JP2009203299A - Non-yellowing polymerizable composition and method for producing polymerized material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-yellowing polymerizable composition inhibiting discoloration, and the oozing out and volatilization of a photopolymerization initiator. <P>SOLUTION: This non-yellowing polymerizable composition comprises a photopolymerization initiator of the figure [wherein, in R<SP>1</SP>to R<SP>8</SP>, only one of them is a (meth)acrylic group] and a radically polymerizable compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a non-yellowing polymerizable composition containing a thioxanthone derivative that can be suitably used as a photopolymerization initiator, and a method for producing the polymer. More specifically, the present invention relates to a material and a method that can be polymerized in a short time and reliably by using the non-yellowing polymerizable composition of the present invention to obtain a polymer having good physical properties. Cast resin, stereolithography resin, sealant, dental polymerization resin, printing ink, inkjet ink, paint, printing plate photosensitive resin, printing color proof, color filter resist, black matrix resist, liquid crystal Photo spacers, rear projection screen materials, optical fibers, plasma display ribs, dry film resists, printed circuit board resists, solder resists, semiconductor photoresists, microelectronics resists, micromachine component resists, etching resists, micros Lens array Materials, hologram materials, optical switches, waveguide materials, overcoat agents, powder coatings, adhesives, adhesives, release agents, optical recording media, adhesives, release coating agents, and image recording using microcapsules The present invention relates to a composition for materials, a non-yellowing polymerizable composition for obtaining a polymer having good physical properties in the fields of various devices, and a method for producing a polymer using the polymerizable composition.

  A photopolymerization initiator is used to cure a polymerizable composition containing acrylate or the like by irradiation with UV light, and a sensitizer is used to obtain a highly hard film in a shorter time. Yes. These photopolymerization initiators and sensitizers are used in a wide range of fields, and commercially available photopolymerization initiators and sensitizers are described in “Photopolymer List”, pages 55 to 72, 1996. Year (Bunshin Publishing), “Latest UV Curing Handbook”, 1-50 pages, 2005 (Technical Information Association), etc.

  Thioxanthone derivatives are widely known as conventional photopolymerization initiators. The thioxanthone derivative is sometimes referred to as a sensitizer because a synergistic effect is observed in curability when used in combination with other photopolymerization initiators. Among thioxanthone derivatives, particularly, 2-chlorothioxanthone, 2- (or 4-) isopropylthioxanthone, 2,4-diethylthioxanthone, and the like can be used to obtain a polymerizable composition having high curability. Derivatives are used in polymerizable compositions in various fields. In order to further improve the curability of these thioxanthone derivatives, novel thioxanthone derivatives have been proposed (Patent Documents 1 to 3). On the other hand, in order to improve the curability of the polymerizable composition, Patent Document 3 discloses a combination of a thioxanthone derivative and an α-aminoketone photopolymerization initiator or an acylphosphine oxide photopolymerization initiator, and Patent Document 4 discloses a thioxanthone derivative. And oxime ester photoinitiators were proposed.

  Furthermore, in order to improve the compatibility with the polymerizable composition, a monomer-type thioxanthone derivative in which the photopolymerization initiator itself is given a function as a monomer has also been proposed (Patent Document 5). However, the thioxanthone derivative described in Patent Document 5 has a low ability as a photopolymerization initiator because of a urethane bond in the structure thereof, and the proportion contained in the polymerizable composition is very high.

  In the polymerizable composition using the photopolymerization initiator of the above prior art, coloring such as yellowing caused by the photopolymerization initiator after curing of the polymerizable composition is a problem. The problem of coloring due to the photopolymerization initiator derived after curing of the polymerizable composition is not preferable because it impairs the color tone of the polymerizable composition, and may further limit the applications that can be used. There is a need for improvement. Furthermore, in the above-described polymerizable composition of the prior art, the photopolymerization initiator and other compositions bleed or volatilize from the cured polymerizable composition, which is a major problem in recent years. . The problem of seepage and volatilization of the photopolymerization initiator that occurs from the polymerizable composition cured after light irradiation not only damages the coating material but also the environment of the coating site, and further degrades the performance of the coating material. Because of this, improvement is needed. Then, the photoinitiator which aimed at the oozing out and the improvement of volatilization of the photoinitiator after polymeric composition hardening was also proposed (patent documents 6-10).

  In the polymerizable composition using these photopolymerization initiators, the bleeding and volatilization of the photopolymerization initiator that occurs from the cured polymerizable composition can be suppressed as compared with conventionally known photopolymerization initiators. Therefore, further suppression is desired. In addition, in the polymerizable composition using these photopolymerization initiators, there is a problem of insufficient curability of the polymerizable composition other than the bleeding and volatilization of the photopolymerization initiator. The problem of insufficient curability of the product is that it becomes difficult to obtain a film with a high hardness in a short time with the polymerizable composition, and some improvement can be achieved by increasing the amount of photopolymerization initiator added. Although possible, it is often difficult to obtain desired physical properties of the polymerizable composition, and thus further improvement in curability is desired. In addition, these polymerizable compositions have not been improved with respect to coloring problems such as yellowing due to the photopolymerization initiator derived after curing of the polymerizable composition.

JP 58-32602 A JP 59-208541 A JP-A-61-34057 JP-A-60-166306 JP-A-4-26687 Japanese Patent Laid-Open No. 8-151404 WO 97/49664 Pamphlet JP 2004-224993 A JP-T-2005-512973 JP 2006-28514 A

  The polymerizable composition containing these conventionally known photopolymerization initiators can be used in various applications. However, from the viewpoint of cost reduction and productivity improvement, a material that can be cured with a small addition amount and a small light irradiation energy, that is, a highly sensitive material is required. On the other hand, in these polymerizable compositions, the photopolymerization initiator exudation or volatilization that occurs from the polymerizable composition after curing may damage the environment of the coated product or the coating site, or deteriorate the performance of the coated product. In this case, improvement is required. In addition, since problems such as yellowing after curing of the polymerizable composition have not yet been solved, it is necessary to suppress coloring as much as possible. In the polymerizable composition, it is difficult to satisfy all the requirements regarding curability, oozing and volatilization of the photopolymerization initiator that occurs from the polymerizable composition, and coloring that occurs after the polymerizable composition is cured. No polymerizable composition has been found that satisfies the requirements regarding the coloration that occurs after curing of the polymerizable composition. Accordingly, an object of the present invention is to provide a polymerizable composition that satisfies all of these requirements.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention. That is, the present invention relates to a non-yellowing polymerizable composition comprising a photopolymerization initiator (A) represented by the following general formula (1) and a radical polymerizable compound (B).

（式中、Ｒ¹〜Ｒ⁸は、それぞれ独立に、水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアルコキシル基、置換もしくは未置換のアリール基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換の複素環基、置換もしくは未置換の複素環オキシ基、置換もしくは未置換のアルケニル基、置換もしくは未置換のアルコキシカルボニル基、または置換もしくは未置換のアシル基、または下記一般式（２）で表される基を表す。但し、Ｒ¹〜Ｒ⁸において、一つのみが下記一般式（２）で表される基である。また、Ｒ¹〜Ｒ⁸において一般式（２）で表される基以外の置換基が隣り合う置換基同士で環を形成してもよい。） General formula (1)

Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted acyl group, or the following general formula 2 represents a group represented by (2), provided that only one of R ^{1 to} R ⁸ is a group represented by the following general formula (2), and R ^{1 to} R ⁸ represents a general formula (2 ) A substituent other than the group represented by) may form a ring with adjacent substituents.

General formula (2)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group.)

  Furthermore, this invention relates to the said non-yellowing polymerizable composition which further contains resin (C).

  Furthermore, the present invention relates to the above non-yellowing polymerizable composition further comprising a cleavage type photopolymerization initiator (D).

  Further, the present invention provides the above non-yellowing polymerizable composition, wherein the cleavage type photopolymerization initiator (D) is an α-aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or an oxime ester photopolymerization initiator. Related to things.

  Furthermore, this invention relates to the said non-yellowing polymerizable composition whose (alpha) -amino ketone photoinitiator is following General formula (3).

General formula (3)

(Wherein R ¹⁰ and R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group.
R ¹¹ and R ¹² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group. R ¹¹ and R ¹² may be combined to form a ring.
R ¹⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, substituted or Unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted alkylthio group, Substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted Diarylamino group, substituted or unsubstituted alkylaryl group It represents a cyano group or a halogen atom.
Ar ¹ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. )

  Furthermore, this invention relates to the said non-yellowing polymerizable composition whose acylphosphine oxide type photoinitiator is following General formula (4).

General formula (4)

(In the formula, R ¹⁵ and R ¹⁶ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
R ¹⁷ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group. )

  Furthermore, this invention relates to the said non-yellowing polymerizable composition whose oxime ester photoinitiator is following General formula (5).

General formula (5)

Wherein R ¹⁸ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl Group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted Alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted arylamino group, substituted Or an unsubstituted diarylamino group, a substituted or unsubstituted alkyl group It represents a Ruamino group or a halogen atom.
R ¹⁹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or —CO—Ar ³ .
Ar ² represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.
Ar ³ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
R ²⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
X represents a direct bond or —CO—. )

  Furthermore, the present invention relates to a method for producing a polymer obtained by polymerizing the non-yellowing polymerizable composition by light irradiation.

  The non-yellowing polymerizable composition of the present invention uses a thioxanthone derivative having a specific structure in which at least one carbonyloxy group having a radically polymerizable functional group is introduced as a photopolymerization initiator, thereby allowing a conventionally known polymerization. Compared with the polymerizable composition, the polymerizable composition can be reliably cured in a short time, and the photopolymerization initiator oozes and volatilizes from the polymerizable composition after curing, and occurs after the polymerizable composition is cured. Coloring can be suppressed, and as a result, it is possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions.

  Hereinafter, embodiments of the present invention will be described in detail.

  The non-yellowing polymerizable composition of the present invention represents a polymerizable composition capable of remarkably suppressing coloring that occurs after curing of the polymerizable composition, as compared with a conventionally known polymerizable composition.

  First, the photoinitiator (A) contained in the non-yellowing polymerizable composition of the present invention will be described. The photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1). By having this structure, it functions as a highly sensitive material for light irradiation.

General formula (1)

Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted acyl group, or the following general formula 2 represents a group represented by (2), provided that only one of R ^{1 to} R ⁸ is a group represented by the following general formula (2), and R ^{1 to} R ⁸ represents a general formula (2 ) A substituent other than the group represented by) may form a ring with adjacent substituents.

General formula (2)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group.)

  As shown in the general formula (1), the photopolymerization initiator (A) of the present invention can introduce various substituents as long as the properties are not impaired. By introducing a substituent, the photopolymerization initiator (A) of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as the maximum absorption wavelength and transmittance, and the solubility in monomers, resins and solvents used together. .

Here, the substituted or unsubstituted alkyl group in R ^{1 to} R ⁸ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —CH ₂ —O—CH ₃ and —CH ₂ —CH. _2— O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n1 —CH ₃ (where n1 is 1 to 8) ), — (CH ₂ —CH ₂ —CH ₂ —O) _m1 —CH ₃ (where m1 is an integer of 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH. Examples include _2- CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _2, but are not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following, but are not limited thereto. It is not a thing.

The substituted or unsubstituted alkoxyl group in R ^{1 to} R ⁸ is a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or one having 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkoxyl groups interrupted by the above -O-. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n2 -CH 3 (Where n2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m2 —CH ₃ (where m2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted with one or more —O— include the following, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryl group in R ^{1 to} R ⁸ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples include a phenyl group, a 1-naphthyl group, and 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, 1-acenaphthyl group Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p -Cumenyl group, p-dodecylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3, -Dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, Examples thereof include, but are not limited to, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

Examples of the substituted or unsubstituted aryloxy group in R ^{1 to} R ⁸ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy 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 and the like, but are not limited thereto. In addition, the aryl group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{1 to} R ⁸ of the present invention.

Examples of the substituted or unsubstituted heterocyclic group in R ^{1 to} R ⁸ include an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, 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, Quinolyl group, 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, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthrin Group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl group, 11,3-benzodioxol-5-yl group, 1,4-benzo Although a dioxane-6-yl group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ^{1 to} R ⁸ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 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 can be mentioned, but are not limited thereto. Further, the heterocyclic group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{1 to} R ⁸ of the present invention.

Examples of the substituted or unsubstituted alkenyl group in R ^{1 to} R ⁸ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 2 to 18 carbon atoms, and these include a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples include 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, but are not limited thereto.

Examples of the substituted or unsubstituted alkoxycarbonyl group in R ^{1 to} R ⁸ include an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanyl Phenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, Rophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyl An oxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. are mentioned. In addition, the aryl group and the —OCO— bond may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{1 to} R ⁸ of the present invention.

Examples of the substituted or unsubstituted acyl group in R ^{1 to} R ⁸ include a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, carbon A monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom to which a monocyclic or condensed polycyclic aryl group of 6 to 18 is bonded. Examples include a bonded carbonyl group, and specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentyl Carbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotono Group, oleoyl group, cinnamoyl group benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group and the like. However, it is not limited to these. In addition, the aryl group and the carbonyl group, the heterocyclic group and the carbonyl group may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{1 to} R ⁸ of the present invention. .

Moreover, in R < ¹ > -R < ⁸ >, substituents other than group represented by General formula (2) may form a ring with adjacent substituents.

R ^{1 to} R ⁸ described above may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a carboxyl group, a sulfone group, a sulfonyl chloride group, an amide group, and a cyano group. Nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkyl Amino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzylamino group, dibenzylamino group, alkylsilyl group, alkoxysilyl group and the like 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 a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms and interrupted by one or more —O—. , Branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n1 —CH ₃ (where n1 is 1) 8 of an _{integer), - (CH 2 -CH 2} -CH 2 -O) m1 -CH 3 ( wherein m1 is an integer of 1 to _{5), - CH 2 -CH (CH} 3) -O _{-CH 2 -CH 3 -, - CH} 2 -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, Examples include 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 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 can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

Examples of the alkoxyl group include a straight chain, branched chain, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or a group having 2 to 18 carbon atoms and interrupted by one or more —O—. Examples thereof include a chain, branched chain, monocyclic or condensed polycyclic alkoxyl group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n2 -CH 3 (Where n2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m2 —CH ₃ (where m2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. It is done.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and 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 monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, an ethyldimethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, and a trioctylsilyl group.

  Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Can be mentioned.

  Specific examples of particularly preferred photopolymerization initiators (A) described above are shown below, but the structure of the photopolymerization initiator of the present invention is not limited thereto.

  Next, the cleavage type photopolymerization initiator (D) will be described. Examples of the cleavage type photopolymerization initiator (D) used in the present invention include Irgacure 127, Irgacure 149, Irgacure 184, Irgacure 261, Irgacure 369, Irgacure 379, Irgacure 500, and Irgacure 651. , Irgacure 754, Irgacure 784, Irgacure 819, Irgacure 907, Irgacure 1000, Darocur 1173, Irgacure 1700, Irgacure 1800, Irgacure 1870, Irgacure 2959, Irgacure OXE-01 (CGI124), CGI242 , Darocur TPO, Darocur 4265 (Ciba Specialty Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Den) ), Esacure 1001M, Esacure KIP150, EsacureONE (Lamberti), organic peroxides described in JP-A Nos. 59-1504 and 61-243807, JP-A Nos. 55-127550 and 60 2,4,5-triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-bi described in JP-A No. 202437 Imidazole, JP 2001-264530 A, JP 2001-261661 A, JP 2000-80068 A, JP 2001-233842 A, USP 3558309 (1971), USP4202697 (1980) ), Japanese Patent Laid-Open No. 61-24558, Special Table 2 No. 04-534797, JP-A 2004-359639, oxime ester photopolymerization initiators, JP-A-5-86080, JP-A-5-345790, JP-A-7-278167, and JP 7-278215, an acylphosphine oxide photopolymerization initiator, JP-A-54-99185, JP-A-58-157805, JP-A-59-167546, JP-A-60-84248 Α-aminoketone photopolymerization initiators described in JP-A-61-261104, JP-A-63-264560, and JP-A-2006-206799, and bifunctionals described in JP-T-2002-530372. Photopolymerization initiators, trifunctional photoinitiators described in JP-T-2006-525399, and the like. The present invention is not limited to, et al.

  Among the cleavage type photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime ester photopolymerization initiators are preferably used, and more preferably α-aminoketone. As the photopolymerization initiator, a cleavage type photopolymerization initiator represented by the general formula (3), and as the acylphosphinoxide photopolymerization initiator, a cleavage type photopolymerization initiator represented by the general formula (4). The oxime ester photopolymerization initiator is a cleavage type photopolymerization initiator represented by the general formula (5).

  Next, the α-aminoketone photopolymerization initiator represented by the general formula (3) will be described. As shown in the general formula (3), various substituents can be introduced as long as the characteristics are not impaired. By introducing the substituents, absorption characteristics of energy rays such as absorption maximum wavelength and transmittance are obtained. The solubility in the monomer, resin or solvent used in combination can be appropriately adjusted.

R ¹⁰ and R ¹³ in the general formula (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group.

The substituted or unsubstituted alkyl group for R ^{10 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group in R ^{10 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

The substituted or unsubstituted alkenyl group for R ¹⁰ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ in formula (1).

R ¹¹ and R ¹² in the general formula (3) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group.

The substituted or unsubstituted alkyl group in R ¹¹ and R ¹² has the same meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group in R ¹¹ and R ¹² has the same meaning as the substituted or unsubstituted aryl group described for R ¹ in the general formula (1).

The substituted or unsubstituted alkenyl group in R ¹¹ and R ¹² has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ in formula (1).

R ¹¹ and R ¹² may be combined to form a ring.

When R ¹¹ and R ¹² are combined to form a ring, the formed sites are morpholine ring, thiomorpholine ring, thiazolidine ring, piperazine ring, homopiperazine ring, propyleneimine ring, pyrrolidine ring, piperidine ring Examples thereof include, but are not limited to, forming a pipecoline ring and the like.

R ¹⁴ in the general formula (3) is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted arylamino group Substituted or unsubstituted diarylamino group, substituted or unsubstituted Alkyl arylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group for R ^{14 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group for R ^{14 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic group for R ^{14 has the same} meaning as the substituted or unsubstituted heterocyclic group described for R ¹ in formula (1).

The substituted or unsubstituted alkenyl group for R ¹⁴ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ in formula (1).

The substituted or unsubstituted acyl group for R ¹⁴ has the same meaning as the substituted or unsubstituted acyl group described for R ¹ in formula (1).

The substituted or unsubstituted alkoxyl group in R ¹⁴ has the same meaning as the substituted or unsubstituted alkoxyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryloxy group for R ^{14 has the same} meaning as the substituted or unsubstituted aryloxy group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic oxy group for R ^{14 has the same} meaning as the substituted or unsubstituted heterocyclic oxy group described for R ¹ in formula (1).

As the substituted or unsubstituted acyloxy group for R ¹⁴ , a hydrogen atom, a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or carbon A carbonyloxy group to which a monocyclic or condensed aryl group of 6 to 18 is bonded, or a monocyclic or condensed polycyclic heterocyclic group of 4 to 18 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group. , Palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, Rohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyl Examples thereof include, but are not limited to, an oxy group, a 3-furoyloxy group, a 2-thenoyloxy group, a nicotinoyloxy group, an isonicotinoyloxy group, a 9-anthroyloxy group, and a 5-naphthacenoyloxy group. It is not something. In addition, the aryl group and the carbonyloxy group, the heterocyclic group and the carbonyloxy group may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ¹⁴ of the present invention.

Examples of the substituted or unsubstituted alkoxycarbonyl group for R ¹⁴ include an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and a hexyloxy group. Carbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl Group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyl Nyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy A carbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. are mentioned. Further, the aryl group and the —OCO— bond may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ¹⁴ of the present invention.

Examples of the substituted or unsubstituted alkylthio group in R ¹⁴ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group and an ethylthio group. Propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group, and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylthio group for R ¹⁴ include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, 9 -Anthrylthio group, 9-phenanthrylthio group and the like can be mentioned, but are not limited thereto. The aryl group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ¹⁴ of the present invention.

Examples of the substituted or unsubstituted heterocyclic thio group in R ¹⁴ include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 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 -A carbazolylthio group etc. can be mentioned, However, It is not limited to these. Moreover, the heterocyclic group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ¹⁴ of the present invention.

Examples of the substituted or unsubstituted alkylamino group for R ¹⁴ include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group. Group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octyl Amino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamanta Amino group, and the like can be mentioned 2-Adamantamino group, but is not limited thereto.

Examples of the substituted or unsubstituted dialkylamino group in R ¹⁴ include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, Didecylamino group, didodecylamino group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino Groups, pyrrolidino groups, piperidino groups, piperazino groups, and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylamino group for R ¹⁴ include an N-arylamino group, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group, indolino group, etc. However, it is not limited to these.

Examples of the substituted or unsubstituted diarylamino group in R ¹⁴ include a diarylamino group, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group. However, it is not limited to these.

Examples of the substituted or unsubstituted alkylarylamino group for R ¹⁴ include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, Examples thereof include, but are not limited to, an N-pentylanilino group, an N-ethylanilino group, and an N-methyl-1-naphthylamino group.

Examples of the halogen atom in R ¹⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Ar ¹ in the general formula (3) is a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.

The substituted or unsubstituted arylene group in Ar ¹ is a divalent group formed by removing one hydrogen atom from the same substituent as the substituted or unsubstituted aryl group described for R ¹ in the general formula (1). However, it is not limited to these.
As the substituted or unsubstituted divalent heterocyclic group in Ar ^1, one hydrogen atom is removed from the same substituent as the substituted or unsubstituted heterocyclic group described in R ¹ of the general formula (1). Although the divalent group which can be mentioned can be mentioned, it is not limited to these.

R ^{10 to} R ¹⁴ and Ar ¹ described above may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a carboxyl group, a sulfone group, a sulfonyl chloride group, and an amide group. , Cyano group, nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino Group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzylamino group, dibenzylamino group, alkylsilyl group, alkoxysilyl group and the like.

  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 a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms and interrupted by one or more —O—. , Branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n1 —CH ₃ (where n1 is 1) 8 of an _{integer), - (CH 2 -CH 2} -CH 2 -O) m1 -CH 3 ( wherein m1 is an integer of 1 to _{5), - CH 2 -CH (CH} 3) -O _{-CH 2 -CH 3 -, - CH} 2 -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, Examples include 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 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 can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

Examples of the alkoxyl group include a straight chain, branched chain, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or a group having 2 to 18 carbon atoms and interrupted by one or more —O—. Examples thereof include a chain, branched chain, monocyclic or condensed polycyclic alkoxyl group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n2 -CH 3 (Where n2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m2 —CH ₃ (where m2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. It is done.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and 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 monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, an ethyldimethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, and a trioctylsilyl group.

  Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Can be mentioned.

  Particularly preferred specific examples of the α-aminoketone photopolymerization initiator which is the cleavage type photopolymerization initiator (D) described above are shown below, but the structure of the photopolymerization initiator of the present invention is limited thereto. is not.

  Next, the acylphosphine oxide photopolymerization initiator represented by the general formula (4) will be described. As shown in the general formula (4), various substituents can be introduced as long as the characteristics are not hindered. By introducing the substituents, absorption characteristics of energy rays such as absorption maximum wavelength and transmittance The solubility in the monomer, resin or solvent used in combination can be appropriately adjusted.

R ¹⁵ and R ¹⁶ in the general formula (4) each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

The substituted or unsubstituted alkyl group for R ¹⁵ and R ¹⁶ has the same meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group in R ¹⁵ and R ¹⁶ has the same meaning as the substituted or unsubstituted aryl group described for R ¹ in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ¹⁵ and R ¹⁶ has the same meaning as the substituted or unsubstituted heterocyclic group described in R ¹ of the general formula (1).

R ¹⁷ in the general formula (4) represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group.

The substituted or unsubstituted alkyl group for R ^{17 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group for R ^{17 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic group for R ^{17 has the same} meaning as the substituted or unsubstituted heterocyclic group described for R ¹ in formula (1).

The substituted or unsubstituted acyl group for R ¹⁷ has the same meaning as the substituted or unsubstituted acyl group described for R ¹ in formula (1).

R ^{15 to} R ¹⁷ described above may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a carboxyl group, a sulfone group, a sulfonyl chloride group, an amide group, and a cyano group. Nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkyl Amino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzylamino group, dibenzylamino group, alkylsilyl group, alkoxysilyl group and the like 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 a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms and interrupted by one or more —O—. , Branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n1 —CH ₃ (where n1 is 1) 8 of an _{integer), - (CH 2 -CH 2} -CH 2 -O) m1 -CH 3 ( wherein m1 is an integer of 1 to _{5), - CH 2 -CH (CH} 3) -O _{-CH 2 -CH 3 -, - CH} 2 -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, Examples include 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 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 can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

Examples of the alkoxyl group include a straight chain, branched chain, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or a group having 2 to 18 carbon atoms and interrupted by one or more —O—. Examples thereof include a chain, branched chain, monocyclic or condensed polycyclic alkoxyl group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n2 -CH 3 (Where n2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m2 —CH ₃ (where m2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. It is done.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and 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 monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, an ethyldimethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, and a trioctylsilyl group.

  Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Can be mentioned.

  Particularly preferred specific examples of the acylphosphine oxide photopolymerization initiator which is the cleavage type photopolymerization initiator (D) described above are shown below, but the structure of the photopolymerization initiator of the present invention is limited to them. is not.

  Next, the oxime ester photopolymerization initiator represented by the general formula (5) will be described. As shown in the general formula (5), various substituents can be introduced as long as the characteristics are not hindered. By introducing the substituents, absorption characteristics of energy rays such as an absorption maximum wavelength and transmittance are obtained. The solubility in the monomer, resin or solvent used in combination can be appropriately adjusted.

R ¹⁸ in the general formula (5) is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted arylamino group Substituted or unsubstituted diarylamino group, substituted or unsubstituted Alkyl arylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group for R ^{18 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group for R ^{18 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic group for R ^{18 has the same} meaning as the substituted or unsubstituted heterocyclic group described for R ¹ in formula (1).

The substituted or unsubstituted alkenyl group for R ¹⁸ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ in formula (1).

The substituted or unsubstituted acyl group for R ¹⁸ has the same meaning as the substituted or unsubstituted acyl group described for R ¹ in formula (1).

The substituted or unsubstituted alkoxyl group in R ¹⁸ has the same meaning as the substituted or unsubstituted alkoxyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryloxy group for R ^{18 has the same} meaning as the substituted or unsubstituted aryloxy group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic oxy group for R ^{18 has the same} meaning as the substituted or unsubstituted heterocyclic oxy group described for R ¹ in formula (1).

The substituted or unsubstituted acyloxy group for R ¹⁸ has the same meaning as the substituted or unsubstituted acyloxy group described for R ¹⁴ in formula (3).

The substituted or unsubstituted alkoxycarbonyl group for R ^{18 has the same} meaning as the substituted or unsubstituted alkoxycarbonyl group described for R ¹⁴ in formula (3).

The substituted or unsubstituted alkylthio group for R ¹⁸ has the same meaning as the substituted or unsubstituted alkylthio group described for R ¹⁴ in formula (3).

The substituted or unsubstituted arylthio group for R ¹⁸ has the same meaning as the substituted or unsubstituted arylthio group described for R ¹⁴ in formula (3).

The substituted or unsubstituted heterocyclic thio group for R ^{18 has the same} meaning as the substituted or unsubstituted heterocyclic thio group described for R ¹⁴ in formula (3).

The substituted or unsubstituted alkylamino group for R ^{18 has the same} meaning as the substituted or unsubstituted alkylamino group described for R ¹⁴ in formula (3).

The substituted or unsubstituted dialkylamino group in R ¹⁸ has the same meaning as the substituted or unsubstituted dialkylamino group described for R ¹⁴ in formula (3).

The substituted or unsubstituted arylamino group for R ^{18 has the same} meaning as the substituted or unsubstituted arylamino group described for R ¹⁴ in formula (3).

The substituted or unsubstituted diarylamino group in R ¹⁸ has the same meaning as the substituted or unsubstituted diarylamino group described for R ¹⁴ in formula (3).

The substituted or unsubstituted alkylarylamino group for R ^{18 has the same} meaning as the substituted or unsubstituted alkylarylamino group described for R ¹⁴ in formula (3).

The halogen atom for R ¹⁸ has the same meaning as the halogen atom described for R ¹⁴ in formula (3).

R ¹⁹ in the general formula (5) represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or —CO—. Ar ³ .

The substituted or unsubstituted alkyl group for R ^{19 has the same} meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group for R ^{19 has the same} meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic group for R ^{19 has the same} meaning as the substituted or unsubstituted heterocyclic group described for R ¹ in formula (1).

The substituted or unsubstituted alkenyl group for R ¹⁹ has the same meaning as the substituted or unsubstituted alkenyl group described for R ¹ in formula (1).

Ar ² in the general formula (5) is a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.

The substituted or unsubstituted arylene group in Ar ² has the same meaning as the substituted or unsubstituted arylene group described for Ar ¹ in formula (3).

The substituted or unsubstituted divalent heterocyclic group for Ar ² has the same meaning as the substituted or unsubstituted divalent heterocyclic group described for Ar ¹ in formula (3).

Ar ³ in the general formula (5) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

The substituted or unsubstituted aryl group in Ar ³ has the same meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic group in Ar ³ has the same meaning as the substituted or unsubstituted heterocyclic group described for R ¹ in the general formula (1).

R ²⁰ in the general formula (5) is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The substituted or unsubstituted alkyl group in Ar ³ has the same meaning as the substituted or unsubstituted alkyl group described for R ¹ in formula (1).

The substituted or unsubstituted aryl group in Ar ³ has the same meaning as the substituted or unsubstituted aryl group described for R ¹ in formula (1).

  X in the general formula (5) is a direct bond or —CO—.

R ^{18 to} R ²⁰ , Ar ² , and Ar ³ described above may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a carboxyl group, a sulfone group, and a sulfonyl chloride. Group, amide group, cyano group, nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic ring Examples include a thio group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group, an alkylsilyl group, and an alkoxysilyl group.

  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 a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms and interrupted by one or more —O—. , Branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n1 —CH ₃ (where n1 is 1) 8 of an _{integer), - (CH 2 -CH 2} -CH 2 -O) m1 -CH 3 ( wherein m1 is an integer of 1 to _{5), - CH 2 -CH (CH} 3) -O _{-CH 2 -CH 3 -, - CH} 2 -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, Examples include 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 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 can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

Examples of the alkoxyl group include a straight chain, branched chain, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or a group having 2 to 18 carbon atoms and interrupted by one or more —O—. Examples thereof include a chain, branched chain, monocyclic or condensed polycyclic alkoxyl group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—. _{CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n2 -CH 3 (Where n2 is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m2 —CH ₃ (where m2 is an integer from 1 to 5), —O— _{CH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. It is done.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and 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 monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 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 and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, an ethyldimethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, and a trioctylsilyl group.

  Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Can be mentioned.

  As the oxime ester photopolymerization initiator that is the cleavage type photopolymerization initiator (D) described above, particularly preferred specific examples are shown below, but the structure of the photopolymerization initiator of the present invention is not limited thereto. Absent.

  The synthesis method for obtaining the photopolymerization initiator (A) and the cleavage type photopolymerization initiator (D) of the present invention is not particularly limited, and conventionally known chemical reactions, post-treatment methods, purification methods, and analysis methods are appropriately selected. By combining them, it is possible to easily synthesize and confirm the structure.

  A method for synthesizing the photopolymerization initiator (A) is disclosed in JP-A-56-125383, JP-A-58-79991, JP-A-7-10829, European Patent No. 81280, or West German Patent. Examples include the methods described in the specification of No. 2504642, etc., and the photopolymerization initiator (A) of the present invention can be synthesized by appropriately replacing the raw materials used in the synthesis described in these. is there.

  Examples of the synthesis method of the α-aminoketone photopolymerization initiator include the methods described in European Patent Application No. 3002, Japanese Patent Application Laid-Open No. 58-157805, Japanese Patent Application Laid-Open No. 63-264560, and the like. It is possible to synthesize the α-aminoketone photopolymerization initiator of the present invention by appropriately replacing the raw materials used in the synthesis described in 1.

  Examples of the synthesis method of the acylphosphine oxide photopolymerization initiator include the methods described in JP-A-61-130296, JP-A-5-345790, etc., and the raw materials used in the synthesis described in these methods It is possible to synthesize the acylphosphine oxide photopolymerization initiator of the present invention by appropriately replacing.

  Examples of the synthesis method of the oxime ester photopolymerization initiator include the methods described in JP-A Nos. 61-24558, 2000-80068, 2001-264530, and the like. The oxime ester photopolymerization initiator of the present invention can be synthesized by appropriately replacing the raw materials used in the synthesis described.

  Since the non-yellowing polymerizable composition of the present invention uses a thioxanthone derivative into which one carbonyloxy group having a radical polymerizable functional group is introduced as the photopolymerization initiator (A), a conventionally known thioxanthone derivative is used. Compared to the polymerizable composition, the polymerizable composition can be reliably cured in a short time, and the bleeding and volatilization of the photopolymerization initiator generated from the cured polymerizable composition can be suppressed. In particular, coloring after curing of the polymerizable composition can be remarkably suppressed. As a result, it is possible to realize a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. Below, the utilization method of the photoinitiator of this invention is described.

  The composition containing the photopolymerization initiator (A) and the radical polymerizable compound (B) of the present invention is cured quickly and reliably by irradiation with energy rays, particularly light in the wavelength region of 250 nm to 450 nm, and has good characteristics. It can be used as a polymerizable composition capable of obtaining a cured product having the above.

  The radical polymerizable compound (B) used for the non-yellowing polymerizable composition of the present invention will be described. The radically polymerizable compound (B) in the present invention means a compound having at least one skeleton capable of radical polymerization in the molecule. In addition, these have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and normal pressure.

  Examples of such radically polymerizable compounds (B) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, acid amides and acid anhydrides. Further examples include urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, etc., but the present invention is not limited to these. Absent. Specific examples of the radically polymerizable compound (B) in the present invention are given below.

Examples of acrylates:
Examples of monofunctional alkyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, p Nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate EO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecanedi Methylol diacrylate, isocyanuric acid EO-modified diacrylate.

Examples of trifunctional acrylates:
Glycerin PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, isocyanuric acid EO modified triacrylate, isocyanuric acid EO modified ε-caprolactone modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, cresyl polyethylene glycol methacrylate, p- Cycloalkenyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate and the like.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Bisphenol A dimethacrylate, EO-modified bisphenol A dimethacrylate, PO-modified bisphenol A-dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A dimethacrylate, PO-modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO-modified bisphenol F dimethacrylate, PO-modified bisphenol F dimethacrylate, EO-modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate.

Examples of trifunctional methacrylates:
Glycerin PO-modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone etc.

  Said radically polymerizable compound (B) can be easily obtained as a commercial item of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by KK, "Acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd. "NICHIGO-UV purple light urethane acrylate oligomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. "Carboxylic acid vinyl ester monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd. "Function" manufactured by Kojin Co., Ltd. Monomer "series and the like.

  Moreover, the cyclic compound shown below is also mentioned as a radically polymerizable compound (B).

Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, p. 3169 (1979), vinylcyclopropanes, macromolecular chemi. Rapid Communication (Makromol. Chem. Rapid Commun.), Vol. 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed., Vol. 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. ), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 564 (1985) 2,3-di-vinyl oxiranes described.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Volume 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Volume 21, page 373 (1983), 2-methylene-1,3-dioxepane, polymer pre-prints (Polym. Preprints), No. 34, 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), 20, 361 (1982) ), Macromolecular Chemie, Volume 183, 1913 (1982) and Macromolecular Chemie, Volume 186, 1-Methylene-4-phenyl-1,3-dioxepane described in page 1543 (1985), Macromolecules, Vol. 15, page 1711 (1982) 4,7-dimethyl-2- Methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3-diosepan described in Polymer Prepreprints, Vol. 34, 154 (1985).

  Furthermore, the radically polymerizable compound (B) can also include those described in the following literature. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  The radically polymerizable compound (B) of the present invention may be used alone or in a mixture of two or more at any ratio in order to improve desired properties.

  Next, the resin (C) used in the non-yellowing polymerizable composition of the present invention will be described. The resin (C) in the present invention means a resin having no skeleton capable of radical polymerization in the molecule. In addition, these have a liquid or solid chemical form at normal temperature and normal pressure.

  Examples of the resin having no skeleton capable of radical polymerization in the molecule include alkyd resin, polyester resin, polyvinyl chloride, poly (meth) acrylic ester, epoxy resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, cellulose acetate). , Nitrocellulose), vinyl chloride vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, and synthetic rubber such as butadiene-acrylonitrile copolymer. These resins can be used alone or in combination of two or more thereof.

  Furthermore, the non-yellowing polymerizable composition of the present invention is used by adding a carboxyl group-containing polymer (E) shown below for the purpose of using it for image formation as a so-called alkali development type photoresist material. Also good. Since the carboxyl group-containing polymer (E) has solubility in an alkaline aqueous solution, if the film prepared using the non-yellowing polymerizable composition of the present invention is partially cured, the so-called difference in solubility in the alkaline aqueous solution results in so-called It is possible to form a negative resist pattern. Here, the carboxyl group-containing polymer (E) is a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylic acid, and vinyl that can be copolymerized with these. Examples thereof include a copolymer with a monomer. These copolymers may be used alone or in combination of two or more.

  Here, as the acrylic ester, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid-t-butyl, acrylic acid-2-ethylhexyl, etc. C1-C18 alkyl esters of acrylic acid, hydroxyl-containing acrylic esters such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., nitrogen containing dimethylaminoethyl acrylate, diethylaminoethyl acrylate, etc. Acrylic esters, glycidyl acrylate, tetrahydrofurfuryl acrylate, morpholyl acrylate, isobornyl acrylate, cyclohexyl acrylate, and the like can be mentioned, but are not limited thereto. Not to.

  As the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid-t-butyl, methacrylic acid- C1-C18 alkyl esters of methacrylic acid such as 2-ethylhexyl, hydroxyl-containing methacrylic esters such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, dimethyl methacrylate Nitrogen-containing methacrylates such as aminoethyl and diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, morpholyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate It can be mentioned other methacrylic acid esters such as Le, but is not limited thereto.

  (Meth) acrylic acid ester, (meth) acrylic acid and vinyl monomers copolymerizable therewith include tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2, Examples include 2,3,3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

  The photopolymerization initiator (A) of the present invention is preferably used in the range of 0.005 to 50 parts by weight and more preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). Is preferably used. Moreover, 0.1-600 weight part is preferable with respect to 100 weight part of radically polymerizable compounds (B), and, as for resin (C), More preferably, it is 0.1-200 weight part. The cleavage type photopolymerization initiator (D) is preferably used in the range of 0.005 to 50 parts by weight, and more preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). It is preferable to use it. The carboxyl group-containing polymer (E) is preferably used in the range of 20 to 500 parts by weight, more preferably in the range of 50 to 150 parts by weight, with respect to 100 parts by weight of the radical polymerizable compound (B).

  The non-yellowing polymerizable composition of the present invention is mixed with a binder such as an organic polymer in order to enhance the film formability, and is applied to a polymer film such as glass plate, aluminum plate, other metal plate, polyethylene terephthalate or polyethylene. It can be applied and used.

  Further, binders that can be used by mixing with the non-yellowing polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, and polycarbonates. And polymers such as polystyrenes and polyvinyl esters, and copolymers, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, and novolak resin. , Phenolic resin, epoxy resin, alkyd resin, etc., supervised by Kiyoshi Akamatsu, “New Practical Technology of Photosensitive Resin” (CMC, 1987) and “Chemical Products of 10188”, pages 657-767 (Chemical Industry) Hosha include 1988) industry known organic polymer according.

  The non-yellowing polymerizable composition of the present invention can be used by adding a solvent as necessary for the purpose of improving coating suitability including viscosity adjustment. The solvent that can be used by adding to the non-yellowing polymerizable composition of the present invention is not particularly limited, and any solvent can be used as long as it can be uniformly mixed with the non-yellowing polymerizable composition of the present invention. Can also be used. For example, known solvents such as alcohols, ketones, esters, aromatics, hydrocarbons, and halogenated hydrocarbons may be used, but the invention is not limited thereto.

  Further, the non-yellowing polymerizable composition of the present invention has sufficient sensitivity without using other sensitizers, but for the purpose of further improving the sensitivity and improving the film properties after curing, the sensitizers. And other photopolymerization initiators can be used in combination.

  Sensitizers that can be used in combination with the non-yellowing polymerizable composition of the present invention include benzophenone derivatives, unsaturated ketone derivatives typified by chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives Polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenyl polymers, etc. Filin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives , Tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and other specific examples include Okawara Shin et al., “Dye Handbook” (1986, Kodansha), edited by Nobu Okawara et al., "Chemicals of Functional Dye" (1981, CMC), edited by Chusaburo Ikemori et al., "Special Functional Materials" (1986, CMC) Examples include, but are not limited to, dyes and sensitizers that absorb light in the ultraviolet to near-infrared region, and these are optional. Two or more of them may be used in the ratio. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). ) And the like, but are not limited thereto.

  Other polymerization initiators that can be used in combination with the non-yellowing polymerizable composition of the present invention include Irgacure 651, Irgacure 127, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure. 2959, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 754, IRGACURE 784, IRGACURE 261, IRGACURE OXE- 01 (CGI124), CGI242 (Ciba Specialty Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Denka), EsacureKIP , EsacureONE, Esacure1001M (Lamberti), triazine derivatives described in JP-B-59-1281, JP-B-69-1621 and JP-A-60-60104, JP-A-59-1504 and JP Organic peroxides described in Japanese Utility Model Publication No. 61-243807, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604 and US Pat. No. 3,567,453, Japanese Patent Publication No. Organic azide compounds described in USP 2,848,328, USP 2,852,379 and USP 2,940,853, JP-B 36-22062, JP-B 37-13109, JP-B 38-18015, and Published in Japanese Patent Publication No. 45-9610 Ortho-quinonediazides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203, and “MACROMOLECULES”, Vol. 10, page 1307 (1977). Various onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging. Science (J.IMAG.SCI.), Vol. 30, page 174 (1986), metal allene complexes, titanocenes described in JP-A No. 61-151197, “COORDINATION CHEMISTRY” REVIEW), 84, 85-277 (1988) and JP-A-2 Transition metal complexes containing a transition metal such as ruthenium described in Japanese Patent No. 182701, an aluminate complex described in Japanese Patent Application Laid-Open No. 3-209477, a borate compound described in Japanese Patent Application Laid-Open No. 2-157760, and Japanese Patent Application Laid-Open No. 55-127550 2,4,5-triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl described in JP-A-60-202437 -1,1'-biimidazole, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, JP-A-5-213861, JP-A-5-255347, JP-A-5-255421 JP, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, and Japanese Patent Application No. 2004-05. No. 009, and the sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-263413, JP-A No. 2001-264530, JP-A No. 2001-261661, JP-A No. 2000-80068, JP-A No. 2001-233842. Oxime esters described in US Pat. No. 3,558,309 (1971), US Pat. No. 4,202,697 (1980), JP-A-61-2558, JP-T 2004-534797, and JP-A-2004-359639. Compounds, bifunctional photoinitiators described in JP-T-2002-530372, and the like. These polymerization initiators are from 0.01 to 100 parts by weight of a compound having an ethylenically unsaturated bond capable of radical polymerization. It is contained in the range of 40 parts by weight preferable.

  In addition, a polymerization inhibitor can be added to the non-yellowing polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the polymerization inhibitor that can be added to the non-yellowing polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The polymerization inhibitor is preferably added in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the radical polymerizable compound (B).

  Further, the non-yellowing polymerizable composition of the present invention can be added with a polymerization accelerator or a chain transfer catalyst typified by amine, thiol, disulfide or the like for the purpose of further promoting the polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the non-yellowing polymerizable composition of the present invention include, for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, N-phenylglycine, N, N-diethylaniline, butylamine, dibutylamine, tributylamine, trimethylamine, triethylamine, triisopropylamine, octyldimethylamine, triethanolamine, cyclohexylamine, dicyclohexylamine, benzyldimethylamine, piperidine, piperazine, morpholine, pyridine, phenyldiethanolamine Amines such as 2- (dimethylamino) ethyl acrylate, thiols described in USP No. 4414312 and JP-A 64-13144, and JP-A-2-291561 Thiones described in US Pat. No. 3,558,322 and JP-A 64-17048, and O-acylthiohydroxamates and N-alkoxypyridine thiones described in JP-A-2-291560. .

  The non-yellowing polymerizable composition of the present invention is further used in accordance with the purpose, such as dyes, organic and inorganic pigments, phosphine, phosphonate, phosphite and other oxygen removing agents, reducing agents, antifoggants, antifading agents, and antihalation agents. , Fluorescent brighteners, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, dye precursors, UV absorbers, foaming agents, antifungal agents, antistatic agents, magnetic substances and various other It may be used by mixing with an additive or a diluting solvent that imparts the above characteristics.

  In the polymerization reaction, the non-yellowing 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. As the light source for providing light, a light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a main wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Various light sources such as a xenon lamp, a deuterium lamp, a fluorescent lamp, an Nd-YAG triple wave laser, a He-Cd laser, a nitrogen laser, an Xe-Cl excimer laser, an Xe-F excimer laser, and a semiconductor-excited solid laser can be used. In addition, the definition of ultraviolet rays, visible light, near infrared rays, and the like referred to in this specification is based on “Iwanami Riken Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, various inks, ink-jet inks, overcoat varnishes, various printing plate materials, photoresists, electrophotography, direct printing plate materials, optical fibers, hologram materials, and other photosensitive materials, microcapsules, etc. It can be applied to various recording media, as well as adhesives, pressure-sensitive adhesives, adhesives, release coating agents, sealants, and various paints.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In addition, unless otherwise indicated, a part shows a weight part in an example. First, the compounds used in Examples and Comparative Examples are shown in Table 1, and Synthesis Examples are shown for the compounds (1) to (11) that are the photopolymerization initiator (A) of the present invention.

Table 1

Synthesis example (1)
Photopolymerization initiator: synthesis of compound (1) 24.0 g of 2-hydroxythioxanthone, 13.2 g of methacrylic acid and 600 ml of dichloromethane were added and stirred at room temperature. Thereafter, 34.2 g of dicyclohexylcarbodiimide and 4.3 g of 4-dimethylaminopyridine were added and stirring was continued for 4 hours. Then, it washed with hydrochloric acid water and extracted with dichloromethane. The organic layer was dried over magnesium sulfate, and the desiccant was filtered off. The residue was purified by silica gel column chromatography using ethyl acetate / hexane = 2/1 as a developing solvent to obtain 37.8 g of compound (1). Obtained.

Synthesis examples (2) to (11)
By applying the method of Synthesis Example 1 described above, compounds (2) to (11) which are the photopolymerization initiator (A) of the present invention were obtained.

  Table 2 shows the results of elemental analysis (2400II elemental analyzer manufactured by Perkin Elmer Co., Ltd.) of the photopolymerization initiator (A) of the present invention synthesized in Synthesis Example (1) to Synthesis Example (11) described above.

  (2-1) Curability of non-yellowing polymerizable composition comprising photopolymerization initiator (A), radical polymerizable compound (B), and resin (C)

Examples 1-11, Comparative Examples 1-6
3 parts by weight of the compound shown in Table 3 as the photopolymerization initiator (A), 2 parts by weight of 2-ethylhexyl 4- (dimethylamino) benzoate as the sensitizer, and ditrimethylolpropanetetra as the radical polymerizable compound (B) 85 parts by weight of acrylate and 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as resin (C) were blended and melted by heating to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product was irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 lamp), then rubbed with a cotton cloth and judged at a conveyor speed at which the film was not damaged. The results are shown in Table 3. The conveyor speed (m / min) of the ultraviolet irradiation device indicates that the larger the number, the better the curability.

Table 3

  The non-yellowing polymerizable composition using the photopolymerization initiator (A) of the present invention has high curability as compared with a polymerizable composition using a photopolymerization initiator that is generally used. It became clear that.

  (2-2) Curing of a non-yellowing polymerizable composition comprising a photopolymerization initiator (A), a radical polymerizable compound (B), a resin (C), and a cleavage type photopolymerization initiator (D) sex

Examples 12-30, Comparative Examples 7-16
3 parts by weight of the compound shown in Table 4 as the photopolymerization initiator (A), 85 parts by weight of ditrimethylolpropane tetraacrylate as the radical polymerizable compound (B), and Daptot DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as the resin (C) ) 10 parts by weight, 2 parts by weight of a compound shown in Table 4 as a cleavage type photopolymerization initiator (D) was blended and melted by heating to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product was irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 lamp), then rubbed with a cotton cloth and judged at a conveyor speed at which the film was not damaged. The results are shown in Table 4. In addition, the conveyor speed (m / min) of an ultraviolet irradiation device shows that curability is so good that a number is large.

Table 4

  It has been clarified that the non-yellowing polymerizable composition using the photopolymerization initiator (A) of the present invention exhibits further curability when used in combination with the cleavage type photopolymerization initiator (D). As compared with the polymerizable composition in which the cleavage type photopolymerization initiator (D) is used in combination with the photopolymerization initiator used, it is also clear that the combination effect of the cleavage type photopolymerization initiator (D) is high. It was.

  (2-3) Yellowing of a non-yellowing polymerizable composition comprising a photopolymerization initiator (A), a radical polymerizable compound (B), and a resin (C)

Examples 31-41, Comparative Examples 17-22
3 parts by weight of the compound shown in Table 5 as the photopolymerization initiator (A), 2 parts by weight of 2-ethylhexyl 4- (dimethylamino) benzoate as the sensitizer, and ditrimethylolpropane tetraacrylate as the radical polymerizable compound (B) 85 parts by weight and 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.) as a resin (C) were blended and melted by heating to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product is irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 light) at a conveyor speed (10 m / min) at which the coated product is completely cured using a belt conveyor type ultraviolet irradiation device. After complete curing, 10 panelists judged yellowing before and after curing in the coated product. The determination was made by relative evaluation in five stages from 1 (bad) to 5 (good). The results are shown in Table 5.

Table 5

  The non-yellowing polymerizable composition using the photopolymerization initiator (A) of the present invention is markedly superior in yellowing compared to a polymerizable composition using a photopolymerization initiator that is generally used. It became clear that. The reason is presumed that the photopolymerization initiator (A) used in the present invention has a specific structure in which one carbonyloxy group having a radical polymerizable functional group is introduced to thioxanthone. Yes.

  (2-4) Yellow of a non-yellowing polymerizable composition comprising a photopolymerization initiator (A), a radical polymerizable compound (B), a resin (C), and a cleavage type photopolymerization initiator (D) Degeneration

Examples 42-60, Comparative Examples 23-32
3 parts by weight of the compound shown in Table 6 as the photopolymerization initiator (A), 85 parts by weight of ditrimethylolpropane tetraacrylate as the radical polymerizable compound (B), and Daptot DT170 (diallyl phthalate manufactured by Tohto Kasei Co., Ltd.) as the resin (C) Resin) 10 parts by weight, 2 parts by weight of a compound shown in Table 6 as a cleavage type photopolymerization initiator (D) were blended and melted by heating to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product is irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 light) at a conveyor speed (10 m / min) at which the coated product is completely cured using a belt conveyor type ultraviolet irradiation device. After complete curing, 10 panelists judged yellowing before and after curing in the coated product. The determination was made by relative evaluation in five stages from 1 (bad) to 5 (good). The results are shown in Table 6.

Table 6

  Even in a non-yellowing polymerizable composition in which a cleavage type photopolymerization initiator (D) is used in combination with the photopolymerization initiator (A) of the present invention, the photopolymerization initiator generally used is cleaved. When compared with the polymerizable composition using the type photopolymerization initiator (D), it was revealed that yellowing was remarkably superior. The reason is presumed that the photopolymerization initiator (A) used in the present invention has a specific structure in which one carbonyloxy group having a radical polymerizable functional group is introduced to thioxanthone. Yes.

  (2-5) Exudation amount of non-yellowing polymerizable composition comprising photopolymerization initiator (A), radical polymerizable compound (B), and resin (C)

Examples 61-71, Comparative Examples 33-38
3 parts by weight of the compound shown in Table 7 as the photopolymerization initiator (A), 2 parts by weight of 2-ethylhexyl 4- (dimethylamino) benzoate as the sensitizer, and ditrimethylolpropane tetraacrylate as the radical polymerizable compound (B) 85 parts by weight and 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.) as resin (C) were blended and melted by heating to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product is irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 light) at a conveyor speed (10 m / min) at which the coated product is completely cured using a belt conveyor type ultraviolet irradiation device. After completely cured, place an uncoated pet film on the coated material, leave it at a temperature of 60 ° C. and a pressure of 15 g / cm ² for 1 day, and ooze out (transfer) to the uncoated pet film. The amount of photopolymerization initiator was determined. The results are shown in Table 7.

Table 7

  From the examples of the amount of oozing and the comparative example, it can be seen that the photopolymerization initiator having a polymerizable substituent capable of reacting with a monomer or the like in the polymerizable composition in the photopolymerization initiator has a small amount of oozing. It was revealed that the amount of exudation in the non-yellowing polymerizable composition using the photopolymerization initiator (A) of the present invention was remarkably small. For this reason, the photopolymerization initiator of the present invention is most excellent in curability according to the curable examples, so that the polymerizable substituent of the photopolymerization initiator of the present invention is highly reactive with the monomers in the polymerizable composition. It is speculated that the amount of oozing could be minimized because the photoinitiator was incorporated into the polymerizable composition.

  (6) Exudation amount of non-yellowing polymerizable composition comprising photopolymerization initiator (A), radical polymerizable compound (B), resin (C), and cleavage type photopolymerization initiator (D)

Examples 72-90, Comparative Examples 39-48
3 parts by weight of the compound shown in Table 8 as the photopolymerization initiator (A), 85 parts by weight of ditrimethylolpropane tetraacrylate as the radical polymerizable compound (B), and Daptot DT170 (diallyl phthalate manufactured by Tohto Kasei Co., Ltd.) as the resin (C) Resin) 10 parts by weight, 2 parts by weight of a compound shown in Table 8 as a cleavage type photopolymerization initiator (D) were blended and melted by heating to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product is irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 light) at a conveyor speed (10 m / min) at which the coated product is completely cured using a belt conveyor type ultraviolet irradiation device. After completely cured, place an uncoated pet film on the coated material, leave it at a temperature of 60 ° C. and a pressure of 15 g / cm ² for 1 day, and ooze out (transfer) to the uncoated pet film. The amount of photopolymerization initiator was determined. The results are shown in Table 8.

Table 8

  Even in the non-yellowing polymerizable composition in which the cleavage type photopolymerization initiator (D) is used in combination with the photopolymerization initiator (A) of the present invention, it is compared with the general polymerizable composition shown in the comparative example. As a result, it was found that the amount of the photopolymerization initiator that oozes out from the cured polymerizable composition was remarkably small. For this reason, the non-yellowing polymerizable composition of the present invention has the most excellent curability according to the curable examples, so that the crosslinking density of the polymerizable composition is high, and the photopolymerization initiator is contained in the coating film after curing. I guess it is because it has become difficult to ooze out. Moreover, since the same tendency as the result in the Example / Comparative Example of the amount of exudation of (2-5) was observed, it was more presumed that the photopolymerization initiator was less likely to exude from the polymerizable composition after curing. I think it is the result of making it certain.

  According to the above examples and comparative examples, the non-yellowing polymerizable composition using the photopolymerization initiator (A) of the present invention is compared with the polymerizable composition using a photopolymerization initiator that is generally used. Even so, it became clear that the curability was excellent. In addition, the polymerizable composition using the photopolymerization initiator of the present invention was able to suppress oozing out of the photopolymerization initiator after curing of the polymerizable composition as compared with a general polymerizable composition. . In particular, it has been clarified that coloring after curing of the polymerizable composition can be remarkably suppressed as compared with a general polymerizable composition. In the case of a non-yellowing polymerizable composition using the photopolymerization initiator (A) of the present invention, it is possible to satisfy all these requirements that were difficult with a polymerizable composition using a conventional photopolymerization initiator. It became clear. Furthermore, even in the non-yellowing polymerizable composition in which the photopolymerization initiator (A) of the present invention and the cleavage type photopolymerization initiator (D) are used in combination, further curability is exhibited and at the same time after curing of the polymerizable composition. It is possible to suppress coloring and bleeding of the photopolymerization initiator, and it is clear that it is superior to a polymerizable composition using a photopolymerization initiator and a cleavage type photopolymerization initiator that are generally used in combination. became. Even in the case of a non-yellowing polymerizable composition in which the photopolymerization initiator (A) and the cleavage type photopolymerization initiator (D) of the present invention are used in combination, it is difficult with a polymerizable composition using a conventional photopolymerization initiator. It became clear that all these requirements were met.

  The present invention provides a polymerizable composition that is very sensitive to irradiation with energy rays, particularly irradiation with light of 250 to 450 nm. Therefore, the polymerizable composition of the present invention can rapidly and surely proceed polymerization, crosslinking reaction and the like using a radical generated by irradiation of energy rays, which has been conventionally used, as a result. It can be expected to increase the sensitivity to energy rays or to improve the characteristics of various applications by sufficiently proceeding the reaction. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Ink-jet ink, paint, photosensitive resin for printing plates, color proof for printing, resist for color filters, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display, dry film resist, Resist for printed circuit boards, solder resist, photoresist for semiconductor, resist for microelectronics, resist for manufacturing micromachine parts, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat Agent, powder coatings, adhesives, pressure-sensitive adhesives, release agents, optical recording media, adhesive, release coat agent composition for image recording materials using microcapsules, various devices and the like.

Claims (7)

A non-yellowing polymerizable composition comprising a photopolymerization initiator (A) represented by the following general formula (1), a radical polymerizable compound (B), and a resin (C).
General formula (1)

Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted acyl group, or the following general formula 2 represents a group represented by (2), provided that only one of R ^{1 to} R ⁸ is a group represented by the following general formula (2), and R ^{1 to} R ⁸ represents a general formula (2 ) A substituent other than the group represented by) may form a ring with adjacent substituents.
General formula (2)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group.)   The non-yellowing polymerizable composition according to claim 1, further comprising a cleavage type photopolymerization initiator (D).   The non-yellowing polymerizable composition according to claim 2, wherein the cleavage type photopolymerization initiator (D) is an α-aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or an oxime ester photopolymerization initiator. . The non-yellowing polymerizable composition according to claim 3, wherein the α-aminoketone photopolymerization initiator is represented by the following general formula (3).
General formula (3)

(Wherein R ¹⁰ and R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group.
R ¹¹ and R ¹² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group. R ¹¹ and R ¹² may be combined to form a ring.
R ¹⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, substituted or Unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted alkylthio group, Substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted Diarylamino group, substituted or unsubstituted alkylaryl group It represents a cyano group or a halogen atom.
Ar ¹ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. ) The non-yellowing polymerizable composition according to claim 3, wherein the acylphosphine oxide photopolymerization initiator is represented by the following general formula (4).
General formula (4)

(In the formula, R ¹⁵ and R ¹⁶ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
R ¹⁷ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group. ) The non-yellowing polymerizable composition according to claim 3, wherein the oxime ester photopolymerization initiator is represented by the following general formula (5).
General formula (5)

Wherein R ¹⁸ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl Group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted Alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted arylamino group, substituted Or an unsubstituted diarylamino group, a substituted or unsubstituted alkyl group It represents a Ruamino group or a halogen atom.
R ¹⁹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or —CO—Ar ³ .
Ar ² represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.
Ar ³ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
R ²⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
X represents a direct bond or —CO—. )   The manufacturing method of the polymer obtained by making it polymerize by light-irradiating the non-yellowing polymerizable composition in any one of Claims 1-6.