JP2007034153A - Energy line-sensitive polymerizable composition, negative resist using the same and pictorial pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high sensitivity polymerizable composition which efficiently generates active radicals upon irradiation with an energy line, particularly light, and in which a radical polymerizable compound can polymerize in a very short time. <P>SOLUTION: The energy line-sensitive polymerizable composition contains a radical polymerization initiator (A) represented by formula (1), the radical polymerizable compound (B) and a chain transfer agent (C), wherein R<SB>1</SB>-R<SB>3</SB>each independently denote a group selected from alkyl, aryl, alkenyl, alkynyl, alkoxyl, aryloxy, alkylthio, arylthio and amino, provided that two or more of R<SB>1</SB>-R<SB>3</SB>are not simultaneously aryl; and R<SB>4</SB>-R<SB>7</SB>each independently denote a group selected from alkyl, aryl, alkenyl and alkynyl, provided that 2 or more of R<SB>1</SB>-R<SB>3</SB>are are not simultaneously aryl group and all of R<SB>4</SB>-R<SB>7</SB>are not simultaneously aryl group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an energy-sensitive polymerizable composition, a negative resist using the same, and an image pattern forming method using the same. More specifically, active radicals are efficiently generated by irradiation of energy rays, particularly light, radically polymerizable compounds are polymerized in a short time, and exposure through a mask film in which a pattern is recorded in advance or direct drawing by a laser light source To obtain cured products with good physical properties in the fields of spacers for liquid crystal displays, solder resists, resists for circuit board creation, resists for semiconductors, resists for microelectronics, hologram materials, various devices, etc. The present invention relates to a polymerizable composition, a negative resist using the same, and an image pattern forming method using the same.

In recent years, a photoresist method using a photosensitive resin has been used in various fields. In this photoresist method, for example, a photosensitive resin layer is formed on a substrate surface on which a desired image is to be provided by coating or transfer from another base material, and then an original image is formed on the photosensitive resin layer. In general, a method of forming an image corresponding to the original image by removing an unexposed portion by a developing treatment with a solvent or an aqueous alkaline solution after exposure by irradiating with an energy ray is generally used. As an example using such a photoresist method, for example, a certain type of negative resist is disclosed as a material for forming a display panel spacer (see Patent Documents 1 to 3). Also, certain types of negative resists have been disclosed as materials for manufacturing electrical / electronic components and printed circuit boards (see Patent Documents 4 to 6). Recently, a resist composition using an onium salt typified by a certain sulfonium salt as a photopolymerization initiator is known as a more sensitive resist composition, and a material for forming a spacer for a display panel. A certain type of negative resist is disclosed (see Patent Document 7). In addition, a certain type of negative resist is disclosed as a material for manufacturing electrical / electronic components and printed circuit boards (see Patent Document 8).
Thus, negative resist compositions using an onium salt typified by a sulfonium salt as a polymerization initiator are being proposed, but in recent years, in order to cope with improved productivity and various newly proposed processes, Addition of higher functions and new functions to resist compositions, especially in situations where resist compositions that require higher sensitivity, clear pattern formation, and high adhesion to substrates are required Neither is enough.

JP-A-11-174464 JP 2001-226449 A JP 2002-341931 A Japanese Patent Laid-Open No. 10-198033 JP 2002-236362 A JP 2002-249644 A Japanese Patent Laid-Open No. 08-278505 JP 08-314138 A

  An object of the present invention is to provide a highly sensitive polymerizable composition capable of efficiently generating active radicals upon irradiation with energy rays, particularly light, and capable of polymerizing a radical polymerizable compound in an extremely short time. A further object of the present invention is that the curing speed is extremely high, and it can be suitably used for very clear pattern exposure or direct drawing by an energy beam, and has excellent adhesion to a substrate, in particular. An object of the present invention is to provide a negative resist material having alkali developability suitably used for a photoresist material and an image pattern forming method using the negative resist.

（但し、式中Ｒ₁ 、Ｒ₂およびＲ₃ はそれぞれ独立に、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアミノ基より選ばれる基を、
Ｒ₄、Ｒ₅、Ｒ₆およびＲ₇はそれぞれ独立に、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基よりえらばれる基を示す。
但し、Ｒ₁ 、Ｒ₂およびＲ₃はその２個以上の基が結合している環状構造であってもよく、Ｒ₁ 、Ｒ₂およびＲ₃の２つ以上が同時に置換基を有してもよいアリール基となることはなく、
Ｒ₄、Ｒ₅、Ｒ₆およびＲ₇全てが同時に置換基を有してもよいアリール基となることはない。） As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, the present invention
The present invention relates to an energy-sensitive polymerizable composition comprising a radical polymerization initiator (A) represented by the following general formula (1), a radical polymerizable compound (B), and a chain transfer agent (C).
General formula (1)

(In the formula, R ₁ , R ₂ and R ₃ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. , An alkynyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. A group selected from an arylthio group which may be substituted, and an amino group which may have a substituent,
R ₄ , R ₅ , R ₆ and R ₇ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, a substituted group The group selected from the alkynyl group which may have a group is shown.
However, R ₁ , R ₂ and R ₃ may be a cyclic structure in which two or more groups are bonded, and two or more of R ₁ , R ₂ and R ₃ have a substituent at the same time. Is not a good aryl group,
R ₄ , R ₅ , R ₆ and R _{7 do not} all become an aryl group which may have a substituent at the same time. )

  Furthermore, this invention relates to the said energy-sensitive-polymerizable composition whose chain transfer agent (C) is a compound which has a thiol group.

（但し、式中Ａｒは、ヘテロ原子を含んでよい炭素数４〜３０の置換基を有してもよい単環または縮合多環アリール基を、
Ｒ₁₁およびＲ₁₂はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基を、
Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆およびＲ₇はそれぞれ独立に、一般式（１）中のそれらと同様のものを示す。
但し、Ａｒ、Ｒ₁₁、Ｒ₁₂、Ｒ₂およびＲ₃はその２個以上の基が結合している環状構造であってもよい。） Furthermore, this invention relates to the said energy sensitive ray polymeric composition whose photoradical polymerization initiator (A) is a compound represented by General formula (3).
General formula (2)

(In the formula, Ar represents a monocyclic or condensed polycyclic aryl group which may have a substituent having 4 to 30 carbon atoms and may contain a hetero atom,
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently the same as those in general formula (1).
However, Ar, R ₁₁ , R ₁₂ , R ₂ and R ₃ may have a cyclic structure in which two or more groups are bonded. )

  Furthermore, this invention relates to the said energy sensitive ray polymeric composition which further contains a sensitizer (D).

  Furthermore, this invention relates to the said energy sensitive ray polymeric composition which further contains alkali-soluble resin (E).

  Furthermore, the present invention relates to a negative resist comprising the energy-sensitive polymerizable composition.

  The present invention also relates to a method for producing an image pattern, comprising laminating the negative resist on a substrate, partially irradiating and curing an energy ray, and removing an unirradiated portion with an alkali developer. .

  The present invention also relates to an image pattern manufactured by the above-described image pattern manufacturing method.

  The energy-sensitive polymerizable composition of the present invention efficiently generates active radicals by irradiation with energy rays, particularly light, and is highly sensitive and capable of polymerizing radically polymerizable compounds in a short time. It is an energy-sensitive polymerizable composition that can be suitably used for clear pattern exposure or direct drawing, and has excellent adhesion to a substrate. Therefore, it was possible to provide a highly sensitive negative resist suitably used for a photoresist material and an image pattern forming method using the negative resist.

The present invention will be described in detail.
[Radical polymerization initiator (A)]
The radical polymerization initiator (A) of the present invention will be described. The radical polymerization initiator (A) of the present invention is characterized by having an onium salt structure composed of a sulfonium cation and a borate anion represented by the general formula (1).

  The sulfonium cation in general formula (1) is demonstrated.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the alkyl group which may have a substituent is a linear or branched chain having 1 to 30 carbon atoms, Examples thereof include monocyclic or condensed polycyclic alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl. Group, t-butyl group, 1-ethylpentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, trifluoromethyl group, 2-ethylhexyl group Phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylthiophenacyl group, -Phenylthiophenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, Examples thereof include, but are not limited to, a 3-nitrophenacyl group and a benzyl group.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the aryl group which may have a substituent is preferably an aryl group having 4 to 30 carbon atoms, such as phenyl Group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, turnanaphthalenyl, quarternaphthalenyl, Phthalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrilenyl group, phenalenyl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, triphenylenyl group, pyrenyl group, chrysenyl group Group, naphthacenyl group, preadenyl group, picenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group , And the like, but are not limited thereto, and these aryl groups may be bonded to a sulfur atom at a substitution position other than those described above, and these are also R ₁ and R of the present invention. ₂ Hoyo Included in the scope of the substituents denoted by R _3.

Further, the substituent on the sulfonium cation in the general formula (1) and the aryl group which may have a substituent in R ₁ , R ₂ and R ₃ are nitrogen atom, oxygen atom, sulfur atom, phosphorus atom and the like. It may have a hetero atom, for example, 2-thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, 3-thiantenyl group, 2-furyl group, pyranyl group, isobenzofura Nyl group, chromenyl group, xanthenyl group, 2-phenoxathiinyl group, 2-benzofuryl group, 2-benzothienyl group, 2H-pyrrolyl group, 2-pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, Pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-inda Zolyl group, purinyl group, 4H-quinolidinyl group, 4-isoquinolyl group, 4-quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3 -Carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, 3-phenixazinyl group, phenalsadinyl group, isothiazolyl group, 3-phenothiazinyl group, 2 -Thianthrenyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group Examples include piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, 3-coumarinyl group, etc., but are not limited to these, and aryl groups containing these heteroatoms include And may be bonded to a sulfur atom at a substitution position other than those described above, and these are also included in the category of the substituent represented by R ₁ , R ₂ and R ₃ of the present invention.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , an alkenyl group which may have a substituent is a straight chain or branched chain having 1 to 30 carbon atoms, A monocyclic or condensed polycyclic alkenyl group, which may have a plurality of carbon-carbon double bonds in the structure, for example, vinyl group, 1-propenyl group, allyl group, 2-butenyl group 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4- Hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group, etc. It is not limited to these.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, for example, ethynyl Groups, propynyl groups, propargyl groups, and the like, but are not limited thereto.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the alkoxyl group which may have a substituent is a linear or branched chain having 1 to 30 carbon atoms, Monocyclic or condensed polycyclic alkoxyl groups are preferred, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, Octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclo Propyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclo Hexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, 2-ethylhexyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyl Examples thereof include, but are not limited to, an oxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, and cyanomethyloxy group.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms. , Phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy Group, 4-methylthiophenyloxy group, 4-phenylthiophenyl Oxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carba A zolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, a 9-acridinyloxy group, and the like are exemplified, but the invention is not limited thereto.

In the substituents on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the alkylthio group which may have a substituent is preferably an alkylthio group having 1 to 20 carbon atoms, for example, methylthio Group, ethylthio group, propylthio group, isopropylthio group, butylthio group, hexylthio group, cyclohexylthio group, octylthio group, 2-ethylhexylthio group, decanoylthio group, dodecanoylthio group, octadecanoylthio group, cyanomethylthio group, methoxymethylthio group However, it is not limited to these.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the arylthio group which may have a substituent is preferably an arylthio group having 6 to 30 carbon atoms. Group, 1-naphthylthio group, 2-naphthylthio group, 2-chlorophenylthio group, 2-methylphenylthio group, 2-methoxyphenylthio group, 2-butoxyphenylthio group, 3-chlorophenylthio group, 3-trifluoromethyl Phenylthio group, 3-cyanophenylthio group, 3-nitrophenylthio group, 4-fluorophenylthio group, 4-cyanophenylthio group, 4-methoxyphenylthio group, 4-methylthiophenylthio group, 4-phenylthio Phenylthio group, 4-dimethylaminophenylthio group, 9-anthrylthio group, 9-phenane Tolylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4- Although carbazolylthio group etc. are mentioned, it is not limited to these.

In the substituent on the sulfonium cation in the general formula (1), R ₁ , R ₂ and R ₃ , the amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino Group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylthiophenylamino group, N-4-phenylthiophenylamino group, N-4 -Dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, Examples thereof include, but are not limited to, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, and the like.

The substituents R ₁ , R ₂ and R ₃ may be a cyclic structure in which two or more groups are bonded.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An aryloxy group that may have a substituent, an acyloxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent. The hydrogen atom of the amino group which may have a good arylthio group or a substituent may be further substituted with another substituent.

Examples of such other substituents include hydroxyl group, mercapto group, cyano group, nitro group, halogen atom, alkyl group, aryl group, acyl group, alkoxyl group, aryloxy group, acyloxy group, alkylthio group, arylthio group, An amino group etc. can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 30 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, t-butyl, sec-pentyl, t-pentyl, Examples include t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.
Examples of the aryl group include a monocyclic or condensed polycyclic aryl group having 4 to 30 carbon atoms that may contain a hetero atom, and specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group, 2-furanyl group, 2-thienyl group, 2-indolyl group , 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like.
As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 30 carbon atoms is bonded, or a carbon atom which may contain a hetero atom is 4 carbon atoms. To 30 monocyclic or condensed polycyclic aromatic bonded carbonyl groups, which may have an unsaturated bond in the structure. Specific examples include formyl group, acetyl group, propanoyl group, Butanoyl group, isobutanoyl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group , Benzoyl group, 2-methylbenzoyl group, 4-metho Shibenzoiru group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru group, 5-Nafutasenoiru group and the like.
Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 30 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-decyl Cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.
Examples of the aryloxy group include a monocyclic or condensed polycyclic aryloxy group having 4 to 30 carbon atoms which may contain a hetero atom. Specific examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, 9 -Anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluore Nyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like.
The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 30 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples thereof include a carbonyloxy group having 4 to 30 monocyclic or condensed polycyclic aromatic groups bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth Examples include a loyloxy group and a 5-naphthacenoyloxy group.
Examples of the alkylthio group include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 30 carbon atoms. Specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.
Examples of the arylthio group include a monocyclic or condensed polycyclic arylthio group having 4 to 30 carbon atoms which may contain a hetero atom, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3 -Carbazolylthio group, 4-carbazolylthio group, etc. are mentioned.
Examples of the amino group include alkylamino groups such as methylamino group and cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, etc. Is mentioned.

Further, alkoxycarbonyl group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group , A phosphono group, a trimethylammoniumum group, a dimethylsulfoniumum group, a triphenylphenacylphosphoniumyl group, and the like, but are not limited thereto.

In general formula (1), at least one of R ₁ , R ₂ and R ₃ has a phenacyl group which may have a substituent, a benzyl group which may have a substituent or a substituent. A structure in which R ₄ is an alkyl group which may have a substituent, and R ₅ , R ₆ and R ₇ are aryl groups which may have a substituent. It is. A particularly preferable structure is a structure represented by the general formula (3).

For this reason, it is required to increase the decomposition efficiency of the radical polymerization initiator (A) represented by the general formula (1), particularly in light, but at least one of R ₁ , R ₂ and R ₃ is And a phenacyl group which may have a substituent, a benzyl group which may have a substituent, or an allyl group which may have a substituent, particularly a phenacyl group represented by the general formula (3). By introducing arylcarbonylmethyl groups, it is considered that these groups decompose preferentially and efficiently from sulfonium cations to generate radicals, and an improvement in sensitivity is recognized.

  The substituent Ar on the sulfonium cation in the general formula (3) represents a monocyclic or condensed polycyclic aryl group which may have a substituent having 4 to 30 carbon atoms and may contain a hetero atom, for example, a phenyl group , Biphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1 -Indenyl group, 2-azurenyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m- and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, turnanaphthalenyl, quarternaphthalenyl, heptareni Group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, triphenylenyl group, pyrenyl group, chrysenyl group , Naphthacenyl group, preadenyl group, picenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, Ovalenyl group, 2-thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthine Nyl group, 2-phenoxathiinyl group, 2-benzofuryl group, 2-benzothienyl group, 2H-pyrrolyl group, 2-pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, Indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, 4-isoquinolyl group, 4-quinolyl group, phthalazinyl group, naphthyridinyl group, Quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl Group, phenazinyl group, 3- Enixazinyl group, phenalsadinyl group, isothiazolyl group, 3-phenothiazinyl group, 2-thianthrenyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group A pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, a morpholinyl group, a thioxanthryl group, a 3-coumarinyl group, and the like are exemplified, but not limited thereto.

In the substituents R ₁₁ and R ₁₂ on the sulfonium cation in the general formula (3), examples of the alkyl group which may have a substituent include the substituents on the sulfonium cation in the general formula (1), R ₁ and R _2. In addition, the same substituents as those exemplified as the alkyl group which may have a substituent in R ₃ can be exemplified, but the invention is not limited thereto.

In the substituents R ₁₁ and R ₁₂ on the sulfonium cation in the general formula (3), the aryl group which may have a substituent includes substituents on the sulfonium cation in the general formula (1), R ₁ and R _2. In addition, the same substituents as those exemplified as the aryl group which may have a substituent in R ₃ can be exemplified, but the invention is not limited thereto.

The substituents R ₂ and R ₃ on the sulfonium cation in the general formula (3) and the substituents R ₄ , R ₅ , R ₆ and R ₇ on the borate anion in the general formula (3) are respectively represented by the general formula (1). Are the same as the substituents R ₂ and R ₃ on the sulfonium cation and the substituents R ₄ , R ₅ , R ₆ and R ₇ on the borate anion in the general formula (1). Specific examples of the substituent that may be used include the same substituents as those described in the general formula (1), but are not limited thereto.

Furthermore, the monocyclic or condensed polycyclic aryl group which may have a substituent having 4 to 30 carbon atoms that may include a hetero atom in the substituent Ar on the sulfonium cation in the general formula (3), the general formula (3) hydrogen atoms of the aryl group which may have a substituent group in the substituents R ₁₁ and R ₁₂ in the substituent alkyl group which may have a general formula (3) in the substituents R ₁₁ and R ₁₂ in the), Further, it may be substituted with another substituent.

Specific examples of such other substituents include those described as the substituents on the sulfonium cation in the general formula (1), and other substituents which may be substituted in R ₁ , R ₂ and R ₃ . Although the same thing is mentioned, it is not limited to these.

The substituents Ar, R ₁₁ , R ₁₂ , R ₂ and R ₃ on the sulfonium cation in the general formula (3) may be a cyclic structure in which two or more groups are bonded.

  Next, the borate anion in the general formula (1) will be described.

  The borate anion in the general formula (1) can be synthesized relatively easily, has higher sensitivity, high solubility, and high safety and hygiene, and therefore is particularly suitable as a counter anion for the onium salt represented by the general formula (1). It can be preferably used.

In the general formula (1), the substituents on the borate anion, R ₄ , R ₅ , R ₆ and R ₇ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent. And a group selected from an alkenyl group which may have a substituent and an alkynyl group which may have a substituent.

In the substituent on the borate anion in the general formula (1), R ₄ , R ₅ , R ₆ and R ₇ , the alkyl group which may have a substituent is a linear or branched chain having 1 to 30 carbon atoms. Examples thereof include a chain, monocyclic or condensed polycyclic alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, 2-ethylhexyl group, benzyl Examples include, but are not limited to, groups.

In the substituent on the borate anion in the general formula (1), R ₄ , R ₅ , R ₆ and R ₇ , the aryl group which may have a substituent includes a phenyl group, an o-tolyl group, and an m-tolyl group. Group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, cumenyl group, p-methoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 2,4-bis (tri Fluoromethyl) phenyl group, p-fluorophenyl group, p-chlorophenyl group, p-bromophenyl group, and the like, but are not limited thereto.

In the substituents on the borate anion in the general formula (1), R ₄ , R ₅ , R ₆ and R ₇ , the alkenyl group which may have a substituent is a linear or branched chain having 1 to 30 carbon atoms. Examples thereof include a chain, monocyclic or condensed polycyclic alkenyl group, which may have a plurality of carbon-carbon double bonds in the structure, for example, vinyl group, 1-propenyl group, allyl group, 2 -Butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like. However, it is not limited to these.

In the substituents on the borate anion in the general formula (1), R ₄ , R ₅ , R ₆ and R ₇ , the alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, Examples include, but are not limited to, ethynyl group, propynyl group, propargyl group, 2-tert-butylethenyl group, 2-phenylethenyl group and the like.

  Furthermore, the hydrogen atom of the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, and the alkynyl group which may have a substituent May be further substituted with another substituent.

Examples of such a substituent include those on the sulfonium cation in the general formula (1), and those exemplified as substituents which may be further substituted with other substituents in the description of R ₁ , R ₂ and R _3. The same substituents can be exemplified, but are not limited thereto.

The substituents on the borate anion in the general formula (1), R ₄ , R ₅ , R ₆ and R ₇ are preferably each independently an alkyl group which may have a substituent or a substituent. An aryl group etc. are mentioned, More preferably, although a methyl group, an ethyl group, a butyl group, a phenyl group, a mesityl group, 4-methylphenyl group, 3-fluorophenyl group etc. are mentioned, it is not limited to these. .
When one of the four substituents bonded to boron is an alkyl group that may have a substituent, and three are phenyl groups that may have a substituent, the radical generating ability is improved. This is preferable.

  Therefore, as the structure of the borate anion in the general formula (1), specifically, tert-butyl triethyl borate, phenyl triethyl borate, tributyl benzyl borate, diethyl dibutyl borate, dibutyl diphenyl borate, methyl triphenyl borate, ethyl triphenyl borate Propyl triphenyl borate, isopropyl triphenyl borate, butyl triphenyl borate, sec-butyl triphenyl borate, tert-butyl triphenyl borate, dodecyl triphenyl borate, benzyl triphenyl borate, vinyl triphenyl borate, ethynyl triphenyl borate, Butyltrimesitylborate, butyltris (p-methoxyphenyl) borate, butyltris (p-fluorophenyl) borate Butyl tris (p-bromophenyl) borate, sec-butyltris (p-methoxyphenyl) borate, sec-butyltris (p-fluorophenyl) borate, tert-butyltris (p-methoxyphenyl) borate, butyltris [3,5- Bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, butyltri (m-fluorophenyl) borate, tetraphenylborate, pentafluorophenyltrifluoroborate, 3,5-bis (trifluoromethyl) phenyltrifluoro Roborate, bis (pentafluorophenyl) difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, tris 3,5-bis (trifluoromethyl) phenyl] fluoroborate, although tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and the like, but is not limited thereto.

  Of these, butyltriphenylborate is particularly preferable as the borate anion in the general formula (1).

  The radical polymerization initiator (A) represented by the general formula (1) of the present invention comprises a combination of the sulfonium cation and borate anion exemplified above.

Specific structures are shown below, but the structure of the radical polymerization initiator of the present invention is not limited thereto. X ⁻ in the following structural formula may be any borate anion selected from the borate anion structure described above.

[Radically polymerizable compound (B)]
The radically polymerizable compound of the present invention will be described. The radical polymerizable compound of the present invention is a compound having an ethylenically unsaturated bond capable of radical polymerization, and the compound having an ethylenically unsaturated bond capable of radical polymerization is an ethylenically unsaturated compound capable of radical polymerization in the molecule. Any compound may be used as long as it has at least one bond, and it has a chemical form such as a monomer, an oligomer or a polymer. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the intended characteristics.

  Examples of such a compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, Examples include urethane, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and other radical polymerizable compounds, but the present invention is not limited thereto. It is not something.

  Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neo Pentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate , Pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, etc. Acrylic acid derivatives, methyl methacrylate, n-butyl methacrylate, 2-hexyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol di Methacrylate, polypropylene Methacrylic acid derivatives such as recall dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, allyl glycidyl ether, diallyl phthalate, triallyl trimelli Derivatives of allyl compounds such as tate, etc., and more specifically, edited by Shinzo Yamashita et al., “Crosslinking Agent Handbook” (1981, Taiseisha), edited by Sato Kato, “UV / EB Curing Handbook (raw material) Ed.) "(1985, Polymer Press Society), edited by Radtech Research Group," Application and Market of UV / EB Curing Technology ", 79, (1989, CMC), Akamatsu Kiyoshi edited, Practical Technology of Resin Resin ”(1987, CMC), Shinichiro Takiyama,“ Polyester Resin Handbook ", (1988, Nikkan Kogyo Shimbun, Inc.) or commercially available radically polymerizable or crosslinkable monomers, oligomers and polymers known in the industry, but are not limited thereto.

  The amount of the radical polymerization initiator (A) represented by the general formula (1) of the present invention is usually 0.1 to 100 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). Preferably 3 to 60 parts by weight.

[Chain transfer agent (C)]
The chain transfer agent of the present invention will be described. The chain transfer agent of the present invention is not particularly limited as long as it inhibits polymerization inhibition by oxygen and causes a uniform photocuring reaction even under high light shielding conditions, but a thiol compound is preferable, and a polyfunctional thiol is particularly preferable. Compounds are preferred.

  The compound having a thiol group used as the chain transfer agent (C) in the present invention is not particularly limited as long as it has at least one thiol group in the molecule, and has been conventionally used for a polymerizable composition. It can be arbitrarily selected from those that are used. Examples of the compound having such a thiol group include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 5-chloro-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 5-mercapto-1-methyltetrazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 2-mercapto-1-methyl Examples thereof include, but are not limited to, imidazole, 2-mercaptothiazoline, and octanethiol.

  Particularly preferred polyfunctional thiol compounds include compounds having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, 1,4-butanediolbis (3-mercaptopropio 1, 4-butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylol Propanetris (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), 2,5-hexanedithiol, 2,9-decandithio 1,4-bis (1-mercaptoethylbenzene), phthalic acid bis (1-mercaptoethyl ester), phthalic acid bis (2-mercaptopropyl ester), phthalic acid bis (3-mercaptobutyl ester), phthalic acid bis (3-mercaptoisobutyl ester), ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3- Mercaptobutyrate), 1,3-butanediol bis (3-mercaptobutyrate), 1,2-butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-Mel Captobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate) Rate), 1,4-butanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol tetrakis (2 -Mercaptoisobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate) Rate), 1,4-butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexakis ( 3-mercaptoisobutyrate), 1,8-octanediol bis (3-mercaptobutyrate), 1,8-octanediol bis (2-mercaptopropionate), 1,8-octanediol bis (3-mercapto) Isobutyrate), 2,4,6-trimercapto-S-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-S-triazine, and the like. is not.

  In the present invention, these chain transfer agents can be used alone or in combination of two or more.

  The chain transfer agent (C) of the present invention is used in an amount of usually 5 to 3000 parts by weight, preferably 100 parts by weight of the radical polymerization initiator (A) represented by the general formula (1) of the present invention. Is 20 to 1000 parts by weight.

[Sensitizer (D)]
The energy-sensitive polymerizable composition of the present invention can be combined with a sensitizer that absorbs ultraviolet to near-infrared light to increase the activity with respect to light from the ultraviolet to the near-infrared region. It is possible to obtain a polymerizable composition.

  Specific examples of such sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , Naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, Oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzopo Filin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives , Spirooxazine derivatives, thiospiropyran derivatives, carbazole derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, etc. Other specific examples include Ogahara Shin et al., “Dye Handbook” (1986, Kodansha), Okawara Sensitizers described in Shin et al., "Chemicals of Functional Dyes" (1981, CMC), edited by Tadasaburo Ikemori et al., "Special Functional Materials" (1986, CMC) However, the present invention is not limited to these, and other sensitizers that absorb light from the ultraviolet to the near-infrared region can be used, and these may be used in an arbitrary ratio as needed. . Among the sensitizers, examples of the sensitizer that can particularly preferably sensitize the radical polymerization initiator of the present invention include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, and the like. It is not limited to.

[Alkali-soluble resin (E)]
The alkali-soluble resin of the present invention will be described. The alkali-soluble resin of the present invention acts as a binder, and when forming an image pattern, the developer used in the development processing step, particularly preferably, it is soluble in an alkali developer. It is not particularly limited. Among these, an alkali-soluble resin which is a carboxyl group-containing copolymer is preferable, and an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ) And other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as “copolymerizable unsaturated monomers”) (hereinafter simply referred to as “carboxyl group-containing copolymers”). Is preferred).

  Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Unsaturated dicarboxylic acids such as acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acrylic acid) Divalent or higher polyvalent carboxylic acids such as leuoxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters; ω-carboxypolycaprolactone monoacrylate, ω-carboxypoly It can be mentioned mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as caprolactone monomethacrylate. Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name. The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

  Examples of the copolymerizable unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxy. Styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. Aromatic vinyl compounds, indenes such as indene and 1-methylindene,

  Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate , 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate , Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate,

  2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate,

  Unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, vinyl carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate, vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether Saturated ethers, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacryl Unsaturated amides such as amide, unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 1,3-butadiene, isoprene, chloroprene Aliphatic conjugated dienes such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, etc., at the end of the polymer molecular chain, a monoacryloyl group or a monomethacryloyl group And macromonomers having These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  The carboxyl group-containing copolymer in the present invention includes (a) acrylic acid and / or methacrylic acid as an essential component, and in some cases, succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyl). A carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group of (Roxyethyl), ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate, and (b) styrene, methyl Acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol mono A copolymer with at least one selected from the group of methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer (hereinafter referred to as “carboxyl group-containing copolymer (1)”) is preferred.

  Specific examples of the carboxyl group-containing copolymer (1) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid. / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / Polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, ( (Meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,

  (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- ( (Meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer And (meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

  In the carboxyl group-containing copolymer, a substituent present in the molecule may be further modified with another material. For example, a part of the carboxyl group present in the polymer is modified by reacting with a monomer having a functional group reactive with a carboxyl group, such as a known glycidyl group, and crosslinking that can participate in radical polymerization in the molecule. It is also possible to provide points. As such a monomer, glycidyl (meth) acrylic acid alkyl ester can be used, for example, glycidyl (meth) acrylic acid, glycidyl (meth) methyl acrylate, glycidyl (meth) ethyl acrylate, glycidyl (meth). Examples thereof include butyl acrylate and 2-ethylhexyl glycidyl (meth) acrylate. In addition, a hydroxyl group present in the polymer is condensed with 2-acryloyloxyethyl isocyanate, 2-methacryloylethyl isocyanate (“Karenz MOI” manufactured by Showa Denko KK), etc., to provide a similar polymerization crosslinking point. Is also possible.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight. In this case, if the copolymerization ratio is less than 5% by weight, the solubility of the resulting resist composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight, the solubility in an alkaline developer becomes excessive. When developing with an alkali developer, the resist film tends to drop off from the substrate and the image surface tends to become rough. The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 3,000 to 300,000, Preferably it is 5,000-100,000. Further, the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 3,000-60, 000, preferably 5,000 to 25,000. In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition having excellent developability can be obtained, whereby an image pattern having sharp pattern edges can be obtained. In addition to being able to be formed, residues, background stains, film residues and the like are less likely to occur on the unirradiated substrate and the light shielding layer during development. Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably 1 to 5, particularly preferably 1 to 4.

  Examples of the alkali-soluble resin (E) other than the carboxyl group-containing copolymer include novolac resins and resins having a phenolic hydroxyl group such as polyhydroxystyrene. E).

  In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types. The usage-amount of the alkali-soluble resin in this invention is 10-500 weight part normally with respect to 100 weight part of radically polymerizable compounds (B).

[Other photopolymerization initiators]
The energy-sensitive polymerizable composition of the present invention is sufficiently sensitive only with the radical polymerization initiator (A) represented by the general formula (1), and further the improvement of the surface curability of the polymerizable composition and the substrate It can be used in combination with other polymerization initiators for the purpose of improving the adhesiveness.

  Other polymerization initiators that can be used in combination with the energy-sensitive polymerizable composition of the present invention are described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Triazine derivatives, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 And diazonium compounds described in USP 3,567,453, organic azide compounds described in USP 2,848,328, USP 2,852,379 and USP 2,940,853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. JP 37-13109, JP 38-30015, and JP 45-961. Ortho-quinonediazides described in Japanese Patent Publication No. JP-A-55-39162, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977). Various onium compounds including compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, EP-A-109851, EP-A-126712, “Journal of・ Metal allene complexes described in Imaging Science (J.IMAG.SCI.), Volume 30, page 174 (1986), Titanocenes described in JP-A-61-1151197, “Coordination Chemistry Review” (COORDINATION CHEMISTRY REVIEW) ”, Volume 84, Pages 85-277 (1988) A transition metal complex containing a transition metal such as ruthenium described in JP-A-2-302701, an aluminate complex described in JP-A-3-209477, a borate compound described in JP-A-2-157760, 2,4,5-triarylimidazole dimer described in JP-A-55-127550 and JP-A-60-202437, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP 2001-264530 A, JP 2001-261661 A, JP 2000-80068 A, JP 2001-233842 A, USP 3558309 (1971), USP4202697 (1980), Disclosed in JP-T-2004-534797 and JP-A-61-24558 Examples include, but are not limited to, oxime ester compounds.

These polymerization initiators are preferably contained in an amount of 0 to 100 parts by weight or less based on 100 parts by weight of the radical polymerization initiator (A) represented by the general formula (1) of the present invention.

[binder]
The polymerizable composition of the present invention can be used by mixing with a binder such as an organic polymer and applying it to a polymer film such as a glass plate, an aluminum plate, another metal plate, or polyethylene terephthalate.

  Examples of binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, Epoxy resins, alkyd resins, etc., supervised by Kiyoshi Akamatsu, “New Photosensitive Resin Technology” (1987, CMC) and “10308 Chemical Products”, pages 657-767 (1988, Chemical Industries Day) Company) industry known organic polymer described, and the like.

[Additive]
Further, the energy-sensitive polymerizable composition of the present invention is further, depending on the purpose, oxygen removing agent and reducing agent such as phosphine, phosphonate, phosphite, chain transfer catalyst, polymerization accelerator, antifoggant, antifading agent, Antihalation agent, fluorescent brightener, surfactant, colorant, extender, plasticizer, flame retardant, antioxidant, ultraviolet absorber, foaming agent, antifungal agent, thermal polymerization inhibitor, antistatic agent, magnetic You may mix and use the additive which provides a body and other various characteristics.

[solvent]
The energy sensitive ray polymerizable composition of the present invention can be used by adding a solvent for the purpose of improving workability in coating and film formation. The added solvent can be substantially removed by heat drying or vacuum drying after coating. Specific examples of the solvent that can be added to the energy-sensitive polymerizable composition of the present invention include ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-n -Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoe Ether, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

  Ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, ethyl butyrate, isopropyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy Esters such as methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Chill, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methyl propionate, ethyl 2-methoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. Esters;

  Aromatic hydrocarbons such as toluene and xylene, and amides such as N-methylpyrrolidone and N, N-dimethylacetamide can be exemplified.

  These solvents can be used alone or in admixture of two or more.

[Image pattern formation method]
The energy-sensitive polymerizable composition of the present invention is applied to a substrate, used to form an image pattern in which an energy beam is partially exposed and cured, and an unexposed portion is removed with an alkali developer. It can be used as a negative resist. An image pattern forming method using the energy-sensitive polymerizable composition of the present invention will be described. First, after applying the liquid composition of the energy-sensitive polymerizable composition on the surface of the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is partially exposed to a pattern according to the mask through a photomask, then developed using an alkali developer, and the unexposed part of the coating film is dissolved and removed, and then as necessary. The target image pattern can be formed by post baking.

  When the liquid composition of the energy-sensitive polymerizable composition is applied to the substrate, a known coating method such as spray coating, spin coating, slit coating, roll coating or the like can be employed. The coating thickness can be appropriately changed depending on the application, but is usually 0.1 to 200 μm, preferably 0.2 to 100 μm, as the film thickness after drying.

  In addition, the energy-sensitive polymerizable composition layer of the present invention is provided on a base film mainly composed of polyester, polypropylene, polyethylene and the like typified by polyethylene terephthalate, and the energy-sensitive polymerizable composition is formed with a protective film as necessary. It is also possible to use the energy-sensitive polymerizable composition of the present invention in a form called a so-called dry film known in the industry with the layers sandwiched therebetween. The dry film is usually used by laminating the protective film and adhering it to a substrate on which a resist pattern is to be formed, and laminating the substrate on a substrate under heating and pressure conditions as necessary. To do. Pattern exposure in the case of using the energy-sensitive polymerizable composition of the present invention in the form of a dry film may be carried out without peeling off the base film, in which case the base film is removed after exposure. Execute alkali development.

  In the polymerization reaction, the energy-sensitive polymerizable composition of the present invention can be polymerized by applying energy such as ultraviolet rays, visible rays, near infrared rays, electron beams, etc., to obtain a desired polymer. The definitions of ultraviolet rays, near-ultraviolet rays, visible light, near-infrared rays, infrared rays, and the like referred to in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Accordingly, the energy-sensitive polymerizable composition of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a pulsed emission xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon lamp. Various lasers such as ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser A target polymer or cured product can be obtained by applying energy by a light source.

Therefore, in the image pattern forming method of the present invention, it is possible to use energy rays from the light source during exposure. In particular, energy rays having a wavelength in the range of 190 to 450 nm are preferable. The amount of exposure depends on the film thickness and cannot be determined uniquely, but is usually 0.5 to 100,000 J / m ² .

  Examples of the base material used in the image pattern forming method of the present invention include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, glass epoxy film or substrate, but are not limited thereto. Is not to be done. In addition, these base materials may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  As a developing method used in the image pattern forming method of the present invention, for example, any of a liquid filling method, a dipping method, a shower method, a spray method and the like may be used, and the developing time is 20 to 30 ° C., preferably 5 to 300 seconds. Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like. Secondary amines such as di-n-propylamine, tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine, tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine, pyrrole , Piperidine, N-methylpiperidine, N-methylpyrrolidine, tertiary amines such as 30-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene Tetramethylammonium Rokishido, aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetraethylammonium hydroxide can be used. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited only to the following. First, the acrylic resin solution used for the Example and the comparative example is demonstrated. This acrylic resin solution corresponds to the alkali-soluble resin (F) of the present invention.

(Preparation of acrylic resin solution (1))
Add 800 parts by weight of cyclohexanone to the reaction solution, heat to 100 ° C. while injecting nitrogen gas into the container, and drop the mixture of the following monomers and thermal polymerization initiator at the same temperature over 1 hour to conduct the polymerization reaction. It was.
Styrene 60.0 parts by weight Methacrylic acid 60.0 parts by weight Methyl methacrylate 65.0 parts by weight Butyl methacrylate 65.0 parts by weight Azobisisobutyronitrile 10.0 parts by weight After dropping, the reaction was further carried out at 100 ° C. for 3 hours. Then, 2.0 parts by weight of azobisisobutyronitrile dissolved in 50.0 parts by weight of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour, so that the weight average molecular weight was about 40,000. An acrylic resin solution was obtained. After cooling to room temperature, sample about 2 g of the resin solution, heat dry at 300 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. Thus, an acrylic resin solution (1) was prepared.

(Preparation of acrylic resin solution (2))
After adding the following solvent, monomer and thermal polymerization initiator to the reaction vessel, and then substituting with nitrogen, the temperature of the solution was raised to about 70 ° C. while gently stirring, and the temperature was maintained for 5 hours for polymerization. Reaction was performed.
2,2'-azobis (2,4-dimethylvaleronitrile) 5 parts by weight diethylene glycol methyl ethyl ether 200 parts by weight Methacrylic acid 20 parts by weight Glycidyl methacrylate 45 parts by weight Styrene 10 parts by weight cyclohexyl methacrylate 25 parts by weight An acrylic resin solution having a weight average molecular weight of about 22,000 was obtained. After cooling to room temperature, sample about 2 g of the resin solution, dry under reduced pressure at 70 ° C., measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. An acrylic resin solution (2) was prepared.

  The radical polymerization initiators and sensitizers used in Examples and Comparative Examples of the present invention are shown in the following Table (1).

[Examples 1 to 13 and Comparative Examples 1 to 4]
100 parts by weight of dipentaerythritol pentaacrylate (Sartomer, SR399) as the radical polymerizable compound (B), 500 parts by weight of the acrylic resin solution (1) as the alkali-soluble resin (E), 400 parts by weight of cyclohexanone as the solvent, As the chain transfer agent (C), 0 or 6 parts by weight of trimethylolpropane tristhiopropionate, the radical polymerization initiator (A), and the materials shown in Table (2) as sensitizers are shown in the same table. Only the indicated weight was added and mixed to prepare a uniform polymerizable composition solution.

The polymerizable composition solution is filtered through a 0.2 μm pore size disk filter, coated on a stainless steel plate (# 600 polishing) using a spin coater, and heated and dried in an oven at 80 ° C. for 3 minutes. The solvent was removed. After drying, the film thickness of the polymerizable composition formed on the stainless steel plate was 2 μm. The polymerizable composition film is irradiated with light (9 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm, and the IR spectrum of the polymerizable composition film Was measured, and the consumption rate of the acrylic group after 30 seconds of light irradiation was calculated from the change in the absorption intensity at 810 cm ⁻¹ , which is the characteristic absorption of the acrylic group. The results are shown in Table (2).

  When the radical polymerization initiator (A) and the chain transfer agent (C) represented by the general formula (1) of the present invention are used in combination, the sensitivity is higher than when each is used alone. It can be seen that there is an improvement (Examples 3, 6, 7 and Comparative Examples 2 to 5). Furthermore, sufficient sensitivity is not obtained when the cation of the radical polymerization initiator (A) is not a sulfonium cation but an ammonium cation (Comparative Example 1). Further, when the polymerizable composition before light irradiation formed on the stainless steel plate of Example 1 to Example 13 was immersed in an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.2% by weight at 20 ° C. for about 1 minute, an appropriate amount was obtained. It was confirmed that the polymerizable composition of the present invention was developed with respect to an alkaline developer.

[Examples 14 to 26 and Comparative Examples 6 to 8]
100 parts by weight of dipentaerythritol pentaacrylate (Sartomer, SR399) as the radical polymerizable compound (B), 500 parts by weight of the acrylic resin solution (2) as the alkali-soluble resin (E), and propylene glycol monomethyl ether acetate as the solvent 200 parts by weight, as chain transfer agent (C), 0 parts by weight or 6 parts by weight of trimethylolpropane tristhiopropionate, radical polymerization initiator (A), and materials shown in Table (3) as sensitizers Were added in the weights listed in the table, and mixed to prepare a uniform polymerizable composition solution.

  The polymerizable composition solution is filtered through a 0.2 μm pore size disk filter, coated on a 1 mm thick glass plate using a spin coater, and heated and dried in an oven at 80 ° C. for 3 minutes to remove the solvent. Removed. After drying, the film thickness of the polymerizable composition formed on the glass plate was 5 μm. This polymerizable composition film was exposed using a JASCO Corp. SS-25CP type spectral irradiator by changing the irradiation energy amount of the high-pressure mercury lamp (that is, irradiation time) in 13 stages, The development was carried out with a 1% aqueous sodium carbonate solution at 20 ° C. for 1 minute, and the minimum amount of energy required to insolubilize the polymerizable composition at an irradiation wavelength of 365 nm was defined as sensitivity, and the results are shown in Table (3). .

  When the radical polymerization initiator (A) represented by the general formula (1) of the present invention is used in combination with the chain transfer agent (C), it is compared with the case where the chain transfer agent (C) is not used together. It can be seen that the sensitivity is improved (Examples 16, 19, 20 and Comparative Examples 6 to 8).

[Examples 26 to 38 and Comparative Examples 9 to 11]
The polymerizable composition film on the glass substrate prepared in Examples 14 to 26 and Comparative Examples 6 to 8 was exposed to 365 nm with an exposure gap of about 100 μm using a predetermined pattern mask (20 μm × 20 μm resolution). Light from a high-pressure mercury lamp with an energy of 10 mW / cm ² was irradiated for 15 seconds. Thereafter, development was performed at room temperature for 60 seconds with a 0.2% by weight tetramethylammonium hydroxide aqueous solution to remove unexposed portions, and after washing with pure water, the resulting cured product was placed in an oven at 230 ° C. Heated for 30 minutes. The pattern shape obtained on the glass substrate was evaluated by the following method. The results are shown in Table (4).

(Pattern shape)
The pattern shape obtained on the glass substrate was evaluated by a) the linearity of the pattern and b) the cross-sectional shape of the pattern.
About a), it observed and evaluated with the optical microscope. The rank of evaluation is as follows.
○: Good linearity Δ: Partially good linearity ×: Poor linearity b) was evaluated by observing with a scanning electron microscope (SEM). The rank of evaluation is as follows.
○: Forward tapered shape △: Non-tapered shape ×: Reverse tapered shape

  When the radical polymerization initiator (A) and chain transfer agent (C) represented by the general formula (1) of the present invention are used in combination, the linearity and cross-sectional shape of the pattern shape obtained on the glass substrate Both were good (Example 26 to Example 38), but when the chain transfer agent (C) was not used together (Comparative Examples 9 to 11), either the linearity of the pattern shape or the cross-sectional shape However, it was not possible to obtain anything that was all good.

[Example 39 to Example 51 and Comparative Example 12 to Comparative Example 14]
After performing the PCT (pressure cooker) test on the pattern-formed substrates prepared in Example 26 to Example 38 and Comparative Example 9 to Comparative Example 11 under the conditions of 121 ° C., 100% RH, 2 atm, 24 hours, A cellophane tape was affixed to the 20 μm pattern portion and a peeling test was performed to evaluate pattern adhesion. The results are shown in Table (5).
The rank of evaluation is as follows.
○: No peeling of the 20 μm pattern is observed X: No peeling of the 20 μm pattern is recognized

  When the radical polymerization initiator (A) represented by the general formula (1) of the present invention and the chain transfer agent (C) are used in combination, the adhesion of the pattern obtained on the glass substrate to the substrate is good. In contrast, when the chain transfer agent (C) was not used together (Comparative Examples 12 to 14), sufficient adhesion of the pattern to the substrate was obtained. There wasn't.

  The present invention relates to a high-sensitivity polymerizable composition, a negative resist using the same, and an image pattern forming method using the same, for example, a spacer for liquid crystal display, MVA (multiple divided vertical alignment) system Ribs, solder resists, circuit board creation resists, semiconductor photoresists, microelectronics resists, hologram materials, various devices, etc. used in various fields, etc. It can be a material and technique for obtaining.

Claims (8)

An energy-sensitive polymerizable composition comprising a radical polymerization initiator (A) represented by the following general formula (1), a radical polymerizable compound (B), and a chain transfer agent (C).
General formula (1)

(In the formula, R ₁ , R ₂ and R ₃ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. , An alkynyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. A group selected from an arylthio group which may be substituted, and an amino group which may have a substituent,
R ₄ , R ₅ , R ₆ and R ₇ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, a substituted group The group selected from the alkynyl group which may have a group is shown.
However, R ₁ , R ₂ and R ₃ may be a cyclic structure in which two or more groups are bonded, and two or more of R ₁ , R ₂ and R ₃ have a substituent at the same time. Is not a good aryl group,
R ₄ , R ₅ , R ₆ and R _{7 do not} all become an aryl group which may have a substituent at the same time. )
The energy-sensitive polymerizable composition according to claim 1, wherein the chain transfer agent (C) is a compound having a thiol group.
The energy-sensitive ray-polymerizable composition according to any one of claims 1 to 3, wherein the radical polymerization initiator (A) is a compound represented by the general formula (2).
General formula (2)

(In the formula, Ar represents a monocyclic or condensed polycyclic aryl group which may have a substituent having 4 to 30 carbon atoms and may contain a hetero atom,
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently the same as those in general formula (1).
However, Ar, R ₁₁ , R ₁₂ , R ₂ and R ₃ may have a cyclic structure in which two or more groups are bonded. )
The energy-sensitive polymerizable composition according to any one of claims 1 to 3, further comprising a sensitizer (D).
The energy-sensitive polymerizable composition according to any one of claims 1 to 4, further comprising an alkali-soluble resin (E).
A negative resist comprising the energy-sensitive polymerizable composition according to claim 5.
A method for producing an image pattern, comprising: laminating the negative resist according to claim 6 on a substrate, partially irradiating and curing an energy ray, and removing an unirradiated portion with an alkali developer.
An image pattern produced by the method for producing an image pattern according to claim 7.