20 fused di such as an inden ring and a naphthalene ring). Cyclic hydrocarbon rings, preferably C10-C16 fused bicyclic hydrocarbon rings), fused tricyclic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) and other fused two to tetracyclic hydrocarbon rings. Can be mentioned. Examples of the preferred fused polycyclic aromatic hydrocarbon ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable. The ^two rings Z4 substituted at the 9-position of fluorene may be the same or different rings, and usually may be the same ring.

The substitution position of the ring Z4 to be substituted at the ⁹ -position of fluorene is not particularly limited, and for example, the naphthyl group substituted at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group or the like. In particular, it is preferably a 2-naphthyl group.

Further, in the above formula (P1-8), examples of the substituent represented by ^RP35 include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a hydrocarbon group [for example, an alkyl group, Non-reactive substituents such as an aryl group (C6 to C10 aryl group such as phenyl group)] can be mentioned, and in particular, it is often a halogen atom, a cyano group or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C1-C6 alkyl groups (for example, C1-C4 alkyl groups, particularly methyl groups) such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group. When there are a plurality of (2 or more) k1, the ^RP35s may be different from each other or may be the same. Further, the ^RP35s substituted with the two benzene rings constituting the fluorene (or the fluorene skeleton) may be the same or different. Further, the bond position (substitution position) of ^RP35 with respect to the benzene ring constituting fluorene is not particularly limited. Preferred k1 is 0 to 1, especially 0. In the two benzene rings constituting fluorene, k1 may be the same as or different from each other.

Examples of the ^RP36 to be substituted with the ring Z ⁴ include C1 to C12 alkyl groups such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, preferably a C1 to C8 alkyl group, more preferably a C1 to C8 alkyl group). Is a C1-C6 alkyl group, etc.), a cycloalkyl group (eg, a C5-C8 cycloalkyl group such as a cyclohexyl group, preferably a C5-C6 cycloalkyl group, etc.), an aryl group (eg, a phenyl group, a trill group, etc.). C6 to C14 aryl groups such as xylyl group, preferably C6 to C10 aryl group, more preferably C6 to C8 aryl group and the like, aralkyl group (for example, C6 to C10 aryl group such as benzyl group and phenethyl group and C1 to C4 A hydrocarbon group such as an arylyl group formed by bonding with an alkyl group; an alkoxy group (for example, a C1 to C8 alkoxy group such as a methoxy group, preferably a C1 to C6 alkoxy group), a cycloalkoxy group (C5 to C10). Groups such as cycloalkyloxy groups, aryloxy groups (C6 to C10 aryloxy groups, etc.)-OR ^P38 [In the formula, ^RP38 indicates a hydrocarbon group (hydrogen group, etc. exemplified above). ]; Groups such as alkylthio groups (eg, C1-C8 alkylthio groups such as methylthio groups, preferably C1-C6 alkylthio groups and the like)-SR ^P38 (in the formula, ^RP38 is the same as above); acyl groups (eg, the same as above); 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) Atomic, 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.

Of these, ^RP36 is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group and the like, and particularly preferably. Preferred ^RP36s are hydrocarbon groups [eg, alkyl groups (eg, C1-C6 alkyl groups)], alkoxy groups (C1-C4 alkoxy groups, etc.), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms). Etc.) etc.

When there are a plurality (2 or more) of k2 in the same ring Z ⁴ , the RP ^36s may be different from each other or may be the same. Further, in the two rings Z ⁴ , the ^{RP 36} may be the same or different. Further, the preferred k2 may be 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably 0 to 4, and particularly preferably 0 to 2 (for example, 0 to 1). In the two rings Z ⁴ , k2 may be the same as or different from each other.

In the above formula (P1-8), ^RP37 is a hydrogen atom or a methyl group, and preferable ^RP37 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, and particularly 1. It should be noted 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, and may be substituted at an appropriate substitution position of ring Z ⁴ . In particular, the epoxy group-containing group is at least substituted with a hydrocarbon ring (for example, the 5-position, 6-position, etc. of the naphthalene ring) different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring. In many cases.

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

(Polymer having an epoxy group)
The polymer having an epoxy group may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group, and may be a hydroxyl group, a carboxy group, or an amino group. An epoxy group may be introduced into a polymer having a functional group having a reactivity such as, for example, by using a compound having an epoxy group such as epichlorohydrin. Further, a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain such as 1,2-polybutadiene can also be suitably used as a polymer having an epoxy group. Such partial oxides contain epoxy groups produced by oxidation of unsaturated bonds contained in the side chains.

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

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

The (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group, which will be described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Further, the (meth) acrylic acid ester having an epoxy group may contain an aromatic group. Among the (meth) acrylic acid esters having an epoxy group, among the (meth) acrylic acid esters having a chain aliphatic epoxy group, the aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group, from the viewpoint of the transparency of the cured product formed by using the 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 esters containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. , 4-Glysidyloxyphenylmethyl (meth) acrylate, 3-Glysidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate and the like.

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

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

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, the compounds represented by the following formulas (a2-1) to (a2-5) are preferable, and the compounds represented by the following formulas (a2-1) to (a2-3) are more preferable.

In the above formula, ^Ra 20 represents a hydrogen atom or a methyl group, Ra ²¹ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and ^Ra 22 represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms. It indicates a hydrocarbon group, and t indicates an integer of 0 to 10. As ^Ra21 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group and a cyclohexylene group are preferable.

As the polymer having an epoxy group, either a homopolymer of a (meth) acrylic acid ester having an epoxy group or a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer is used. However, the content of 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 and 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 storage stability of the energy-sensitive composition and chemical resistance of the cured product formed by using the energy-sensitive composition to alkalis and the like, the (meth) acrylic acid ester having an epoxy group and other monomers The copolymer with is preferably free of units derived from unsaturated carboxylic acids.

Examples of unsaturated carboxylic acids 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 direct acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Chain or branched alkyl (meth) acrylates; chloroethyl (meth) acrylates, 2,2-dimethylhydroxypropyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, trimethylolpropane mono (meth) acrylates, benzyls. Examples include (meth) acrylates, furfuryl (meth) acrylates; (meth) acrylic acid esters having a group having an alicyclic skeleton. Among the (meth) acrylic acid esters having no epoxy group, the (meth) acrylic acid ester having a group having an alicyclic skeleton is selected from the viewpoint of transparency of the cured product formed by using the energy-sensitive composition. preferable.

In the (meth) acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. 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, a tetracyclododecyl group and the like.

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

In the above formula, Ra ²³ represents a hydrogen atom or a methyl group, Ra ²⁴ represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and Ra ²⁵ represents a hydrogen atom or 1 carbon atom. Shows up to 5 alkyl groups. As R ^a24 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a25 , a methyl group and an ethyl group are preferable.

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

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

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 trill ether, vinyl chlorophenyl ether, vinyl-2,4- Vinyl aryl ethers such as dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; and the like can be mentioned.

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

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene. Alkylstyrene such as ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Examples thereof include styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, halostyrene such as 4-fluoro-3-trifluoromethylstyrene; 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 preferable because it is easy to obtain and synthesize. Partial oxidation of 1,2-polybutadiene gives epoxidized polybutadiene having an oxylanyl group and a vinyl group in the side chain. The ratio of the oxylanyl 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 oxylanyl group and the vinyl group. preferable. As the epoxidized polybutadiene, JP-100 and JP-200 commercially available from Nippon Soda Co., Ltd. can be preferably used.

The molecular weight of the polymer having an epoxy group described above is not particularly limited as long as it does not impair the object of the present invention, 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), a compound represented by the following formula (P1-6) can be 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 the formula (P1-6), ^RP31 to ^RP33 are linear, branched or cyclic alkylene groups, arylene groups, -O-, -C (= O)-, -NH- and these. It is a group consisting of a combination, and may be the same or different from each other. E ¹ to E ³ are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate. At least one substituent or hydrogen atom selected from the group consisting of a group, a thiol group, a carboxy group, a hydroxyl group and an succinic acid anhydride group. However, at ^{least one} of E1 to E3 is an epoxy group. And at least one selected from the group consisting of oxetanyl groups.)

In the formula (P1-6), for example, at least one of the groups represented by ^RP31 and E ^{1 , RP32} and E2, and ^RP33 and E3 is a group represented by the following formula ( ^P1-6a ). It is preferable that at least two of them are groups represented by the following formula (P1-6a), and each of them is a group represented by the following formula (P1-6a). Is even more preferable. The group represented by the formula (P1-6a) bonded to one compound is 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. C is at least one selected from the group consisting of an epoxy group and an oxetanyl group. In the formula (P1-6a), L and C may be bonded to form a cyclic structure.)

In the formula (P1-6a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is a carbon atom. An arylene group having a number of 5 to 10 is preferable. In the formula (P1-6a), L is a linear group consisting of an alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C (= O)-, -NH-, and a combination thereof. At least one of a linear alkylene group having 1 to 3 carbon atoms such as a methylene group and a phenylene group, or with these, —O—, −C (= O) − and NH— A group consisting of a combination of at least one of the above is preferable.

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 a structure having an epoxy group), an organic group represented by the following formula (P1-6b) or (P1-6c) can be mentioned.

（式（Ｐ１－６ｂ）中、Ｒ^Ｐ３４は、水素原子又はメチル基である。）

(In the formula (P1-6b), ^RP34 is a hydrogen atom or a methyl group.)

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

Further, as the compound (P1), for example, a siloxane compound having two or more glycidyl groups in the molecule (hereinafter, also referred to as “siloxane compound (B)”) can be mentioned.

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

As the siloxane compound (B), a compound having a cyclic siloxane skeleton represented by the following formula (B-1) is particularly excellent in curability and the obtained cured product is particularly excellent in heat resistance and transparency (hereinafter, 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 the formula ( ^B -1), RB1 and ^RB2 represent a monovalent group or an alkyl group containing a glycidyl group. However, of the n RB1 and n ^RB2 in the compound represented by the formula ( ^B -1), at least two are monovalent groups containing a glycidyl group. Further, n in the equation (B-1) indicates an integer of 3 or more. In addition, RB1 and ^RB2 in the compound represented by the formula ( ^B -1) may be the same or different. Further, the plurality of ^RB1s may be the same or different. The plurality of ^RB2s may be the same or different.

As the monovalent group containing the glycidyl group, a glycidyl ether group represented by —DOR ^B3 [D represents an alkylene group and ^RB3 represents a glycidyl group] is preferable. Examples of the D (alkylene group) include a linear or branched alkylene group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group and a trimethylene group. be able to.

Examples of the alkyl group include a linear chain 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. Alkyl groups in the form of or branched chains can be mentioned.

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

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

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

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

More specifically, the siloxane compound (B) includes a cyclic siloxane represented by the following formula and having two or more glycidyl groups in the molecule. Examples of the siloxane compound (B) include trade names "X-40-2701", "X-40-2728", "X-40-2738", and "X-40-2740" (above, Shin-Etsu Chemical). Commercially available products such as (manufactured by Kogyo Co., Ltd.) can be used.

[(P2) A compound that increases its solubility in a developing solution under the action of an acid]
Examples of compounds that increase the solubility in a developing solution under the action of an acid (hereinafter, also referred to as “compound (P2)”) include oligomers and polymers that can be obtained by copolymerizing the monomers listed below. , 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-norbornen-2-tert-butyl ester, 8-ethyl-8-tricyclodecanyl (meth) acrylate , (2-Tetrahydropyranyl) oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl) oxymethyltricyclododecanemethanol methacrylate, trimethylsilylmethyl (meth) acrylate, (2-tetrahydropyranyl) oxynorbornyl alcohol acrylate , (2-Tetrahydropyranyl) oxymethyltricyclododecanemethanol methacrylate, trimethylsilylmethyl (meth) acrylate], o- / m- / p- (3-oxocyclohexyloxy) styrene, o- / m- / p- ( 1-Methyl-1-phenylethoxy) styrene, o- / m- / p-tetrahydropyranyloxystyrene, o- / m- / p-adamantyloxystyrene, o- / m- / p-cyclohexyloxystyrene, o -/ M- / p-norbornyloxystyrene, acyclic or cyclic alkoxycarbonylstyrene [eg o-/m-/p-tert-butoxycarbonylstyrene, o-/m-/p-(3-oxocyclohexyloxy) Carbonyl) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonyl) styrene, o- / m- / p-tetrahydropyranyloxycarbonylstyrene, o- / m- / p-adamantyloxy Carbonylstyrene, o- / m- / p-cyclohexyloxycarbonylstyrene, o-/m-/p-norbornyloxycarbonylstyrene], acyclic or cyclic alkoxycarbonyloxystyrene [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 [eg] o- / m- / p-butoxycarbonylmethoxystyrene, p-tert-butoxycarbonylmethoxystyrene, o-/m-/p-(3-oxocyclohexyloxycarbonylmethoxy) styrene, o- / m- / p- ( 1-Methyl-1-phenylethoxycarbonylmethoxy) styrene, o- / m- / p-tetrahydropyranyloxycarbonylmethoxystyrene, o- / m- / p-adamantyloxycarbonylmethoxystyrene, o- / m- / p -Cyclohexyloxycarbonylmethoxystyrene, o- / m- / p-norbornyloxycarbonylmethoxystyrene, trimethylsiloxystyrene, dimethyl (butyl) siloxystyrene], unsaturated alkyl acetate (eg, isopropenyl acetate, a derivative thereof), 5 -Norbornenyl-2-tert-butyl ester

Monomer carrying an acid instability group with low activation energy [eg, p- or m- (1-methoxy-1-methylethoxy) styrene, p- or m- (1-methoxy-1-methylethoxy)- Methyl styrene, p- or m- (1-methoxy-1-methylpropoxy) styrene, p- or m- (1-methoxy-1-methylpropoxy) methyl styrene, 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 Styline, p- or m- (1-ethoxy-1-methylpropoxy) styrene, p- or m- (1-ethoxy-1-methylpropoxy) methylstyrene, p- or m- (1-ethoxyethoxy) styrene, p- or m- (1-ethoxyethoxy) -methylstyrene, p- (1-ethoxyphenylethoxy) styrene, p- or m- (1-n-propoxy-1-methylethoxy) -styrene, p- or m -(1-n-propoxy-1-methylethoxy) methylstyrene, p- or m- (1-n-propoxyethoxy) -styrene, p- or m- (1-n-propoxyethoxy) methylstyrene, p- Or m- (1-isopropoxy-1-methylethoxy) -styrene, p- or m- (1-isopropoxy-1-methylethoxy) methylstyrene, p- or m- (1-isopropoxyethoxy) -styrene , P- or m- (1-isopropoxyethoxy) methylstyrene, p- or m- (1-isopropoxy-1-methylpropoxy) styrene, p- or m- (1-isopropoxy-1-methylpropoxy) -Methyl styrene, p- or m- (1-iso-propoxypropoxy) styrene, p- or m- (1-isopropoxypropoxy) -methyl styrene, p- or m- (1-n-butoxy-1-methyl) Ethoxy) styrene, p- or m- (1-n-butoxyethoxy) styrene, p- or m- (1-isobutoxy-1-methyl-ethoxy) -styrene, p- or m- (1-tert-butoxy-) 1-Methylethoxy) styrene, p- or m- (1-n-pentyloxy-1-methylethoxy) styrene, p- or m- (1-isoamyloxy-1-methylethoxy) styrene, p- or m- (1-n-hexyloxy-1-methyl- Ethoxy) Styrene, p- or m- (1-cyclohexyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy) -1-Methylethoxy) -methylstyrene, p- or m- (1-benzyloxy-1-methylethoxy) styrene, p- or m- (1-benzyloxy-1-methylethoxy) methylstyrene, p- or m- (1-methoxy-1-methylethoxy) styrene, p- or m- (1-methoxy-1-methylethoxy) -methylstyrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy)- Styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) methylstyrene]

The compound (P2) may be a polymer having an alkoxyalkyl ester acid unstable group. Examples of polymers with alkoxyalkyl ester acid unstable groups can be revealed in US5225316 and EP829766. Examples of polymers with acetal protecting groups include, for example, US5670299, EP780732, US5627006, US55558976, US5558971, US546589, EP704762, EP762206, EP342498, EP5533737, and ACS Symp. Ser. 614, Microelectronics Technology, pp. 35-55 (1995), J. Mol. Photopolymer Sci. Technol. Vol. 10, No. 4 (1997), pp. 571-578, J. Mol. Photopolymer Sci. Technol. Vol. 12, no. 4 (1999) pp. 591-599 and "Proceedings of SPIE", Advances in Resist Technology and Processing XVII, Vol. 3999, Part One, pp. 579-590, 28. Feb. -1. Described in March 2000. However, the suitable polymers for the compositions according to this embodiment are not limited to them.

In addition, monomers having an acid unstable group may, where appropriate, other free radically polymerizable monomers that do not carry an acid unstable group [eg, styrene, acrylonitrile, methyl] in order to establish specific solubility and adhesion. It can be copolymerized with (meth) acrylate, (meth) acrylic acid, 4-hydroxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-vinylcyclohexanol, norbornene, ethylnorbornene, maleic anhydride]. Alternatively, the acid unstable group can only be subsequently introduced in a polymer-like reaction. It is also known to those skilled in the art that the prepolymer can be modified in a targeted manner prior to such polymer-like reactions, for example by partial hydrogenation, partial alkylation, partial acetylation. That is, the polymer having an acid unstable group does not have to be synthesized from the monomer by copolymerization in all cases.

For example, H. -T. Schacht, P.M. Falcino, N.M. Muenzal, R. et al. Schulz and A. Medina, ACS Symp. Ser. 706 (Micro-and Nanopatterning Polymers), pp. 78-94, 1997; H. -T. Schacht, N.M. Muenzal, P. et al. Falcino, H. et al. Holzworth and J. Schneider, J. Mol. Photopolymer Science and Technology, Vol. As described in 9, (1996), 573-586, it is also possible to introduce an acid unstable crosslink. Such an acid cross-linking system is preferable from the viewpoint of thermal stability. Further, such acid unstable cross-linking can be obtained by reaction with a phenol group-containing polymer (for example, 4-hydroxystyrene copolymer) with a di- and polyfunctional vinyl ether.

Another example of compound (P2) is a monomer compound in which each of the carboxylic acid group or the phenolic OH group is blocked by an acid unstable protective group (for example, a carboxylic acid and a phenol group-containing compound). Such acid instability blocking may be, 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. This can be done by converting the carboxy group to a sex ester group. 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 acrylic acid ester-containing copolymer and a methacrylic acid ester-containing copolymer. Are energy-sensitive compositions that are at least one compound, wherein their copolymers carry functional groups that increase the solubility of the polymer in an alkaline developer after reaction with an acid.

[(Px) Radical Polymerizable or Crosslinkable Compound]
Examples of the radically polymerizable or crosslinkable compound (also referred to as “compound (Px)” in the present specification) include acrylates having a reactive functional group. The reactive functional group 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. Also, the compound (Px) may have any desired structure (eg, it may contain units such as polyester, polyacrylate, polyether, etc.), but it may contain ethylenically unsaturated double bonds and Further, it contains a free OH group, a COOH group, an NH ₂ group or an NCO group.

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

であって、ＣＨ_２＝ＣＨＣＯＯＨと

との反応により得られるものである。

And CH ₂ = CHCOOH

It is obtained by the reaction with.

Another possible way to obtain 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 the following formula (Px-1) can be 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 the formula (Px-1), ^RP31 to ^RP33 are linear, branched or cyclic alkylene groups, arylene groups, -O-, -C (= O)-, -NH- and these. It is a group consisting of a combination, and may be the same or different from ^each other. E4 to ^E6 are between the compound (P1) and the compound represented by the formula (Px-1), or. It is a functional group or a hydrogen atom that can be radically polymerized or crosslinked between the compounds represented by the formula (Px ^{- 1} ). However, at least one of E4 to E6 is the functional group. .)

^In the formula (Px-1), the groups represented by ^RP31 and E4, ^RP32 and E5, and ^RP33 and ^E6 are, for example, at ^least one group represented by the following formula (Px-1a). It is preferable that at least two of them are groups represented by the following formula (Px-1a), and each of them is a group represented by the following formula (Px-1a). Is even more preferable. The group represented by the formula (Px-1a) bound to one compound is preferably the same group.
-L'-C'(Px-1a)
(In the formula (Px-1a), L'is a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (= O)-, -NH- and a group consisting of a combination thereof. C'is from 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 acid anhydride group. It is at least one substituent selected from the above group. Further, in the formula (Px-1a), L'and C'may be bonded to form a cyclic structure.)

In the formula (P1-6a), the linear, branched or cyclic alkylene group as L'is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is carbon. An arylene group having 5 to 10 atoms is preferable. In the formula (Px-1a), L'consists of a linear alkylene group having 1 to 6 carbon atoms, a phenylene group, -O-, -C (= O)-, -NH-, and a combination thereof. It is preferably a group, and at least one of 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 preferable. When the branched alkylene group and the succinic anhydride group are bonded to form a cyclic structure, specific examples thereof include cyclohexane-1,2-dicarboxylic acid anhydride.

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

As the compound component (P), 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 two or more kinds are used in combination, it is preferable to contain the compound (P1). In this case, the content of the compound (P1) is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more in the compound component (P). When the content of the compound (P1) is in the above range, the effect of improving the thermogravimetric stability is particularly large. When the energy-sensitive composition is used for 3D printing, the compound (P1) may be combined with the compound (Px), and in that case, it is preferable to use a photopolymerization initiator such as a radical photopolymerization initiator in combination.

[(Q) Sulfonium salt represented by the above formula (a1)]
The sulfonium salt represented by the above formula (a1) (hereinafter, also referred to as “sulfonium salt (Q)”) is in the ortho position with respect to the carbon atom to which A ¹ is bonded in the benzene ring in the above formula (a1). It is characterized in that a methyl group is bonded to the carbon atom of. Since the sulfonium salt (Q) has a methyl group at the above position, it is more likely to generate protons than the conventional sulfonium salt and has high sensitivity to active energy rays such as ultraviolet rays.

In the above formula (a1), it is preferable that both ^R1 and ^R2 are groups represented by the above formula (a2). R ¹ and R ² may be the same or different from each other.
In the above formula (a1), when R ¹ and R ² are bonded to each other 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. It is preferably a 5- to 7-membered ring, more preferably a 5- to 7-membered ring. The ring formed may be a polycyclic ring, and is preferably a condensed 5- to 7-membered ring.
^In the above formula (a1), R3 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 is 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 and an amino which may be substituted. It is preferably a group or a nitro group, and more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom.
In the above formula (a2), m1 can be selected according to the ^type of ring Z1, and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. ..

^In the above formula (a3), R5 may be an alkylene group; a hydroxy group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or a group represented by the above formula (a5). It is more preferable that the group is represented by the above formula (a5).
In the above formula (a3), R ⁶ may be 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). It is more preferable that the group is represented by the above formula (a6).
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 independently represented by an alkylene group; a hydroxy group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or the above formula (a5). 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), it is preferable that both R ⁹ and R ¹⁰ are groups represented by the above formula (a2). R ⁹ and R ¹⁰ may be the same or different from each other.
In the above formula (a4), when R ⁹ and R ¹⁰ are bonded to each other 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. It is preferably a 5- to 7-membered ring, more preferably a 5- to 7-membered ring. The ring formed may be a polycyclic ring, and is preferably a condensed 5- to 7-membered ring.
^In the above formula (a4), A3 is preferably S or O, and more preferably S.
In the above formula (a4), n2 is preferably 0.

In the above formula (a5), R ¹¹ is preferably an alkyl group which may be substituted with a halogen atom, a hydroxy group, an amino group which may be substituted, 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), m2 can be selected according to the type of ring Z ² , and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. ..

In the above formula (a6), R ¹² is an alkyl group, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, which may be substituted with a halogen atom, or an amino which may be substituted. It is preferably a group or a nitro group, and more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom.
In the above formula (a6), m3 can be selected according to the type of ring Z3 ^, and may be, for example, an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. ..

In the above formula (a1), X ⁻ corresponds to an acid (HX) generated by irradiating a sulfonium salt (Q) with active energy (heat, visible light, ultraviolet light, electron beam, X-ray, etc.) 1 It is a valence anion. When the sulfonium salt (Q) is used as an acid generator, monovalent polyatomic anions are preferably mentioned as X- ^, MY _a- ^, (Rf) _b PF _6-b- ^, R ^x1 _c BY _4- . Anions represented by _c- ^, R ^x1 _c GaY _4-c- ^, R ^x2 SO _3- ^, (R ^x2 SO ₂ ) ₃ C- ^, or (R ^x2 SO ₂ ) ₂ N ^- are more preferred. Further, 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 (preferably a fluorine atom).

Rf represents an alkyl group in which 80 mol% or more of hydrogen atoms are substituted with a fluorine atom (an alkyl group having 1 to 8 carbon atoms is preferable). Alkyl groups to be Rf by fluorine substitution include linear alkyl groups (methyl, ethyl, propyl, butyl, pentyl and octyl, etc.), branched chain alkyl groups (isopropyl, isobutyl, sec-butyl and tert-butyl, etc.) and cyclo. Examples thereof include alkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.). The ratio of hydrogen atoms of these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms possessed by the original alkyl group. % Or more, particularly preferably 100%. When the substitution ratio by the fluorine atom is in these preferable ranges, the photosensitivity of the sulfonium salt (Q) becomes further good. Particularly preferred Rf are CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, CF _{3 CF 2 CF 2-, CF 3 CF} ^{2 CF} _{2 CF 2-} ^{, (} _{CF 3} ⁾ _{2 CFCF 2-} , CF ₃ CF ₂ (CF ₃ ) CF ^{- and} (CF ₃ ) ₃ C-. The b Rfs are independent of each other and therefore may be the same or different from each other.

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

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

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

R ^x2 represents an alkyl group 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 chains. It may be cyclic or cyclic, and the alkyl group, fluoroalkyl group, or aryl group may be unsubstituted or have a substituent. Examples of the substituent include a hydroxy group, an amino group which may be substituted (for example, those exemplified in the following description regarding the above formulas (a2) to (a6)), a nitro group and the like. Be 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 (for example, ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonylamide). It may have 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-mentioned substituent, heteroatom or functional group, the number of the above-mentioned substituents, heteroatoms or functional groups may be one. It may be two or more.

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

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

The anions represented by (Rf) _b PF _6-b- ^include (CF ₃ CF ₂ ) ₂ PF _4- ^, (CF ₃ CF ₂ ) ₃ PF _3- ^, ((CF ₃ ) ₂ CF) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CF) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₂ PF _4- ^, (CF ₃ CF ₂ CF ₂ ) ₃ PF _3- ^, ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF _4- ^, ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- or (CF ₃ CF ₂ CF ₂ CF ₂ ⁾ ₃ PF _3- Examples thereof include anions to be formed. Of these, (CF ₃ CF ₂ ) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₃ PF _3- ^, ((CF ₃ ) ₂ CF) ₃ PF _3- ^, ((CF ₃ ) ₂ CF) ₂ Anions represented by PF _4- ^, ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ⁾ ₂ PF _4- are preferred.

The anion represented by R ^x1 _c BY ₄ -c ^- is preferably R ^x1 _c BY _4-c- ^.
(In the formula, R ^x 1 indicates a phenyl group in which at least a part of a hydrogen atom is substituted with a halogen atom or an electron-withdrawing group, Y indicates a halogen atom, and c indicates 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. Examples thereof include anions represented by _2- ^, C ₆ F ₅ BF _3- ^or (C ₆ H ₃ F ₂ ⁾ ₄ B-. Of these, anions represented by (C ₆ F ₅ ) ₄ B ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- are preferred.

The anions represented by R ^x1 _c GaY _4-c- ^include (C ₆ F ₅ ) ₄ Ga- ^, ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga- ^, (CF ₃ C ₆ H ₄ ) ₄ Examples thereof include anions 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, anions represented by (C ₆ F ₅ ) ₄ Ga ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- are preferred.

Examples of the ^anion represented by R ^x2 SO _3- include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutane sulfonic acid anion, pentafluorophenylsulfonic acid anion, and p-toluene. Examples thereof include sulfonic acid anion, benzene sulfonic acid anion, camphor sulfonic acid anion, methane sulfonic acid anion, ethane sulfonic acid anion, propane sulfonic acid anion and butane sulfonic acid anion. Of these, trifluoromethanesulfonic acid anion, nonafluorobutane sulfonic acid anion, methanesulfonic acid anion, butane sulfonic acid anion, camphor sulfonic acid anion, benzenesulfonic acid anion or p-toluene sulfonic acid anion are preferable.

The anions represented by (R ^x2 SO ₂ ⁾ ₃ C- include (CF ₃ SO ₂ ) ₃ C- ^, (C ₂ F ₅ SO ₂ ) ₃ C- ^, and (C ₃ F ₇ SO ₂ ⁾ ₃ C-. Alternatively, an anion represented by (C ₄ F ₉ SO ₂ ) ₃ C ⁻ may be mentioned.

The anions represented by (R ^x2 SO ₂ ⁾ ₂ N- include (CF ₃ SO ₂ ) ₂ N- ^, (C ₂ F ₅ SO ₂ ) ₂ N- ^, and (C ₃ F ₇ SO ₂ ⁾ ₂ N-. Alternatively, an anion represented by (C ₄ F ₉ SO ₂ ) ₂ N ⁻ can be mentioned.

The monovalent polyatomic anions include MY _a- ^, (Rf) _b PF _6-b- ^, R ^x1 _c BY _4-c- ^, R ^x1 _c GaY _4-c- ^, R ^x2 SO _3- ^, (R ^x2 ). SO ₂ ) In addition to the anion represented by ₃ C- ^or (R ^x2 SO ₂ ) ₂ N-, ^{perhalochloride} ion (ClO _4- ^, BrO _4- ^, etc.), halogenated sulfonate ion (FSO _3- ^, ClSO) ₃ ^- etc.), Sulfate ion (CH ₃ SO _4- ^, CF ₃ SO _{4-, HSO 4 -} ^etc .), Carbonate ion (HCO _3- ^, CH ₃ CO ₃ ^- etc.) ^, Aluminate ion (AlCl _4- ^, AlF) ₄ ^- etc.), Hexafluorobismarate ion (BiF _6- ⁾ , Carboxylic acid ion (CH ₃ COO- ^, CF ₃ COO- ^, C ₆ H ₅ COO- ^, CH ₃ C ₆ H ₄ COO- ^, C ₆ F ₅ COO- ^, CF ₃ C ₆ H ₄ COO- ^, etc.), arylborate ion (B (C ₆ H ₅ ) _4- ^, CH ₃ CH ₂ CH ₂ CH ₂ B (C ₆ H ₅ ) _3- ^, etc.), thiocyanic acid Ions (SCN- ⁾ , nitrate ions (NO _3- ⁾ and the like can be used.

Of 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 ) Anions represented ^by ₃ C- are preferred, 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 preferred, R ^x 1 _c BY _{4 -C} ^- is more preferred.

In the above formulas (a2), (a5), and (a6), the aromatic hydrocarbon ring includes a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, naphthalene). _C8-20 fused dicyclic hydrocarbon ring such as ring, preferably _C10-16 fused bicyclic hydrocarbon ring, fused tricyclic aromatic hydrocarbon ring (for example, anthracene ring, phenanthrene ring, etc.) and the like. Condensation 2 to 4-cyclic aromatic hydrocarbon ring] and the like. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

In the above 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), the alkyl group is a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-. Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched-chain alkyl groups with 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 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 optionally substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. .. Examples of the alkyl group substituted with a halogen atom include the above-mentioned linear alkyl group, branched chain alkyl group, or group in which at least one hydrogen atom in the cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, tri). Fluoromethyl, etc.) and the like. Of the alkyl groups that may be substituted with halogen atoms, the trifluoromethyl group is particularly preferred for ^R1 , ^R2 , ^R9 , or ^R10 , with respect to ^R4 , ^R6 , ^R11 , or ^R12 . Is particularly preferably a methyl group.

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

In the above formulas (a2) to (a6), the alkyl group in the alkylcarbonyl group is the above-mentioned linear alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, or 3 carbon atoms. Examples of the alkylcarbonyl group include up to 18 cycloalkyl groups, and examples of the alkylcarbonyl group include linear, branched or cyclic alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, etc.). 2-Methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl group, cyclohexanoyl group, etc.) and the like.

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

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

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

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

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

In the above formulas (a3) to (a6), the arylthio group includes an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio). , 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxy Phenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy ] Phenylthio, 4- [4- (Phenylthio) phenyl] phenylthio, 4- (Phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl- 3-Methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p) -Ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc.) and the like.

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

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

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

In the above formulas (a3) to (a6), the heterocyclic hydrocarbon group includes a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl). , Pyrimidyl, pyrazinyl, indrill, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantrenyl, phenoxadinyl, phenoxatiynyl, chromanyl, isochromanyl, dibenzothienyl , And dibenzofuranyl, etc.) and the like.

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

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

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.).

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

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

In the above formulas (a2) to (a6), the hydroxy (poly) alkyleneoxy group is HO (AO) _q- (in the formula, AO independently represents an ethyleneoxy group and / or a propyleneoxy group, and q is 1). A hydroxy (poly) alkyleneoxy group represented by (representing an integer of 5) and the like can be mentioned.

In the above formulas (a2) to (a6), the amino groups that may be substituted include an amino group (-NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methyl). Ethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methyl Phenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.) and the like can be mentioned.

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 Group, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, pentan-1,5-diyl group, pentan-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, nonan-1,9 -Diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane -1,15-diyl group, hexadecane-1,16-diyl group, etc.) and the like.

The sulfonium salt (Q) can be synthesized, for example, according to the following scheme. Specifically, the compound represented by the following formula (b2) is reacted with 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) in the presence of a base such as potassium hydroxide. Then, a nitro compound represented by the following formula (b3) is obtained, and then reduction is carried out in the presence of reducing iron to obtain an amine compound represented by the following formula (b4). This amine compound is reacted with a nitrite represented by MaNO ₂ (in the formula, Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom) (for example, sodium nitrite) to obtain a diazo compound. Next, this diazo compound, cuprous halide represented by CuX'(wherein X'indicates a halogen atom such as a bromine atom; the same applies hereinafter), and hydrogen halide represented by HX'. The mixture is mixed and the reaction 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 the Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) in the presence of chlorotrimethylsilane, and represented by the following formula (b7). The sulfonium salt to be obtained can be obtained. Further, this sulfonium salt is referred to as Mb ⁺ X " ^- (in the formula, Mb ⁺ indicates a metal cation, for example, an alkali metal cation such as potassium ion, ^and X" ^-is a monovalent anion represented by X-. The sulfonium salt represented by the following formula (b8) can be obtained by reacting with the salt represented by) represented by the following formula (b8) and performing salt exchange. ^In the following formulas (b2) to (b8) ^{, R1} to R3 and A1 are the same as those in the above formula (a1).

<Scheme>

Specific examples of the cation portion of the sulfonium salt (Q) represented by the above formula (a1) include the following. As a specific example of the anion portion of the sulfonium salt (Q) represented by the above formula (a1), conventionally known ones such as those mentioned in the above explanation of X ⁻ can be mentioned. 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, particularly R. ^x1 _c BY _4-c- ⁽ In the formula, R ^x1 indicates a phenyl group in which at least a part of a hydrogen atom is substituted with a halogen atom or an electron attractant, Y indicates a halogen atom, and c indicates 1 to 4). A combination with an anion represented by (indicating an integer) is preferable.
To.

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 (however, excluding the solvent). It is more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 8% by mass. When the content of the sulfonium salt (Q) is within the above range, the thermogravimetric stability tends to be good. In particular, when the viscosity of the energy-sensitive composition is adjusted to a low viscosity, for example, 1000 mPa · s (1000 cP) or less, which will be described later, the content of the sulfonium salt (Q) is the entire composition (however, the solvent is excluded. ), 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% by mass.

[Other ingredients]
(Other sulfonium salts, etc.)
The energy-sensitive composition of the present embodiment may contain an onium salt other than the sulfonium salt (Q) together with the sulfonium salt (Q).
Examples of the onium salt include an onium salt composed of a monovalent anion represented by X ⁻ in the above formula (a1) and an onium ion different from a cation other than X ⁻ in the above formula (a1). Therefore, a sulfonium salt (also referred to as "sulfonium salt (Q')" in the present specification) is preferable. As the monovalent anion represented by X ⁻ , the above-mentioned 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。）

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

Specific examples of the cation portion 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) (however, in the formula, ^R1 and ^R2 independently represent a group represented by the following formula (a2')). Examples include sulfonium salts.

（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 Z1 and m1 are as described above, and ^{R4'indicates an} aryl group.)

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

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

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

As the solvent, 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, pentanic acid, etc.) Chain alkyl esters such as methyl, ethyl pentanate, methyl hexanoate, ethyl hexanoate, methyl heptate, ethyl heptate; cyclopentyl acetate, cyclohexyl acetate, cyclooctyl acetate, methylcyclohexyl acetate, ethylcyclohexyl acetate, propylcyclohexyl acetate, etc. Cyclic alkyl esters such as isopropylcyclohexyl acetate, butylcyclohexyl acetate, isobutylcyclohexyl acetate, s-butyl cyclohexyl acetate, t-butyl cyclohexyl acetate, pentyl cyclohexyl 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, acetoacetic acid-n-butyl, α-acetyl-γ-butyrolactone, etc.) ); Β-Diketone compounds (acetylacetone, 2,4-hexanedione, 2,4-heptandione, etc.); ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol) Dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.), etc. Can be used alone or in combination of two or more.

In addition, conventionally known ketone solvents, alcohol solvents, amide solvents, and hydrocarbon solvents may be used. Further, a solvent known as a protonic solvent and / or a basic solvent may be used.
Protonic solvents include, for example, monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, diethylene glycol monomethyl ether and alcohols such as polyhydric alcohols such as ethylene glycol and glycerin; acetic acid, formic acid, (meth). Carboxylic acids such as acrylic acids; amines such as ethylenediamine, diethylamine; cyclic amides (lactams) such as N-methylpyrrolidone (NMP); amides such as formamides, N, N-dimethylformamides; phenols, Solvents such as p-butylphenol; active methylene compounds such as acetylacetone, diethyl malonate and the like.
Examples of the basic solvent include, for example, the above-mentioned amines and the above-mentioned nitrogen-containing amides, as well as pyridine, triethylamine, N, N-dimethylacetamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-. Examples thereof include imidazolidinone, N, N, N', N'-tetramethylurea, N, N, 2-trimethylpropionamide and the like.

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

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

As the alkali-soluble resin, (a) dicarboxylic acid or tricarboxylic acid or acid anhydride thereof with respect to the reaction product of the epoxy compound having two glycidyl ether groups derived from bisphenols and the unsaturated group-containing monocarboxylic acid. An alkali-soluble group such as an alkali-soluble resin (A1), a carboxy group, a phenol hydroxyl group, or a sulfo group (-SO _3H ) obtained by reacting (b) a tetracarboxylic acid or an acid dianhydride thereof. Examples thereof include a conventionally known resin (A2) having. In the present specification, the alkali-soluble resin (A2) preferably represents an alkali-soluble resin other than the alkali-soluble resin (A1). These alkali-soluble resins are also preferable when it is desirable that the obtained cured product has heat resistance.

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

The alkali-soluble resin (A2) is not particularly limited, and conventionally known alkali-soluble resins can be used. The 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 reacting a reaction product of an epoxy compound with an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

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

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

In the above general formula (f-2), R ^f1 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, respectively. , W ^f represent a single bond or a group represented by the following formula (f-3).

Further, in the above general formula (f-1), Y ^f indicates a residue obtained by removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides are phthalic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydro. Phthalic anhydride, glutaric anhydride and the like can be mentioned.

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

The alkali-soluble resin having an ethylenically unsaturated group is a polyester obtained by reacting a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid with a (meth) acrylic acid. (Meta) 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 novolac type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy An epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid can also be used.
In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means both acrylate and methacrylate.

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

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids; Will be. Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerizability, alkali solubility of the obtained resin, easy 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, and 6,7-epoxyheptyl (. (Meth) acrylic acid epoxyalkyl esters such as meth) acrylates, 3,4-epoxycyclohexyl (meth) acrylates, 4-oxatetracyclo- [6.2.1.02,700,5] undecanyl (meth) acrylates. Classes; α-alkylacrylic acid epoxyalkyl esters such as α-ethylacrylic acid glycidyl, α-n-propylacrylic acid glycidyl, α-n-butylacrylic acid glycidyl, α-ethylacrylic acid 6,7-epoxyheptyl; Examples thereof include glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoint of copolymerization reactivity, strength of resin after curing, etc. Glysidyl ethers, m-vinylbenzyl glycidyl ethers, and p-vinylbenzyl glycidyl ethers 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, a tetracyclododecyl group and the like. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas.

In the above general formula, Ra ³ represents a hydrogen atom or a methyl group, Ra ⁴ represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and ^Ra 5 represents a hydrogen atom or 1 to 6 carbon atoms. The alkyl group of 5 is shown. As R ^a4 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a5 , for example, a methyl group 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, more preferably 5 to 25% by mass. The proportion of the structural unit derived from the epoxy group-containing unsaturated compound is preferably 71 to 95% by mass, more preferably 75 to 90% by mass. The proportion of the structural unit derived from the alicyclic group-containing unsaturated compound is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and 5 to 15% by mass. Is even more preferable. By setting the above range, the obtained cured product can have sufficient heat resistance while making the alkali solubility of the obtained resin appropriate.

The mass average molecular weight of the alkali-soluble resin is preferably 1000 to 40,000, more preferably 2000 to 30,000. Within the above range, the obtained cured product 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 a siloxane resin 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 a Si atom via a linking group, and the linking group may be, for example, a linear group having 1 to 10 carbon atoms or a branched chain, a cycloalkylene group, or a cycloalkylene group. It is an arylene group or a divalent group in which these are combined.
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 the following formula, * means the end of the bond of R ^r1 that binds to Si in the 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, more preferably 500 to 70,000.

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

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

(Metal oxide particles)
The energy-sensitive composition according to this embodiment may contain metal oxide particles, if necessary. Thereby, the refractive index can be adjusted, and a cured product having low reflectivity and / or high transparency can be obtained. Examples of the metal oxide particles include at least one type of metal oxide particles selected from aluminum, zirconium, titanium, zinc, indium, tin, antimony, lanthanum, cerium, neodymium, gadolinium, holmium, lutetium, hafnium, and tantalum. Can be mentioned. An oxide of zirconium, titanium, or cerium can be preferably used, and a titanium oxide or a cerium oxide is particularly preferable in terms of increasing the refractive index. The shape of these metal oxide particles is not particularly limited, and those having an average particle size of 1 to 200 nm 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 of the energy-sensitive composition excluding the solvent.

Further, in the energy-sensitive composition according to the present embodiment, known additives (radical photopolymerization initiator, sensitizer, pigment, dispersant, filler, antistatic agent, flame retardant, extinguishing agent, extinguishing agent, if necessary. It can contain a foaming agent, a flow conditioner, a light stabilizer, an antioxidant, an adhesion imparting agent, an ion-supplementing agent, a coloring inhibitor, a solvent, a non-reactive resin, a radically polymerizable compound, etc.).
In particular, by combining a radical photopolymerization initiator or the like, the balance between the thermal reactivity and the photoreactivity of the energy-sensitive composition according to the present embodiment can be appropriately adjusted.

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

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

The energy-sensitive composition according to this embodiment is preferably used as a sealing material for an organic EL display element or a curable composition for a wafer level lens. The energy-sensitive composition according to this embodiment has excellent weight stability even when exposed to high temperatures and maintains its quality for a long period of time, and is therefore used as a sealing material for an organic EL display element or a wafer level lens. Is preferable. Further, it is preferable to be used in a composition for 3D printing because it has both thermal reactivity and photoreactivity.

Further, the energy-sensitive composition according to this embodiment was prepared as a coating liquid, for example, and applied to an object to be coated such as a polyimide film using a coating device such as a spin coater, a dip coater, a bar coater, or a slit coater. By post-curing, a hard coat can be formed. The coating liquid can cure the coating liquid 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 curl of the object to be coated due to the above. The film thickness of the object to be coated may be, for example, 10 μm or more.

Further, in general, in order to reduce the viscosity of the composition, a compound having a low molecular weight (P1), for example, an epoxy monomer is used, but on the other hand, the heat resistance is lowered as a compound having a low molecular weight is blended. It is easy and outgas is easily generated. However, it was confirmed that the energy-sensitive composition according to the present embodiment has excellent heat resistance and can reduce the generation of outgas by containing the sulfonium salt (Q) even if the viscosity is low. Surprisingly, even if the amount of the sulfonium salt (Q) added is smaller than the amount of the general cationic polymerization initiator added, the energy-sensitive composition has a low viscosity and heat resistance. It was confirmed by the experiment described later that the effects of improvement and reduction of outgas generation can be obtained.

The energy-sensitive composition according to this embodiment has excellent heat resistance while having a low viscosity, and can reduce the generation of outgas. Therefore, it is also preferably used in inkjet printing in which a low-viscosity ink is required. From the viewpoint of productivity and the like, the inkjet ink is preferably used for a display body such as a touch panel when it is applied to a relatively large area, and is also preferably used as a sealing material for an organic EL display element.

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

The casting molding method includes a simultaneous molding method and an individual piece molding method, each of which has the following steps.

(Simultaneous molding method)
Step 1: The energy-sensitive composition is poured into a wafer-level lens mold having a shape in which a plurality of lens molds are aligned in a certain direction, and is heated and / or irradiated with light to be cured. Step 2: Wafer-level lens mold Step 3: Obtain a cured product having a shape in which a plurality of wafer level lenses are bonded by removing and annealing the cured product. Step 3: Obtain a wafer level lens by disassembling the cured product having a shape in which a plurality of wafer level lenses are bonded.

(Individual piece molding method)
Step 1: The energy-sensitive composition is poured into a wafer-level lens mold having one lens mold and cured by heating and / or irradiating with light. Step 2: The wafer-level lens mold is removed and annealing treatment is performed. , Get a wafer level lens

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

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

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

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

The cured product of the energy-sensitive composition has excellent heat resistance even in a high temperature environment of about 100 to 250 ° C. Therefore, it is possible to efficiently manufacture a wafer level lens having excellent lens center position accuracy even if an annealing treatment is performed after removing the lens from the mold. Therefore, in step 3 of the simultaneous molding method, a plurality of cured products having a shape in which a plurality of wafer level lenses are bonded are stacked, and the position of the cutting line is determined based on the cured product at the top and cut. 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 the present 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 glasses lens, a light beam condensing lens, and a light diffusing lens of a camera (vehicle-mounted camera, digital camera, PC camera, mobile phone camera, surveillance camera and other cameras, especially wafer level camera). For example, it can be suitably used as a wafer level lens for an in-vehicle camera, which is particularly required to have heat resistance.

Furthermore, since the wafer level lens obtained by the energy sensitive composition of this embodiment has excellent heat resistance, it can be soldered by reflow when it is 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) board by the same solder reflow process as surface mounting of other electronic components, which is extremely efficient. Product manufacturing becomes possible.

<Curing product>
The cured product according to the present invention contains at least one compound component (P) selected from the group consisting of the above-mentioned compound (P1), compound (P2), and compound (Px), and a sulfonium salt (Q). It is a cured product obtained by curing an energy-sensitive composition. As described above, the cured product according to the present invention is excellent in weight stability against heat. This is because the inclusion of the sulfonium salt (Q) in the energy-sensitive composition increases the concentration of protons in the system containing the compound component (P) and the sulfonium salt (Q), and thus the compound component (P). It is presumed that the step-growth polymerization is continuously promoted to promote the polymerization, and the number of monomers decomposed by heat is small. The cured product is suitable as, for example, a sealing material for an organic EL display element, a wafer level lens, the above-mentioned hard coat, or the like. It is also suitable for flexible devices.
The cured product of the present 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, an epoxy group-containing fluorene compound as the compound (P1), and the like, which may be used alone or in combination of two or more. It is preferable to use metal oxide particles in terms of increasing the refractive index. The refractive index of the obtained cured product is, for example, a high refractive index of 1.7 or more as a refractive index at a wavelength of 633 nm, and when metal oxide particles are used, it is 1.75 or more, and further 1.8 or more. It is also possible to increase the refractive index. The upper limit of the refractive index at the wavelength of 633 nm is not particularly limited, but is, for example, 1.9 or less, 1.85 or less, and the like.

<Manufacturing method of cured product>
The method for producing a cured product according to the present invention comprises at least one compound component (P) selected from the group consisting of the above-mentioned compound (P1), compound (P2), and compound (Px), and a sulfonium salt (Q). Includes polymerizing and / or cross-linking an energy sensitive composition comprising. Since the energy-sensitive composition has energy sensitivity, it can be polymerized and / or crosslinked and cured by applying active energy. The active energy to be applied may be any energy as long as it has energy for inducing decomposition of the sulfonium salt (Q), and examples thereof include heat, visible light, ultraviolet rays, electron beams, and X-rays.

<Inkjet ink>
The energy-sensitive composition according to the present embodiment has a viscosity measured, for example, at 25 ° C. using an E-type viscometer, and has a viscosity of 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. The viscosity of the energy-sensitive composition of the present embodiment used as an inkjet ink may be, for example, 1 mPa · s (1 cP) or more, or 10 mPa · s (10 cP) or more, as long as it is within the above range. The energy-sensitive composition used as an inkjet ink preferably has a sulfonium salt (Q) content when prepared to have the above-mentioned low viscosity.

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

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

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

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

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

[Sulfonium salt]
-Sulfonium salt represented by the following formula (Q1)

-Sulfonium salt represented by the following formula (z1)

-Sulfone compound represented by the following formula (z2)

-Triphenylsulfonium tetrakis- (pentafluorophenyl) borate

[Evaluation 1]
The mixed liquids obtained in Examples 1 to 3 and Comparative Examples 1 to 9 were subjected to a differential thermal / thermogravimetric measuring device (TG / DTA-6200, manufactured by Seiko Instruments Inc.) in an air stream at a heating rate of 10 ° C. The temperature was raised from 20 ° C. to 250 ° C. under the condition of / min to obtain a TG / DSC curve. In the obtained TG curve, the weight reduction rate from the peak value was calculated. The results are shown in Table 1. The evaluation of the weight loss rate is based on the following criteria.
〇: Weight loss rate is 10% or less Δ: Weight loss rate is more than 10% and less than 40% ×: Weight loss rate is 40% or more

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

[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 loss rate was 10% or less, and Comparative Example 1 It showed better heat resistance than ~ 9. In the DSC curve of Example 3 shown in FIG. 1, a gentle peak was 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 step-growth polymerization is proceeding, and it is presumed that the polymerization is proceeding from a low temperature of around 110 ° C. On the other hand, in the DSC curves of the comparative examples shown in FIGS. 2 to 4, a sharp peak was observed. 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, and as a result, the weight loss rate becomes large. It is inferred that. For example, as shown in FIG. 2, in Comparative Example 7, the weight is reduced by about 65% at around 170 ° C. As shown in FIG. 3, in Comparative Example 8, the weight is reduced by about 30% at 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 showed a sharp peak at 50 ° C. or lower in the DSC curve, and was represented by the formula (P1-2a) at 50 ° C. or lower. It was confirmed that the compound (P1) to be decomposed started to be decomposed, the weight started to decrease from around 100 ° C, and the weight decreased by about 80% at around 165 ° C.

[Evaluation 2]
Obtained by applying a mixed solution in which the mass ratio of the mixed solution obtained in Example 1 was changed to the compound of the formula (P1-1a): the sulfonium salt of the formula (Q1) = 99: 1 on a glass substrate with a spin coater. After irradiating a coating film with a thickness of 20 μm with ghi rays using HMW-532D (manufactured by ORC) with an exposure amount of 1000 mJ / cm ² , the transmittance of the film at a wavelength of 400 nm was changed to MCPD-3000 (Otsuka). It was measured using (manufactured by Electronics). The transmittance was 99.6%.

[Discussion]
From this result, 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 in Examples 6 to 9 described later is also permeated. It is suggested that it will not adversely affect the rate.

<< Examples 4, 5 >>
As the compound (P1), an alicyclic epoxy compound represented by the above formula (P1-1a) or a bis-1-ethyl-3-oxetanylmethyl ether which is an oxetane compound represented by the following formula (P1-7a), and , The sulfonium salt represented by the above formula (Q1) is mixed at the compounding ratio shown in Table 2, and the obtained mixture is exposed to an exposure amount of 100 mJ / cm ² using an ultraviolet curing machine (broadband). When Example 4 was subjected to post-baking at 150 ° C. for 2 minutes and curing was attempted under the curing conditions that no post-baking was performed in Example 5, all the mixtures of Examples 4 and 5 did not cause tack. Hardened. In Table 2, the unit of the compounding ratio is a mass part.

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

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

[Manufacturing method of polyimide film 1]
As a reactor, 832 g of N, N-dimethylacetamide (DMAc) was filled while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler, and then the reactor was charged. After setting the temperature to 25 ° C., 64.0406 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, 31.09 g (0.07 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedidianhydride (6FDA) and 8.83 g (0) of biphenyltetracarboxylic dianhydride (BPDA). After adding .03 mol), the mixture was dissolved and reacted by stirring 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 content concentration of 13% by weight. 25.6 g of pyridine and 33.1 g of anhydrous acetic acid were added to the polyamic acid solution, and the mixture was stirred at 25 ° C. for 30 minutes, further stirred at 70 ° C. for 1 hour, cooled to room temperature, and precipitated in 20 L of methanol. The precipitated solid content was filtered and pulverized, and then dried at 100 ° C. for 6 hours in a vacuum to obtain 111 g of polyimide as a solid content powder.

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

[Manufacturing method of polyimide film 2]
A solution of polysilazane (MOPS-1800, manufactured by Az Materials) having a weight average molecular weight of 2000 g / mol dissolved in dibutyl ether (DBE) at 2 wt% on one surface of the polyimide film 1 was applied with a wire, and then at about 80 ° C. It was dried at a temperature to form a polysilazane film having a thickness of 300 nm. Then, after leaving it at room temperature for about 5 minutes, the polysilazane film is thermoset at a temperature of about 250 ° C. to form a silicon oxide layer, thereby producing a polyimide film 2 having a colorless transparent polyimide film / silicon oxide layer structure. did. The thickness of the obtained polyimide film 2 was 50 μm, the total light transmittance was 92%, and the yellowness (YI) was 1.0.

[Manufacturing method of polyimide film 3]
1000 g of N-methylpyrrolidone (NMP) was added to a 3 L separable flask with a stirring rod equipped with an oil bath while introducing nitrogen gas, and 232.4 g of 3,3- (diaminodiphenyl) sulfone (referred to as diamine 1). The mixture was added with stirring, and then 218.12 g of pyromellitic acid dianhydride was added, and the mixture was stirred at room temperature for 30 minutes. This was heated to 50 ° C. and stirred for 12 hours, and then 105.6 g of both-terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was dissolved in NMP298 g. Addition was made by dropping using a dropping funnel. The temperature was raised to 80 ° C., and after stirring for 1 hour, the oil bath was removed and the temperature was returned to room temperature to obtain a transparent NMP solution of polyamic acid (hereinafter, also referred to as varnish). The weight average molecular weight (Mw) of the obtained polyamic acid was 84000.

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

[Manufacturing method of polyimide film 4]
(Synthesis of imidazole compound (d))
First, 30 g of a cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to methanol. The methanol solution was then stirred at 40 ° C. Methanol was distilled off and the residue was suspended in 200 g of water. 200 g of tetrahydrofuran was mixed with the obtained suspension, 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 separated. 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)
Tetracarboxylic dianhydride (norbornane-2-spiro-α-cyclopentanone) represented by the following formula according to the methods described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518. -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 to create a nitrogen atmosphere in the three-necked flask. After adding 0.2045 g (0.90 mmol: manufactured by Nippon Pure Chemical Industries, Ltd .: DABAN) of 4,4'-diaminobenzanilide in a three-necked flask, N, N, N', N'-tetramethylurea (TMU) Was added in an amount of 3.12 g. 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 contents of the flask were stirred and reacted at room temperature (25 ° C.) for 12 hours under a nitrogen atmosphere. Obtained liquid. In this way, a reaction solution containing 15% by mass of polyamic acid (TMU solvent: 85 parts by mass) was formed in the reaction solution.

(Step of adding imidazole compound (d))
To the reaction solution obtained as described above, the imidazole compound (d) synthesized under a nitrogen atmosphere (0.206 g, 5.6 parts by mass with respect to 100 parts by mass of the reaction solution) was added. Then, 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. A polyimide precursor composition was obtained by adding 1.5 parts by mass of a silane coupling agent represented by the following formula as an additive to 100 parts by mass of the solid content in the composition.

(Preparation of polyimide film)
The polyimide precursor composition obtained as described above is heated on a glass substrate (large slide glass, trade name "S9213" manufactured by Matsunami Glass Ind. Co., Ltd., length: 76 mm, width 52 mm, thickness 1.3 mm). A coating film was formed by spin coating so that the thickness of the coating film after curing was 13 μm. 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 to evaporate and remove the solvent from the coating film.
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. In an inert oven, leave it to stand for 0.5 hours under a nitrogen atmosphere (oxygen concentration 100 ppm) under a temperature condition of 25 ° C, then heat it under a temperature condition of 135 ° C for 0.5 hour, and further heat it under a temperature condition of 300 ° C (final). The coating film was cured by heating at (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. to peel off the polyimide film from the glass substrate to obtain a 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 polyimide film sample is measured using an IR measuring machine (manufactured by Nippon Spectroscopy Co., Ltd., trade name: FT / IR-4100). did. As a result of the measurement, it was found that the C = O expansion / contraction vibration of imidecarbonyl was observed at 1696.2 cm ^-1 in the IR spectrum of the resin which is the material of the polyimide film. From the molecular structure identified based on such results, it was confirmed that the obtained polyimide film was certainly made of a polyimide resin.

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

For the total light transmittance value (unit:%) and yellowness (YI) of the film, JIS K7361- using the trade name "Haze Meter NDH-5000" manufactured by Nippon Denshoku Kogyo Co., Ltd. as a measuring device. It was obtained by making measurements in accordance with 1 (issued in 1997).

[Preparation of coating liquid]
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 liquid 1 having a solvent ratio of 80% by mass was prepared by dissolving it in acetate (PGMEA).

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

[Evaluation 3]
The coating liquid 1 and the coating liquid 2 for comparison were each applied to one surface of the polyimide films 1 to 4 attached to the wafer with a spin coater, and then dried at a temperature of 80 ° C. to obtain a coating film having a thickness of 4 μm. Then, the coating layer was irradiated with 100 mJ / cm ² using an ultraviolet curing machine having a wavelength of 365 nm to obtain each polyimide film having a hard coat (cured film) formed on one surface. Each of the obtained polyimide films was peeled off from the wafer, and the appearance was visually observed.

[Results / Discussion]
In the polyimide films 1 to 4 (Examples 6 to 9) in which the hard coat was formed using the coating liquid 1 according to the present embodiment, the transparency of the film did not decrease, and the coating liquid or the hard coat was cured. It was confirmed that the degree of curl of the film was small and the curing shrinkage was small.
On the other hand, in the polyimide films 1 to 3 (Comparative Examples 10 to 12) in which the hard coat using the comparative coating liquid 2 was formed, the color was slightly discolored to yellow, and the curl due to the curing of the coating liquid or the hard coat was large. It was confirmed that the hard coat made of the coating liquid 1 according to the present embodiment has a smaller curing shrinkage rate than the hard coat made of the coating liquid 2, and the degree of deformation of the polyimide film to be coated is suppressed. rice field.

[Evaluation 4]
In Evaluation 3, the surface resistance value of each hard coat formed on the polyimide films 1 to 4 was measured by Hiresta MCP-HT450 (manufactured by Mitsubishi Analytech Co., Ltd.), probe UR-100, and measurement voltage of 1,000 V. The surface resistance values were all over 1 × 10 ¹⁵ Ω.
From this result, it was confirmed that the coating liquid 1 according to this example can form a hard coat having 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), and the compounds (P1-6d) shown below used in Examples 1 and 3 were used. A sulfonium salt or the like (z3) was mixed at the compounding ratio shown in Table 1 to prepare a mixed solution. In Table 3, the unit of the compounding ratio is a mass part.

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

[Sulfonium salt, etc. (z3)]

[Evaluation 5]
The viscosities of the mixtures obtained in Examples 10 to 14 and Comparative Examples 14 to 15 were measured using an E-type viscometer under the conditions of 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 mixed solution obtained in Examples 10 to 14 and Comparative Examples 14 to 15 was precisely sealed in a glass vial, and the exposure amount was 1500 mJ / cm using an ultraviolet irradiator (HMW-532D, manufactured by ORC). After the exposure in No. ² , post-baking was performed at 100 ° C. for 15 minutes and at 85 ° C. for 100 hours to prepare each sample.

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

[Discussion]
As shown in Table 3, Example 10 using the compound (P1-1a) and the sulfonium salt (Q1) has the same viscosity as Comparative Example 14 without the sulfonium salt (Q1), but outgas. It was confirmed that the amount of sulphate generated was also small. Similarly, Example 14 using the compound (P1-1a), the compound (P1-6d), and the sulfonium salt (Q1) has the same viscosity as Comparative Example 15 without 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 if the amount of the sulfonium salt (Q1) is extremely small, it has the effect of reducing the viscosity of the mixture (energy-sensitive composition) and reducing the outgas. It was confirmed that there was. Similarly, as can be seen from the results of Examples 12 and 13, even if the amount of the sulfonium salt (Q1) is extremely small, the effect of reducing the viscosity of the mixture (energy-sensitive composition) and reducing the outgas. It was confirmed that there was.

From the results of Examples 11 and 12, when the total content of the compound component (P) to the compound (P1) is the same, the compound component (P) to the compound (P1) is more than the compound (P1-1a) alone. It was also confirmed that the combined use of the compound (P1-1a) and the compound (P1-2a) has the effect of lowering the viscosity of the mixed solution (energy-sensitive composition) and reducing the outgas. From this, as the compound component (P) to the compound (P1), the alicyclic epoxy compound represented by the above formula (P1-1) and the alicyclic epoxy compound represented by the formula (P1-2) are used. It is suggested that it may be preferable to use in combination with.

<< Examples 15 to 24 >>
[Preparation of energy sensitive composition with high refractive index]
In Examples 15 to 24, the cationic and / or acid-catalytically polymerizable and / or crosslinkable compound (P1) shown below and a sulfonium salt or the like are mixed at the blending ratio shown in Table 4 to form an energy-sensitive composition. I made a thing. In Table 4, the unit of the compounding ratio is parts by mass, and the compounding 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 total of the component (P1) and (Q1) of Example 15. 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 total of the component (P1) and (Q1) of Example 15. In Examples 15 to 23, the amount of the solvent was adjusted so that the concentration of the components excluding the solvent was 20% by mass. In Example 24, the amount of the solvent was adjusted so that the concentration of the component excluding the solvent was 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, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate 0.34 mol, acrylic acid 0.68 mol, propylene glycol monomethyl ether acetate in a 500 ml four-necked flask. 139.0 g and 2.15 g of tetraethylammonium bromide (TEAB) were charged and reacted by stirring at 100 to 105 ° C. under heating for 20 hours. Next, 0.12 mol of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride and 0.27 mol of 1,2,3,6-tetrahydrophthalic acid anhydride were charged in the flask, and the temperature was 120 to 125 ° C. The reaction was carried out by stirring under heating for 8 hours. Further, 0.28 mol of glycidyl methacrylate was charged and stirred at 100 to 105 ° C. under heating for 8 hours to obtain an alkali-soluble resin (A1a). The solid content concentration of the obtained alkali-soluble resin (A1a) was 57.0 wt%, the acid value (in terms of solid content) was 82 mgKOH / g, and the Mw by GPC analysis was 3500.

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

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate thus obtained and dissolved, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, 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. rice field. The disappearance of the acid anhydride group was confirmed by IR spectrum.
The alkali-soluble resin (A2a) having this cardo structure corresponds to the compound represented by the above-mentioned general formula (f-1).

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

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

[solvent]
(S1) Cyclohexyl acetate (S2) Diethylene glycol monobutyl ether acetate · (S3) Propylene glycol monomethyl ether acetate · (S4) Diethylene glycol methyl ethyl ether · (S5) N-Methylpyrrolidone

[Evaluation 6]
Each energy-sensitive composition of Examples 15 to 24 is applied to a glass substrate using a spin coater, prebaked at 100 ° C. for 120 seconds, and exposed to an exposure amount of 100 mJ / cm ² using an ultraviolet curing machine (broadband). After that, post-baking treatment was performed at 150 ° C. for 20 minutes (in Example 24, 230 ° C. for 20 minutes). The film thickness of the cured film of Examples 15 to 23 was 500 nm, and that of Example 24 was 50 nm. Each cured film has heat resistance. The refractive index of each cured film at a wavelength of 633 nm was measured. It was confirmed that each composition had a high refractive index of 1.7 or more. In particular, the cured film of Example 23 to which cerium oxide, which is a metal oxide particle, is added has a refractive index of 1.75 or more and Example 24 has a refractive index of 1.8 or more, and has a high refractive index (transparency). I was able to plan.

Claims (9)

(P1) Cationic polymerizable compound and
(Q) An energy-sensitive composition containing a sulfonium salt represented by the following formula (a1).

(In the formula, R ¹ and R ² independently indicate an alkyl group which may be 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 and the formula is expressed. A ring may be formed with the sulfur atom inside, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S or Se, and X -Indicates a monovalent anion ^, where R ¹ and R ² are not alkyl groups which may be substituted with a halogen atom at the same time.)

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group or an 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, It indicates an amino group, a cyano group, a nitro group, or a halogen atom which may be substituted, and m1 indicates an integer of 0 or more.)

(In the formula, 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, or a heterocyclic formula. A hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom. An alkylene group which may be substituted or a group represented by the following ^formula (a5) is shown, and R6 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an arylthio. Carbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, An amino group which may be substituted, a cyano group, a nitro group, or an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (a6) is shown, and A ² is a single bond, S, O, It indicates a sulfinyl group or a carbonyl group, and n1 indicates 0 or 1).

(In the formula, R ⁷ and R ⁸ are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, Aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro An alkylene group which may be substituted with a group or a halogen atom or a group represented by the following formula (a5) is shown, and R ⁹ and R ¹⁰ are independently an alkyl group which may be substituted with a halogen atom or the above. Representing a group represented by the formula (a2), R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with the sulfur atom in the formula, and A ³ is a single bond, S, O, sulfinyl group. Alternatively, it indicates a carbonyl group, X ⁻ is as described above, n2 indicates 0 or 1, but R ⁹ and R ¹⁰ are not alkyl groups which may be substituted with a halogen atom at the same time.)

(In the formula, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl which may be substituted with a halogen atom. Oxycarbonyl group, arylthiocarbonyl group, asyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy ( Poly) Indicates an alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 indicates an integer of 0 or more.)

(In the formula, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl 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, It indicates 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 indicates an integer of 0 or more.) The energy-sensitive composition according to claim 1, wherein the sulfonium salt is a boron-containing anion represented by the following general formula in which the monovalent anion represented by X ^- is a boron-containing anion.
R ^x1 _c BY _4- ^c-
(In the formula, R ^x 1 indicates a phenyl group in which at least a part of a hydrogen atom is substituted with a halogen atom or an electron-withdrawing group, Y indicates a halogen atom, and c indicates an integer of 1 to 4.) (P1) Cationic polymerizable compound and
(Q) An energy-sensitive composition containing a sulfonium salt represented by the following formula (a1).

(In the formula, R ¹ and R ² independently indicate an alkyl group which may be 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 and the formula is expressed. A ring may be formed with the sulfur atom inside, 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. As shown, X- indicates a monovalent anion, ^and the monovalent anion is the following general formula R ^x1 _c BY _4-c- ^.
(In the formula, R ^x 1 indicates a phenyl group in which at least a part of a hydrogen atom is substituted with a halogen atom or an electron-withdrawing group, Y indicates a halogen atom, and c indicates an integer of 1 to 4). It is a boron-containing anion to be produced. However, R ¹ and R ² are not alkyl groups that may be substituted with halogen atoms at the same time. )

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group or an 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, It indicates an amino group, a cyano group, a nitro group, or a halogen atom which may be substituted, and m1 indicates an integer of 0 or more.)

(In the formula, 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, or a heterocyclic formula. A hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom. An alkylene group which may be substituted or a group represented by the following ^formula (a5) is shown, and R6 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an arylthio. Carbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, An amino group which may be substituted, a cyano group, a nitro group, or an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (a6) is shown, and A ² is a single bond, S, O, It indicates a sulfinyl group or a carbonyl group, and n1 indicates 0 or 1).

(In the formula, R ⁷ and R ⁸ are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, Aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro An alkylene group which may be substituted with a group or a halogen atom or a group represented by the following formula (a5) is shown, and R ⁹ and R ¹⁰ are independently an alkyl group which may be substituted with a halogen atom or the above. Representing a group represented by the formula (a2), R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with the sulfur atom in the formula, and A ³ is a single bond, S, O, sulfinyl group. Alternatively, it indicates a carbonyl group, X ⁻ is as described above, n2 indicates 0 or 1, but R ⁹ and R ¹⁰ are not alkyl groups which may be substituted with a halogen atom at the same time.)

(In the formula, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl which may be substituted with a halogen atom. Oxycarbonyl group, arylthiocarbonyl group, asyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy ( Poly) Indicates an alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 indicates an integer of 0 or more.)

(In the formula, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryl 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, It indicates 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 indicates an integer of 0 or more.) The energy sensitivity according to any one of claims 1 to 3, wherein the sulfonium salt (Q) represents a group represented by the formula (a3) in which R6 represents a group represented by the ^formula (a6). Composition. The energy according to any one of claims 1 to 4, wherein the compound (P1) is a compound having at least one group selected from the group consisting of an oxylanyl group, an oxetanyl group, and an alicyclic epoxy group. Sensitive composition. The invention according to any one of claims 1 to 5, wherein the weight reduction rate from the peak value is 10% or less in the thermogravimetric measurement (TG) in which the temperature is raised to 230 ° C. Energy sensitive composition. The energy-sensitive composition according to any one of claims 1 to 6, which is a sealing material for an organic EL display element or a curable composition for a wafer level lens. A cured product obtained by curing the energy-sensitive composition according to any one of claims 1 to 7. A method for producing a cured product, which comprises polymerizing and / or crosslinking the energy-sensitive composition according to any one of claims 1 to 7.

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