JP4438636B2 - Radical polymerization initiator, polymerizable composition, and method for producing polymer. - Google Patents

Description

  The present invention relates to a novel radical polymerization initiator, a polymerizable composition, and a method for producing a polymer using the polymerizable composition. More specifically, free radicals are efficiently generated by irradiation with energy rays, particularly light, and the polymerizable composition is reliably polymerized in a short time by a polymerization reaction or a crosslinking reaction using the generated radicals and has good physical properties. Regarding materials and methods capable of obtaining a polymer, further, molding resin, casting resin, stereolithography resin, sealant, dental polymerization resin, printing ink, paint, photosensitive resin for printing plate, printing Color proof, color filter resist, black matrix resist, liquid crystal photo spacer, rear projection screen material, optical fiber, plasma display rib material, dry film resist, printed circuit board resist, solder resist, semiconductor photoresist, Microelectronic resist, Micromass Parts manufacturing resist, etching resist, microlens array, insulation material, hologram material, optical switch, waveguide material, overcoat agent, powder coating, adhesive, adhesive, release agent, optical recording medium, adhesive Novel radical polymerization initiator and polymerizable composition for obtaining a polymer having good physical properties in fields such as adhesives, release coating agents, image recording materials using microcapsules, and various devices And a method for producing a polymer product using the polymerizable composition.

  Photopolymerization initiators that cause polymerization of acrylates and the like by irradiation with UV light are used in a wide range of fields. For commercially available photopolymerization initiators, Photopolymer Social Network, “Sensitive Material List Book”, 55-72. Page, 1996 (Bunshin Publishing).

  In recent years, researches on photopolymerization initiators having higher sensitivity than those of commercially available photopolymerization initiators have been actively conducted, and an example thereof is an α-aminoacetophenone derivative (Patent Document 1). When the above compound has a substituent containing a sulfur atom or an oxygen atom at the 4-position of the phenyl group, the compound is particularly useful as a photocuring photoinitiator containing a pigment such as a UV curable printing ink. It is known to be appropriate (Patent Documents 2 and 3). It is also known that an α-aminoacetophenone derivative having an amino group at the 4-position of a phenyl group is used in combination with a photosensitizer of an aromatic carbonyl compound (Patent Document 4). An α-aminoketone derivative in which the phenyl group of the α-aminoacetophenone derivative is an N-substituted carbazole group is also known (Patent Document 5). It is known that the polymerizable composition containing the α-aminoacetophenone derivative is a highly sensitive polymerizable composition that can be cured with a small amount of light irradiation. However, from the viewpoint of cost reduction and productivity improvement in recent years, while there is a need for a highly sensitive polymerizable composition that can be cured in a shorter time and with a smaller amount of light irradiation, the above α-amino Even systems using a combination of acetophenone derivatives and photosensitizers of aromatic carbonyl compounds have not been sensitive enough to accommodate the various newly proposed processes. Thus, a polymerizable composition containing α-aminoacetophenone containing at least one allyl group or aralkyl group (arylalkyl group) at the α-position as a highly sensitive photoinitiator has been proposed (Patent Document 6). . In addition, α-aminoacetophenone derivatives containing two functional groups in the same molecule have also been proposed as highly sensitive photoinitiators. It is known that an α-aminoacetophenone derivative containing two functional groups in the same molecule not only exhibits high activity but also does not contain volatile substances (Patent Document 7). However, even an α-aminoacetophenone derivative containing at least one allyl group or aralkyl group at the α-position or an α-aminoacetophenone derivative containing two functional groups in the same molecule has a large exposure area. Sensitivity is not sufficient to cope with various newly proposed processes represented by area increase, and higher sensitivity of the polymerization initiator is required.

JP-A-54-99185 JP 58-157805 A JP 59-167546 A JP-A-60-84248 JP 61-21104 A Japanese Unexamined Patent Publication No. 63-264560 JP-T-2002-530372

  The polymerizable composition containing these polymerization 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 amount of light irradiation energy, that is, a highly sensitive material has been required, and a conventionally known radical polymerization initiator is not necessarily sufficient. Needless to say, there is a need for a more sensitive polymerization initiator.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention relates to a radical polymerization initiator represented by the following general formula (1).
General formula (1)

[式中、Ａは、下記一般式（２）、一般式（３）、一般式（４）、または一般式（５）で表わされる基を表し、Ａｒ¹は、基

Wherein A represents a group represented by the following general formula (2), general formula (3), general formula (4), or general formula (5), and Ar ¹ represents a group

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, acyl group, alkoxy group, aryloxy group. , An acyloxy group, an alkoxycarbonyloxy group, an alkylthio group, an arylthio group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, or a halogen atom, and R ^{5 to} R ⁹ are , And together may form an aromatic ring)
R ¹ is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group,
R ² is either the same meanings as R ^1, or a substituted or unsubstituted together with R ^1, an alkylene group or carbon atoms 3 to 9, consisting of 2 to 8 carbon atoms, oxaalkylene groups Or represents an azaalkylene group,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or COR ¹⁰ , or together they have 2 carbon atoms Represents an alkylene group of ˜6, an oxaalkylene group, a thiaalkylene group or an azaalkylene group having 2 to 6 carbon atoms,
R ¹⁰ represents a substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkoxy group, or aryloxy group. ]

General formula (2)

General formula (3)

General formula (4)

General formula (5)

[Wherein Y represents —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═ CH-, also properly it represents a direct bond,
Z is —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, also properly it represents a direct bond,
U represents —O—, —S—, or —N (R ¹¹ ) —;
V represents a nitrogen atom,
W represents a nitrogen atom,
R ¹¹ represents a substituted or unsubstituted alkyl group, A alkenyl group or an alkoxy group. ]

  Moreover, this invention relates to the said radical polymerization initiator whose A is General formula (2).

  The present invention also relates to a polymerizable composition comprising the radical polymerization initiator (A) and the radical polymerizable compound (B).

  The present invention also relates to a method for producing a polymer, wherein the polymerizable composition is polymerized by irradiating with an energy ray containing light in a wavelength region of 250 nm to 450 nm.

The radical polymerization initiator of the present invention has a general formula (2), a general formula (2) having a specific substituent, that is, an aromatic acyl group such as benzoyl, toluoyl, or naphthoyl, in a conventionally known α-aminoacetophenone derivative. 3) By substituting the group represented by the general formula (4) or the general formula (5) , the energy ray, particularly in the wavelength region of 250 nm to 450 nm, has good absorption characteristics, and the wavelength region Therefore, it is possible to function as a photoradical generator with extremely high sensitivity without using a sensitizer together. Therefore, by using the polymerization initiator of the present invention, it is possible to reliably realize a polymerization reaction and a crosslinking reaction using radicals generated from a polymerization initiator of a conventionally known α-aminoacetophenone derivative in a shorter time. As a result, it is possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions.
The ]

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

First, the radical polymerization initiator of the present invention will be described. The radical polymerization initiator of the present invention is characterized by the general formula (2), the general formula (3), the general formula (4), or the general formula (2) in which the benzene ring portion of the α-aminoacetophenone derivative is substituted with an aromatic acyl group. By having a characteristic structure replaced with the group represented by 5), a significant increase in sensitivity to energy rays, particularly light irradiation in the wavelength region of 250 nm to 450 nm, is realized.

The radical polymerization initiator of the present invention has a structure represented by the general formula (1), and the benzene ring portion of the α-aminoacetophenone derivative is substituted with the general formula (2), the general formula ( 3) It has a characteristic structure in which the group represented by the general formula (4) or the general formula (5) is replaced. By introducing the group represented by the general formula (2), the general formula (3), the general formula (4), or the general formula (5), the compound of the present invention is suitable for a wavelength region of 250 nm to 450 nm. Can have absorptive properties. In addition, by having this structure, the compound of the present invention decomposes very efficiently without using a sensitizer in combination with light irradiation in the wavelength region, and as a result, a large amount of radicals can be efficiently decomposed. It can function as a highly sensitive material that occurs in

[式中、Ａは、下記一般式（２）、一般式（３）、一般式（４）、または一般式（５）で表わされる基を表し、Ａｒ¹は、基

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸およびＲ⁹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、アリール基、アルケニル基、アシル基、アルコキシ基、アリールオキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、アルキルチオ基、アリールチオ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ジアリールアミノ基、アルキルアリールアミノ基、またはハロゲン原子を表す。また、Ｒ⁵〜Ｒ⁹は、一体となって芳香環を形成してもよい。）を表し、
Ｒ¹は、置換もしくは未置換の、アルキル基、アリール基、またはアルケニル基であり、
Ｒ²は、Ｒ¹と同じ意味を表すか、またはＲ¹と一緒になって置換もしくは未置換の、炭素原子数２〜８からなるアルキレン基、または炭素原子数３〜９の、オキサアルキレン基もしくはアザアルキレン基を表し、
Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、置換もしくは未置換の、アルキル基、アリール基、アルケニル基、またはＣＯＲ¹⁰であるか、または、それらが一緒になって、炭素原子数２〜６のアルキレン基、炭素原子数２〜６の、オキサアルキレン基、チアアルキレン基もしくはアザアルキレン基を表し、
Ｒ¹⁰は、置換もしくは未置換の、アルキル基、アリール基、アルケニル基、アルコキシ基、またはアリールオキシ基を表す。]
一般式（２）

一般式（３）

一般式（４）

一般式（５）

[式中、Ｙは−Ｏ−、−Ｓ−、＞Ｓ＝Ｏ、＞ＳＯ ₂ 、−Ｎ（Ｒ ¹¹ ）−、−ＣＯ−、−ＣＨ ₂ −、−ＣＨ ₂ ＣＨ ₂ −、−ＣＨ＝ＣＨ−、もしくは直接結合を表し、
Ｚは、−Ｏ−、−Ｓ−、＞Ｓ＝Ｏ、＞ＳＯ ₂ 、−Ｎ（Ｒ ¹¹ ）−、−ＣＯ−、−ＣＨ ₂ −、−ＣＨ ₂ ＣＨ ₂ −、−ＣＨ＝ＣＨ−、もしくは直接結合を表し、
Ｕは、−Ｏ−、−Ｓ−、または−Ｎ（Ｒ ¹¹ ）−を表し、
Ｖは、窒素原子を表し、
Ｗは、窒素原子を表し、
Ｒ ¹¹ は、置換もしくは未置換の、アルキル基、アルケニル基、またはアルコキシ基を表す。] General formula (1)

Wherein A represents a group represented by the following general formula (2), general formula (3), general formula (4), or general formula (5), and Ar ¹ represents a group

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, acyl group, alkoxy group, aryloxy group. , An acyloxy group, an alkoxycarbonyloxy group, an alkylthio group, an arylthio group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, or a halogen atom, and R ^{5 to} R ⁹ are , And together may form an aromatic ring)
R ¹ is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group,
R ² is either the same meanings as R ^1, or a substituted or unsubstituted together with R ^1, an alkylene group or carbon atoms 3 to 9, consisting of 2 to 8 carbon atoms, oxaalkylene groups Or represents an azaalkylene group,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or COR ¹⁰ , or together they have 2 carbon atoms Represents an alkylene group of ˜6, an oxaalkylene group, a thiaalkylene group or an azaalkylene group having 2 to 6 carbon atoms,
R ¹⁰ represents a substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkoxy group, or aryloxy group. ]
General formula (2)

General formula (3)

General formula (4)

General formula (5)

[ Wherein Y represents —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═ CH— or a direct bond,
Z is —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, Or a direct bond,
U represents —O—, —S—, or —N (R ¹¹ ) —;
V represents a nitrogen atom,
W represents a nitrogen atom,
R ¹¹ represents a substituted or unsubstituted alkyl group, alkenyl group, or alkoxy group. ]

  One specific example of the radical polymerization initiator of the present invention is shown as compound (1).

Compound (1)

  The absorption spectrum of compound (1) in acetonitrile is shown in FIG. Moreover, the absorption spectrum of the conventional alpha-amino acetophenone derivative and the compound (16) as a comparative compound is also shown in FIG.

Compound (16)

  As can be seen from FIG. 1, the compound (1) has an even absorption characteristic in the wavelength region of 250 to 450 nm as compared with the compound (16). Therefore, compound (1) can absorb more irradiation light in the wavelength region of 250 to 450 nm than compound (16).

  Further, the compound (1) which is a radical polymerization initiator of the present invention is a relatively transparent material having a molar extinction coefficient of about 4200 at 365 nm corresponding to one of the emission lines of a mercury lamp, for example. Is a material having an innovative function as a radical generator that greatly surpasses the case where the α-aminoacetophenone derivative (16) is used alone or in combination with a sensitizer.

  At present, the details of the mechanism that achieves a significant increase in sensitivity to light irradiation are not clear, but the following two points are considered as the reasons for achieving a significant increase in sensitivity to light irradiation. The first point is that when the radical polymerization initiator (A) is irradiated with light in the ultraviolet region, the excitation to radical generation process is performed more efficiently than the known α-aminoacetophenone derivative. It is. The second point is the absorption characteristic of the initiator of the present invention. Since it has absorption characteristics evenly in the wavelength range of the light source that irradiates light, it can absorb a large amount of light energy necessary to generate radicals.

  The energy ray source used for generating radicals from the radical polymerization initiator (A) of the present invention is not particularly limited, but a light source capable of irradiating light in a wavelength region of 250 nm to 450 nm that expresses particularly suitable sensitivity is preferable, Other energy rays may be emitted simultaneously with the light in the wavelength region. A particularly preferable light source is a light source having a main wavelength of light emission in a wavelength region of 250 nm to 450 nm. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, Examples thereof include, but are not limited to, a power metal halide lamp, a xenon lamp, and a pulse emission xenon lamp. Also emits light in the wavelength range from 250 nm to 450 nm, such as deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excitation solid state laser A laser having a wavelength can also be used as a suitable energy ray source. All of the polymerization initiators (A) of the present invention have suitable absorption in the wavelength region of 250 nm to 450 nm, and the absorption characteristics are slightly different depending on the substituents. It can function as a sensitive radical polymerization initiator. In addition, these light sources can be appropriately irradiated through optical devices such as filters, mirrors, and lenses.

  Next, the structure of the radical polymerization initiator of the present invention will be described in detail.

  As shown in the general formula (1), the radical polymerization initiator of the present invention can introduce various substituents as long as the properties are not impaired. By introducing a substituent, the radical polymerization initiator 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 the resin or solvent used together.

The substituent R ¹ in the general formula (1) is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group. Specifically, the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, An alkenyl group and an aryl group having 4 to 18 carbon atoms.

The linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in the substituent R ¹ in the general formula (1) is a linear, branched, monocyclic or condensed group having 1 to 18 carbon atoms. Examples include polycyclic alkyl groups, and specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, 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, etc. Kill, but is not limited to these.

Examples of the aryl group having 4 to 18 carbon atoms in the substituent R ¹ in the general formula (1) include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms that may contain a hetero atom, Examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group. 2-furanyl group, 2-pyrrolyl group, 9-fluorenyl group, 2-furyl group, 2-thienyl group, 2-indolyl group, 3-indolyl group, 6-indolyl group, 2-benzofuryl group, 2-benzothienyl Group, 4-quinolinyl group, 4-isoquinolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group, 3-phenothiazinyl group 2-phenoxathiinyl group, 3-phenoxazinyl group, 3-thianthrenyl group may be like is mentioned, but not limited thereto.

The linear, branched or cyclic alkenyl group having 1 to 18 carbon atoms in the substituent R ¹ in the general formula (1) is a linear, branched, monocyclic or condensed having 1 to 18 carbon atoms. And a polycyclic alkenyl group, which may have a plurality of carbon-carbon double bonds in the structure. Specific examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, and 2-butenyl. Group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4 -Hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group, etc. DOO but it can not be construed as being limited thereto.

Among the above substituents, R ¹ is preferably an alkyl group or an alkenyl group in terms of the difficulty of synthesis and sensitivity as a radical generator, and specifically includes a methyl group, an ethyl group, a benzyl group, A p-methylbenzyl group or a 2-propenyl group is particularly preferable.

Substituents R ² in the general formula (1) are either the same meanings as R ^1, or a substituted or unsubstituted together with R ^1, an alkylene group composed of from 2 to 8 carbon atoms or carbon atoms, 3 to 9, an oxaalkylene group or an azaalkylene group.

As the alkylene group in the case where the substituent R ² in the general formula (1) is a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms together with R ¹ , R ² is R ¹ and As an example, together with the carbon atoms to which they are attached, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, etc. can be mentioned, It is not limited to these.

The oxa- or azaalkylene group in which the substituent R ² in the general formula (1) is a substituted or unsubstituted oxaalkylene group or azaalkylene group having 3 to 9 carbon atoms together with R ¹ As an example, R ² may be combined with R ¹ together with the carbon atom to which they are bonded to form a tetrahydrofuran ring, a pyrrolidine ring, a piperidine ring, etc., but is not limited thereto. It is not something.

The substituents R ³ and R ⁴ in the general formula (1) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or COR ¹⁰ , or Together, they are an alkylene group having 2 to 6 carbon atoms, an oxaalkylene group, a thiaalkylene group or an azaalkylene group having 2 to 6 carbon atoms.

Examples of the substituted or unsubstituted alkyl group in the substituents R ³ and R ⁴ in the general formula (1) include the same substituents as those exemplified as the alkyl group in the substituent R ¹ .

Examples of the substituted or unsubstituted aryl group in the substituents R ³ and R ⁴ in the general formula (1) include the same substituents as those exemplified as the aryl group in the substituent R ¹ .

The substituted or unsubstituted alkenyl group in the substituents R ³ and R ⁴ in the general formula (1) is a linear, branched or cyclic alkenyl group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms. Examples of the linear or branched alkenyl group include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, which have a plurality of carbon-carbon double groups in the structure. Specific examples include vinyl group, 1-propenyl group, 2-propenyl 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, cyclopent Examples thereof include, but are not limited to, a tenenyl group, a cyclohexenyl group, a 1,3-butadienyl group, a cyclohexadienyl group, and a cyclopentadienyl group.

The substituent R ¹⁰ in the general formula (1) is a substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkoxy group, or aryloxy group.

Examples of the substituted or unsubstituted alkyl group in the substituent R ¹⁰ in the general formula (1) include the same substituents as those exemplified as the alkyl group in the substituent R ¹ .

Examples of the substituted or unsubstituted aryl group in the substituent R ¹⁰ in the general formula (1) include the same substituents as those exemplified as the aryl group in the substituent R ¹ .

Examples of the substituted or unsubstituted alkenyl group in the substituent R ¹⁰ in the general formula (1) include the same substituents as those exemplified as the alkenyl group in the substituent R ¹ .

Examples of the substituted or unsubstituted alkoxy group in the substituent R ¹⁰ in the general formula (1) include linear, branched, monocyclic or condensed polycyclic alkoxy groups having 1 to 18 carbon atoms. Examples include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy, isopropoxy, 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, Examples thereof include a damantyloxy group, a norbornyloxy group, a boronyloxy group, a 4-decylcyclohexyloxy group, a 2-tetrahydrofuranyloxy group, and a 2-tetrahydropyranyloxy group. Absent.

Examples of the substituted or unsubstituted aryloxy group in the substituent R ¹⁰ in the general formula (1) include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms which may contain a hetero atom, Examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy Group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzo Furyloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, - and the like can be mentioned acridinyl group, but is not limited thereto.

As the alkylene group in the case where the substituents R ³ and R ⁴ in the general formula (1) are together alkylene having 2 to 6 carbon atoms, R ³ is bonded to R ⁴ and they are bonded. Examples include, but are not limited to, forming a propyleneimine ring, a pyrrolidine ring, a piperidine ring, or a pipecoline ring together with a nitrogen atom.

Oxaalkylene, thiaalkylene or aza when the substituents R ³ and R ⁴ in the general formula (1) are together an oxaalkylene group, a thiaalkylene group or an azaalkylene group having 2 to 6 carbon atoms Examples of the alkylene group include that R ^{3 and} R ⁴ together with the nitrogen atom to which they are bonded form a morpholine ring, a thiomorpholine ring, a thiazolidine ring, a piperazine ring, or a homopiperazine ring. However, it is not limited to these.

Among the above substituents, the substituents R ³ and R ⁴ are alkyl groups, alkenyl groups, substituents R ³ and R ⁴ together in terms of the difficulty of synthesis and sensitivity as a radical generator. Is preferably an alkylene group having 2 to 6 carbon atoms, or an oxaalkylene group, a thiaalkylene group or an azaalkylene group having 2 to 6 carbon atoms together, specifically, a methyl group, an ethyl group, A morpholino group, a thiomorpholino group, or a piperazino group is particularly preferred.

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸およびＲ⁹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、アリール基、アルケニル基、アシル基、アルコキシ基、アリールオキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、アルキルチオ基、アリールチオ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ジアリールアミノ基、アルキルアリールアミノ基、またはハロゲン原子を表す。また、Ｒ⁵〜Ｒ⁹は、一体となって芳香環を形成してもよい。）である。 Ar ¹ in the general formula (1) is a group

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, acyl group, alkoxy group, aryloxy group. , An acyloxy group, an alkoxycarbonyloxy group, an alkylthio group, an arylthio group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, or a halogen atom, and R ^{5 to} R ⁹ are , And may form an aromatic ring together.

The substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, acyl group, Alkoxy, aryloxy, acyloxy, alkoxycarbonyloxy, alkylthio, arylthio, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, benzylamino, dibenzylamino Or a halogen atom.

Examples of the alkyl group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include the same substituents as those exemplified as the alkyl group in the substituent R ¹ . .

Examples of the aryl group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include the same substituents as those exemplified as the aryl group in the substituent R ¹ . .

Examples of the alkenyl group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include the same substituents as those exemplified as the alkenyl group in the substituent R ¹ . .

As the acyl group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1), a hydrogen atom or a straight chain, branched chain, monocyclic group having 1 to 18 carbon atoms or Examples include a carbonyl group to which a condensed polycyclic aliphatic group is bonded, or a carbonyl group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms, which may contain a hetero atom, is bonded. May have an unsaturated bond, 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, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, Examples include oleoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-anthroyl group, and 5-naphthacenoyl group. However, it is not limited to these.

Examples of the alkoxy group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include the same substituents as those exemplified as the alkoxy group in the substituent R ¹⁰ . .

Examples of the aryloxy group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include the same substituents as those exemplified as the aryloxy group in the substituent R ¹⁰ . Can do.

The acyloxy group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) is a hydrogen atom or a linear, branched, monocyclic or condensed having 1 to 18 carbon atoms. Specific examples include a carbonyloxy group to which a polycyclic aliphatic group is bonded, or a carbonyloxy group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms which may contain a hetero atom is bonded. Is an acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group , Cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy Si group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy Groups, nicotinoyloxy groups, isonicotinoyloxy groups, 9-anthroyloxy groups, 5-naphthacenoyloxy groups, and the like, but are not limited thereto.

Examples of the alkoxycarbonyloxy group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include carbonic acid ester groups having 1 to 12 carbon atoms, and specific examples thereof include tert. -Butoxycarbonyloxy group, tert-pentyloxycarbonyloxy group, 1,1-diethylpropyloxycarbonyloxy group, 1-ethyl-2-cyclopentenyloxycarbonyloxy group, 2-tetrahydropyranyloxycarbonyloxy group, 1- Examples thereof include, but are not limited to, ethylcyclopentyloxycarbonyloxy group.

The alkylthio group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) is linear, branched, monocyclic or condensed polycyclic having 1 to 18 carbon atoms. Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, and octadecylthio group. It is not limited to.

The arylthio group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) is a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6 -Indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group and the like can be mentioned, but are not limited thereto.

Examples of the alkylamino group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, Hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino 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 Group, cyclodode Examples thereof include, but are not limited to, a silamino group, a 1-adamantamino group, and a 2-adamantamino group.

Examples of the dialkylamino group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamino group, Dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropyl Examples thereof include, but are not limited to, an amino group, a methylbutylamino group, a methylisobutylamino group, a cyclopropylamino group, a pyrrolidino group, a piperidino group, and a piperazino group.

As the arylamino group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1), 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 and the like, but are not limited thereto.

Examples of the diarylamino group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include a diarylamino group, a diphenylamino group, a ditolylamino group, and an N-phenyl-1-naphthylamino group. , N-phenyl-2-naphthylamino group, imidazole group, indole group, carbazole group, pyrrole group and the like, but are not limited thereto.

Examples of the alkylarylamino group in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) 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, methylindolino group and the like can be mentioned, It is not limited to these.

Examples of the halogen atom in the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of the above substituents, the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are all simultaneously hydrogen atoms, the substituent R ⁵ is a methyl group and the substituents R ⁶ , R ⁷ , R ⁸ and R ⁹ are simultaneously hydrogen atoms and the substituent R ⁹ is a methyl group. Especially when the groups R ⁵ , R ⁶ , R ⁷ and R ⁸ are simultaneously hydrogen atoms, the substituent R ⁷ is a methyl group and the substituents R ⁵ , R ⁶ , R ⁸ and R ⁹ are simultaneously hydrogen atoms. preferable.

That is, among Ar ^{1 in} the general formula (1), as a particularly preferred structure, all of the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 in the following structure} are simultaneously hydrogen atoms and the substituent R ⁵ is methyl. The substituents R ⁶ , R ⁷ , R ⁸ and R ⁹ are simultaneously hydrogen atoms, the substituent R ⁹ is a methyl group and the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ are simultaneously hydrogen atoms and substituents. R ⁷ is a methyl group and the substituents R ⁵ , R ⁶ , R ⁸ , and R ⁹ are simultaneously hydrogen atoms.

When Ar ¹ in the general formula (1) is an alkyl group, it is inferior in sensitivity as compared with the radical polymerization initiator of the present invention. That is, in order to achieve high sensitivity, Ar ¹ needs to be an aromatic group as in the present invention.

A in general formula (1) is a group represented by general formula (2), general formula (3), general formula (4), or general formula (5) .

Formula (2), the general formula (3), the general formula (4) or a substituent R ¹¹ in the general formula (5), is a substituted or unsubstituted alkyl group, A alkenyl group or an alkoxy group, .

Formula (2), the general formula (3), the general formula (4), or general formula (5) substituted or unsubstituted in the substituents R ¹¹ and the alkyl group, and the A alkenyl group, or an alkoxy group, can be exemplified by the substituents ^{R 5, R 6, R 7} , the alkyl group for R ⁸ and R ^9, a alkenyl group or those exemplified in the alkoxy group and the same substituents.

  As general formula (2), general formula (3), general formula (4), or general formula (5), benzofuranyl group, benzothienyl group, indenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, Fluorenyl group dibenzo [b, e] [1,4] dioxinyl group, phenoxathinyl group, phenothiazinyl group, thianthenyl group, xanthenyl group, thioxanthenyl group, phenoxazinyl group, benzoxazolyl group, benzothiazolyl group, benzimidazolyl group , An indazolyl group, a 1,2-benzisoxazolyl group, an iminostilbenyl group, a xanthonyl group, and the like, but are not limited thereto.

  Of the general formula (2), general formula (3), general formula (4), or general formula (5), a carbazolyl group and dibenzofuran are preferred in terms of synthesis difficulty and sensitivity as a radical generator. Nyl group, dibenzothiophenyl group, fluorenyl group dibenzo [b, e] [1,4] dioxinyl group, phenoxathinyl group, phenothiazinyl group, thiantenyl group, xanthenyl group, thioxanthenyl group, phenoxazinyl group, benzoxazolyl A group, a benzothiazolyl group, a benzimidazolyl group, and an indazolyl group are particularly preferable.

That is, particularly preferable examples of the group represented by the general formula (2), the general formula (3), the general formula (4), or the general formula (5) in A in the general formula (1) include carbazolyl group, dibenzo Furanyl group, dibenzothiophenyl group, fluorenyl group dibenzo [b, e] [1,4] dioxinyl group, phenoxathiinyl group, phenothiazinyl group, thianthenyl group, xanthenyl group, thioxanthenyl group, phenoxazinyl group, benzoxazolyl Group, benzothiazolyl group, benzimidazolyl group and indazolyl group.

Substituents in the substituents R ¹ R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ in the general formula (1) described above are further different. Such other substituents include hydroxyl group, mercapto group, cyano group, nitro group, halogen atom, alkyl group, aryl group, acyl group, alkoxy group, aryloxy group. Groups, acyloxy groups, alkylthio groups, arylthio groups, amino groups, alkylamino groups, dialkylamino groups, arylamino groups, diarylamino groups, alkylarylamino groups, benzylamino groups, dibenzylamino groups 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 linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl 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, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, and the like. Absent.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl. Group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-furanyl group, 2-pyrrolyl group, 9-fluorenyl group, 2-furyl Group, 2-thienyl group, 2-indolyl group, 3-indolyl group, 6-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 4-quinolinyl group, 4-isoquinolyl group, 2-carbazolyl group, 3- Carbazolyl group, 4-carbazolyl group, 9-acridinyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-phenoxazinyl group, 3 , And the like thianthrenyl group, but not limited thereto.

  The acyl group is a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon atom that may contain a hetero atom. Examples thereof include carbonyl groups to which monocyclic or condensed polycyclic aromatics of 4 to 18 are bonded, and they may have an unsaturated bond in the structure. 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, crotonoyl group, isocrotonoyl group, oleo group Oil group, benzoyl group, 1-naphthoyl group, 2-naphthoyl , Cinnamoyl group, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru group, 5-Nafutasenoiru group and the like can be mentioned, but not limited thereto.

  Examples of the alkoxy group include linear, branched, monocyclic or condensed polycyclic alkoxy groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyl. Oxy group, hexyloxy group, heptyloxy 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, Boronil Shi group, 4-decyl cyclohexyl group, 2-tetrahydrofuranyl group, and the like can be mentioned 2-tetrahydropyranyloxy group, but is not limited thereto.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 4 to 18 carbon atoms that may contain a hetero atom, and specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fur Olenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group Group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like. The present invention is not limited to, et al.

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon that may contain a hetero atom. Examples thereof include carbonyloxy groups having a monocyclic or condensed polycyclic aromatic group having 4 to 18 atoms, and specific examples thereof include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovale Ryloxy, pivaloyloxy, lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, acryloyloxy, methacryloyloxy, crotonoyloxy, isocrotonoyloxy Group Oiloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9- Examples include anthroyloxy group and 5-naphthacenoyloxy group, but are not limited thereto.

  Examples of the alkylthio group include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms, and specific examples include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group. Groups, hexylthio groups, octylthio groups, decylthio groups, dodecylthio groups, octadecylthio groups, and the like, but are not limited thereto.

  Examples of the arylthio group include monocyclic or condensed polycyclic arylthio groups having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples thereof include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9- Anthrylthio group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, Examples thereof include, but are not limited to, a 3-carbazolylthio group and a 4-carbazolylthio group.

  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 can be exemplified, but not limited thereto.

  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, Examples include, but are not limited to, piperazino groups.

  Examples of the arylamino group 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- A biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, an indolino group, and the like can be mentioned, but are not limited thereto. It is not a thing.

  Diarylamino groups include diarylamino groups, diphenylamino groups, ditolylamino groups, N-phenyl-1-naphthylamino groups, N-phenyl-2-naphthylamino groups, imidazole groups, indole groups, carbazole groups, pyrrole groups, and the like. It can be mentioned, but is not limited to these.

  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 Examples include, but are not limited to, -ethylanilino group, N-methyl-1-naphthylamino group, and methylindolino group.

Specific structures are shown below, but the structure of the radical polymerization initiator of the present invention is not limited thereto.

  The synthesis method for obtaining the radical polymerization initiator of the present invention is not particularly limited, and the structure can be easily synthesized and confirmed by appropriately combining conventionally known chemical reactions, post-treatment methods, purification methods and analysis methods. Is possible. Examples of methods for synthesizing α-aminoacetophenone derivatives include those described in European Patent Application Publication 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 radical polymerization initiator of the present invention by appropriately replacing the raw materials used in the synthesis.

  Since the radical polymerization initiator of the present invention functions as a very sensitive radical polymerization initiator by irradiation with energy rays, particularly light in the wavelength region of 250 to 450 nm, a conventionally known α-aminoacetophenone derivative-based radical polymerization initiator It is possible to realize a polymerization reaction, a crosslinking reaction, and the like using a polymer in a shorter time, and as a result, it is possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. . The method for using the radical polymerization initiator of the present invention will be described below.

  The composition containing the radical polymerization 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 a 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 in the 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, tricyclodecandi 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.

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 Such.

  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. ”Monomers” series.

Moreover, the cyclic compound shown below is mention | raise | lifted 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, page 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed., Volume 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. ), Vol. 21, page 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, examples of the radical polymerizable compound (B) 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), 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.

  Further, the polymerizable composition of the present invention may be used by adding a carboxyl group-containing polymer (C) shown below for the purpose of using it for image formation as a so-called alkali development type photoresist material. Since the carboxyl group-containing polymer (C) has solubility in an alkaline aqueous solution, if the film prepared using the photopolymerizable composition of the present invention is partially cured, the so-called negative type is obtained due to the difference in solubility in the alkaline aqueous solution. It is possible to form a resist pattern. Here, the carboxyl group-containing polymer (C) is a copolymer of acrylic acid ester or methacrylic acid ester and acrylic acid, or a copolymer of methacrylic acid ester, methacrylic acid and a vinyl monomer copolymerizable therewith. Is mentioned. These copolymers may be used alone or in combination of two or more.

  Here, as the methacrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, etc. Is mentioned.

  Methacrylic acid ester, methacrylic acid and vinyl monomers copolymerizable therewith include tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3, Examples include 3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

  The polymerization initiator (A) of the present invention is preferably used in the range of 0.01 to 60 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). The carboxyl group-containing polymer (C) 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, based on 100 parts by weight of the radical polymerizable compound (B). .

  The polymerizable composition of the present invention is mixed with a binder such as an organic polymer in order to improve the film formability, and is applied to a polymer film such as glass plate, aluminum plate, other metal plate, polyethylene terephthalate or polyethylene. It is possible to use.

  Examples of binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, Epoxy resins, alkyd resins, etc., supervised by Kiyoshi Akamatsu, "New Technology of Photosensitive Resins" (CMC, 1987) and "10188 Chemical Products", pages 657-767 (Chemical Industry Daily, 198) Year) industry known organic polymer described, and the like.

  The polymerizable composition of the present invention can be used by adding a solvent as necessary for the purpose of improving the coating suitability including viscosity adjustment. The solvent that can be used by adding to the 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 polymerizable composition of the present invention. For example, known solvents such as alcohol-based, ketone-based, ester-based, aromatic-based, hydrocarbon-based, and halogenated hydrocarbon-based solvents can be used, but the present invention is not limited to these.

  In addition, the 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, other sensitizers and other sensitizers may be used. It can be used in combination with a photopolymerization initiator.

  Sensitizers that can be used in combination with the polymerizable composition of the present invention include benzophenones, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and 1 represented by benzyl and camphorquinone. , 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, etc. Dye, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative , Triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetra Examples include filin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and other specific examples, edited by Nobu Okawara et al., “Dye Handbook” (1986, Kodansha) Dye and sensitization described in Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Tadasaburo et al., “Special functional materials” (1986, CMC) However, it is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region are included, and these may be used in any ratio as necessary. The above may be used. 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-diethylamino). Marine) and the like can be mentioned, but not limited thereto.

  Other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 907, Cure 369, IRGACURE 379, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01 (CGI124), CGI242 Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Denka), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 6 Triazine derivatives described in JP-A-69621 and JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-2243807, JP-B-43-23684, As described in JP-B-44-6413, JP-B-47-1604 and diazonium compounds described in USP 3,567,453, USP 2,848,328, USP 2,852,379 and USP 2,940,853 Organic azide compounds, ortho-quinonediazides described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610, JP-B 55-39162, JP 59-140203 A and “Macro” Various onium compounds including iodonium compounds described in “Moleculars”, Vol. 10, page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, Metal allene complexes described in European Patent No. 109851 and European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986) , Titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) and JP-A-2-182701. Transition metal complexes containing transition metals such as ruthenium, described in JP-A-3-209477 Aluminate complex, borate compound described in JP-A-2-157760, 2,4,5-triarylimidazole dimer described in JP-A-55-127550 and JP-A-60-202437, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, carbon tetrabromide and organic halogens described in JP-A-59-107344 Compounds, JP-A-5-213861, JP-A-5-255347, JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, The sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-053009 and Japanese Patent Application No. 2004-263413 JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, USP3558309 (1971), USP4202697 (1980) Oxime ester compounds described in JP-A Nos. 61-24558, 2004-534797, and 2004-359639, and bifunctional photoinitiators described in JP-A-2002-530372. These polymerization initiators are preferably contained in the range of 0.01 to 40 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

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

  Specific examples of the thermal polymerization inhibitor that can be added to the 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 the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B).

  Moreover, the polymerization composition of this invention can add the polymerization accelerator represented by amine, thiol, disulfide, etc. and a chain transfer catalyst for the purpose of further promoting superposition | polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP No. 4414312 Thiols described in the specification, JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples include O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

  Further, the polymerizable composition of the present invention can be used depending on the purpose, such as dyes, organic and inorganic pigments, phosphine, phosphonate, phosphite and other oxygen scavengers and reducing agents, antifoggants, antifading agents, antihalation agents, fluorescent enhancers. Whitening agents, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, dye precursors, UV absorbers, foaming agents, antifungal agents, antistatic agents, magnetic substances and other various properties You may mix and use the additive to add, a dilution solvent, etc.

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

Therefore, various inks, various printing plate materials, photoresists, electrophotography, direct printing plate materials, optical fibers, hologram recording materials and other recording media such as microcapsules, and adhesion can be applied to the substrate together with a binder. It can be applied to adhesives, pressure-sensitive adhesives, adhesives, release coating agents, sealants and various paints.

  The radical polymerization initiator (A) of the present invention functions as a radical polymerization initiator that is sensitive to irradiation light in a wavelength region of 250 to 450 nm. The reason why the radical polymerization initiator (A) of the present invention is more sensitive than the known α-aminoacetophenone derivative is not clear at present, but 1) for the radical polymerization initiator (A) of the present invention. When the light in the ultraviolet region is irradiated, the process of excitation to radical generation is performed more efficiently than known α-aminoacetophenone derivatives, or 2) the radical polymerization initiator (A) of the present invention is light Because it has absorption characteristics evenly in the wavelength range of the light source to irradiate, it can be absorbed by a large amount of light energy necessary to generate radicals. It is done.

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, prior to the examples, some of the synthesis examples of the above-described radical polymerization initiator (A) of the present invention are shown.

Synthesis example (1)
Synthesis of compound (1)

Synthesis of N-ethyl-3-benzoyl-carbazole Dissolve 100.0 g of N-ethyl-carbazole in 1280 ml of benzene, add 73.4 g of aluminum chloride and stir at 0 ° C., and then 68.4 g of benzoyl chloride. The solution dissolved in 120 ml was added over 30 minutes. After completion of the addition, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 4000 g of ice water and extracted with 4000 ml of benzene. The organic layer is dried over magnesium sulfate, the desiccant is filtered off to remove the solvent, the residue is purified by column chromatography (eluent: chloroform), recrystallized from ethyl acetate-hexane, N- 93.6 g of ethyl-3-benzoyl-carbazole was obtained (61% yield).

Synthesis of 2-bromo-2-methyl-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -propan-1-one 58.0 g of N-ethyl-3-benzoyl-carbazole was dissolved in 200 ml of dichloromethane. Further, 28.0 g of aluminum chloride was added, and a solution prepared by dissolving 50.5 g of 2-bromoisobutyryl bromide in 100 ml of dichloromethane was added over 30 minutes while stirring at 0 ° C. After completion of the addition, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 800 g of ice water and extracted with 200 ml of chloroform. The organic layer is dried over magnesium sulfate, the desiccant is filtered off, the solvent is distilled off, the residue is purified by column chromatography (eluent: chloroform), recrystallized from ethyl acetate-hexane, 2- 62.5 g of bromo-2-methyl-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -propan-1-one was obtained (yield 72%).

Synthesis of 2,2-dimethyl-1-methoxy- (N-ethyl-6-benzoyl-carbazol-3-yl) -oxirane 2-bromo-2-methyl-1- (N-ethyl-6-benzoyl-carbazole- 3-yl) -propan-1-one (18.0 g) was dissolved in THF (50 ml), sodium methoxide (28% methanol solution, 3.0 g) was added, and the mixture was stirred at room temperature for 5 hours. The solution was added with 300 ml of ice water, the crystals precipitated in the aqueous solution were filtered, and the obtained crystals were dried to give 2,2-dimethyl-1-methoxy- (N-ethyl-6-benzoyl-carbazole-) as white crystals. 15.2 g of 3-yl) -oxirane was obtained (95% yield).

Synthesis of 2-methyl- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-morpholinopropan-1-one (compound (1)) 2,2-dimethyl-1-methoxy- (N-ethyl A solution consisting of 13.4 g of -6-benzoyl-carbazol-3-yl) -oxirane, 29.4 g of morpholine, and 10 mL of acetonitrile was heated at 60 ° C. with stirring, and 18.2 g of anhydrous lithium perchlorate and morpholine 29 were added to this solution. A solution consisting of .4 g was added and stirred at 60 ° C. in nitrogen for 6 hours. The reaction mixture was cooled, diluted with water and extracted with toluene. The organic layer was dried over magnesium sulfate, the desiccant was filtered to remove the solvent, cooled to 0 ° C., and hexane was added dropwise. The produced crystals are filtered, washed with hexane, and dried to give 2-methyl- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-morpholinopropan-1-one (compound (1)). As a white crystal, 13.2 g was obtained (yield 87%).

(Synthesis Example 2)
Synthesis of compound (2)

Synthesis of 2-methyl- [N-ethyl-6- (o-toluoyl) -carbazol-3-yl] -2-morpholinopropan-1-one (Compound (2)) The benzoyl chloride of Synthesis Example 1 is o The target 2-methyl- [N-ethyl-6- (o-toluoyl) -carbazol-3-yl] -2-morpholino was prepared in the same manner as in (Synthesis Example 1) except that it was replaced with toluoyl chloride. Propan-1-one (compound (2)) was obtained.

(Synthesis Example 3)
Synthesis of Compound (3) Synthesis of N-2- (2-methoxyethoxy) ethyl-carbazole To a suspension of 13.0 g of carbazole in 20 ml of toluene was added 0.5 g of trimethylbenzylammonium chloride and 50 ml of 50% NaOH aqueous solution, Next, 20.0 g of 1-bromo-2- (2-methoxyethoxy) ethane was added and stirred at 80 ° C. for 2 hours. After cooling, the mixture is extracted with chloroform, the organic layer is dried over magnesium sulfate, the desiccant is filtered off, the solvent is distilled off, the residue is purified by column chromatography (eluent: chloroform), and N-2. 16.3 g of-(2-methoxyethoxy) ethyl-carbazole was obtained (yield 80%).

Synthesis of 2-methyl- [N-2- (2-methoxyethoxy) ethyl-carbazol-3-yl] -2-morpholinopropan-1-one (Compound (3)) N-ethyl- of Synthesis Example 1 The target 2-methyl- [N-2- (2-methoxyethoxy) ethyl was obtained in the same manner as in (Synthesis Example 1) except that carbazole was replaced with N-2- (2-methoxyethoxy) ethyl-carbazole. -Carbazol-3-yl] -2-morpholinopropan-1-one (compound (3)) was obtained.

(Synthesis Example 4)
Synthesis of compound (4)

Synthesis of 2-methyl- (2-benzoyl-phenoxathiin-7-yl) -2-morpholinopropan-1-one (Compound (4)) N-ethyl-carbazole of Synthesis Example 1 was replaced with N-2- The target 2-methyl- (2-benzoyl-phenoxathiin-7-yl) -2-morpholinopropane was prepared in the same manner as in (Synthesis Example 1) except that (2-methoxyethoxy) ethyl-carbazole was used. -1-one (compound (4)) was obtained.

(Synthesis Example 5)
Synthesis of Compound (6) Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-bromobutan-1-one N-ethyl synthesized in the synthesis section of Compound (1) under light shielding A solution in which 33.7 g of -3-benzoyl-carbazole was dissolved in 150 ml of dichloromethane, 33.7 g of aluminum chloride was further added and stirred at 0 ° C., and 30 g of 2-bromobutyryl bromide was dissolved in 30 ml of dichloromethane for 30 minutes. Added over time. After completion of the addition, the mixture was stirred at 25 ° C. for 4 hours. The reaction mixture was poured into 300 g of ice water and extracted with 100 ml of chloroform. The organic layer is dried over magnesium sulfate, the desiccant is filtered to remove the solvent, the residue is purified by column chromatography (eluent: chloroform), recrystallized from chloroform-hexane, and 1- ( 46.9 g of N-ethyl-6-benzoyl-carbazol-3-yl) -2-bromobutan-1-one was obtained (93% yield).

Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-butan-1-one 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2- Bromobutan-1-one (5 g) was dissolved in THF (35 ml). This solution was slowly added dropwise at 0 ° C. to a mixture of 3.0 g of dimethylamine in 35 ml of THF. After stirring this mixture at 0 ° C. for 12 hours, excess dimethylamine was removed at room temperature by blowing N ₂ at room temperature, and the suspension was poured into 200 ml of ice water and extracted with 200 ml of ethyl acetate. The organic layer is dried over magnesium sulfate, the desiccant is filtered to remove the solvent, the residue is recrystallized from ethyl acetate-hexane, and 1- (N-ethyl-6-benzoyl-carbazole-3- Yl) -2-dimethylamino-butan-1-one was obtained 4.3 g (yield 92%).

Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-2-benzyl-butan-1-one (compound (6)) 1- (N-ethyl-6-benzoyl) -Carbazol-3-yl) -2-dimethylamino-butan-1-one 10.0 g was dissolved in 100 ml of ethyl acetate, and 8.5 g of benzyl bromide was slowly added dropwise. After stirring for 12 hours, the solvent was distilled off, the residue was dissolved in 35 ml of DMF, and the solution was heated to 60 ° C. At this temperature, 5.4 g of a 34% NaOH aqueous solution was dropped, and after the dropping, the mixture was stirred for 5 hours. This mixed solution was poured into 200 ml of ice water, and the precipitate was filtered. The obtained precipitate was purified by alumina column chromatography (eluent: ethyl acetate / toluene = 1: 4) and recrystallized from ethyl acetate-hexane to give 1- (N-ethyl-6-benzoyl-carbazole- 9.2 g of 3-yl) -2-dimethylamino-2-benzyl-butan-1-one (compound (6)) was obtained (yield 75%).

(Synthesis Example 6)
Synthesis of compound (7)

Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-morpholino-butan-1-one 1- (N-ethyl-6- 6) synthesized in the synthesis section of Synthesis Example 5 Benzoyl-carbazol-3-yl) -2-bromobutan-1-one (5.0 g) was dissolved in 25 mL of THF, and 7.2 g of morpholine was added dropwise to the solution, followed by stirring at room temperature for an hour. The reaction solution was poured into 100 g of ice water and extracted with 150 ml of ethyl acetate. The organic layer is dried over magnesium sulfate, the desiccant is filtered to remove the solvent, the residue is recrystallized from ethyl acetate-hexane, and 1- (N-ethyl-6-benzoyl-carbazole-3- Yl) -2-morpholino-butan-1-one (4.9 g) was obtained (yield 97%).

Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-morpholino-2-ethylpent-4-en-1-one (compound (7)) 55% hydrogenation in 10 ml hexane A dispersion of 0.3 g of sodium was diluted with 10 ml of DMF, and a solution of 3.0 g of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-morpholino-butan-1-one in 10 ml of DMF was stirred. The solution was added dropwise over 30 minutes. After stirring for 1 hour, 0.9 g of allyl bromide was added dropwise at room temperature over 30 minutes and the reaction mixture was stirred at 110 ° C. until no starting material could be found in the sample by thin layer chromatography. After cooling, the reaction mixture was poured into 100 ml of ice water and extracted with toluene. The organic layer is dried over magnesium sulfate, the desiccant is filtered to remove the solvent, and the residue is recrystallized from toluene-hexane to give 1- (N-ethyl-6-benzoyl-carbazol-3-yl. 1.7 g of 2-morpholino-2-ethylpent-4-en-1-one (compound (7)) was obtained (yield 52%).

(Synthesis Example 7)
Synthesis of compound (8)

Synthesis of 2-bromo-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -ethyl-1-one N-ethyl-3-benzoyl-carbazole 9 synthesized in the synthesis section of compound (1) 0.5 g was dissolved in 50 ml of dichloromethane, and 9.1 g of aluminum chloride was further added, and a solution of 7.2 g of bromoacetyl bromide dissolved in 50 ml of dichloromethane was added over 30 minutes with stirring at 0 ° C. After completion of the addition, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 200 g of ice water and extracted with 150 ml of chloroform. The organic layer is dried over magnesium sulfate, the desiccant is filtered off to remove the solvent, the residue is purified by column chromatography (eluent: chloroform), recrystallized from chloroform-hexane, and then 2-bromo. 12.4 g of -1- (N-ethyl-6-benzoyl-carbazol-3-yl) -ethyl-1-one was obtained (93% yield).

Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-ethan-1-one 1- (N-ethyl-6-benzoyl-carbazole-3 of Synthesis Example 5) (Synthesis Example 5) except that -yl) -2-bromobutan-1-one was replaced with -bromo-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -ethyl-1-one In the same manner, the target 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-ethan-1-one was obtained.

Synthesis of 2-dimethylamino-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -4-penten-1-one 1- (N-ethyl-6-benzoyl-carbazol-3-yl)- 4.0 g of 2-dimethylamino-ethane-1-one was dissolved in 30 mL of THF, and 1.5 g of allyl bromide was slowly added dropwise to this solution at about 25 ° C. After the addition, the reaction mixture was stirred for 12 hours at room temperature. The solvent was distilled off and the residue was dissolved in DMF at 60 ° C. To this solution was slowly added 1.6 g of 34% NaOH aqueous solution, and the mixture was cooled to room temperature. The mixture was poured into ice water, and the precipitated solid was filtered to give 2-dimethylamino-1- (N-ethyl). 2.2 g of -6-benzoyl-carbazol-3-yl) -4-penten-1-one was obtained (yield 50%).

Synthesis of 2-dimethylamino-2-allyl-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -4-penten-1-one (compound (8)) 2-dimethylamino-1- ( 2.5 g of N-ethyl-6-benzoyl-carbazol-3-yl) -4-penten-1-one was dissolved in 25 mL of THF, and 1.0 g of allyl bromide was slowly added dropwise to this solution at about 25 ° C. After the addition, the reaction mixture was stirred for 12 hours at room temperature. The solvent was distilled off and the residue was dissolved in 30 ml of DMF at 60 ° C. To this solution, 1.5 g of 34% NaOH aqueous solution was slowly added and cooled to room temperature, and then the mixture was poured into ice water and extracted with toluene. The organic layer is dried over magnesium sulfate, the desiccant is filtered to remove the solvent, the residue is purified by alumina column chromatography (eluent: ethyl acetate / toluene = 1: 4), and 2-dimethyl 0.9 g of amino-2-allyl-1- (N-ethyl-6-benzoyl-carbazol-3-yl) -4-penten-1-one (compound (5)) was obtained (yield 33%).

(Synthesis Example 8)
Synthesis of Compound (10) Synthesis of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-2-phenacyl-butan-1-one (Compound (10)) (Synthesis Example 5) In a solution of 7.0 g of 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-butan-1-one synthesized in 1) in 120 mL of ethyl acetate, phenacyl bromide 6. A solution obtained by dissolving 8 g in 30 mL of ethyl acetate was slowly added dropwise at room temperature. After stirring at 60 ° C. for 8 hours, the mixture was cooled, 150 ml of diethyl ether was added dropwise to the mixed solution, and the precipitate was collected by filtration. The obtained solid content was dissolved in 50 mL of DMF and stirred at about 60 ° C. To the mixed solution, 3.0 g of 34% NaOH aqueous solution was slowly added dropwise and stirred at about 60 ° C. for 5 hours. The reaction solution was poured into ice water, the precipitated solid was filtered, recrystallized from toluene-hexane, and 1- (N-ethyl-6-benzoyl-carbazol-3-yl) -2-dimethylamino-2- 2.7 g of phenacyl-butan-1-one (compound (10)) was obtained (yield 30%).

(Synthesis Example 9)
Synthesis of N-methyl-2-benzoyl-indole Dissolve 24 g of N-methyl-indole in 50 ml of dichloromethane, add 24.4 g of aluminum chloride and stir at 0 ° C., and then add 24.9 g of benzoyl chloride to 50 ml of dichloromethane. The dissolved solution was added over 2 hours. After completion of the addition, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 200 g of ice water and extracted with 200 ml of chloroform. The organic layer is dried over magnesium sulfate, the desiccant is filtered to remove the solvent, the residue is purified by column chromatography (eluent: toluene), recrystallized from ethyl acetate-hexane, N- 9.1 g of methyl-2-benzoyl-indole was obtained (22% yield).

(Synthesis Examples 10 to 15)
By applying the methods of Synthesis Example 1 to Synthesis Example 8 described above, Compound (5), Compound (9), and Compound (11), which are radical polymerization initiators of the present invention, were obtained. Moreover, the compound (12) -compound (15) was also able to be obtained as a comparative example.

  The results of elemental analysis of the radical polymerization initiators of the present invention synthesized in Synthesis Examples 1 to 15 are shown in Table 1.

Example 1
From 5 parts by weight of the compound (1) which is a radical polymerization initiator of the present invention, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 50 parts by weight of polymethyl methacrylate as a binder, and 325 parts by weight of cyclohexanone as a solvent The polymerizable composition was blended with the composition shown in Table 2 to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. This coating film was irradiated with light from a high-pressure mercury lamp at an intensity of 9.0 mW / cm ² through a band-pass filter that selectively transmits only 365 nm light and an ND filter for light intensity adjustment. During this light irradiation, a reflection IR was used to monitor the absorption intensity of 810 cm ⁻¹ corresponding to the characteristic absorption of the acrylic group of the coating film on the stainless steel plate. From the change in absorption intensity over time, the acrylic monomer consumption rate based on the intensity of the above characteristic absorption before light irradiation was calculated. After 10 seconds of light irradiation, the acrylic monomer consumption rate was 13%, and after 30 seconds of light irradiation. The consumption rate was 17%.

(Examples 2 to 10 and Comparative Examples 1 to 9)
In Example 1, compound (1) was used as a radical polymerization initiator, but an experiment was conducted in the same manner as in Example 1 except that it was replaced with compounds (2) to (17). The results are summarized in Table 2. The sensitivity of the initiator system used was expressed in terms of acrylic monomer consumption rate. The greater the acrylic monomer consumption rate, the higher the sensitivity of the tested system. In Comparative Examples 7 to 12, Compound (18), Compound (19), Compound (20), or Compound (21) was also added as a sensitizer.

  In Examples 1 to 11 of the present invention, irradiation with light of 365 nm generates radicals involved in polymerization without using a sensitizer and consumes an acrylic group. When the α-aminoketone skeleton is the same skeleton from comparison between Examples 1 to 5 and 11 and Comparative Examples 1 to 5 and comparison between Examples 6 and 9 and Comparative Examples 4 and 6, the present invention This radical polymerization initiator is clearly more sensitive to light irradiation at 365 nm than known radical polymerization initiators other than the present invention. Further, the comparison between Example 1 and Comparative Example 2, the comparison between Example 6 and Comparative Example 4, and the compound (1) and compound (6) substituted with an aromatic acyl group were substituted with alkanoyl. The compound (13) and the compound (15) are clearly more sensitive. In addition, compared with Examples 1 to 11 and Comparative Example 3, the compounds (1) to (11) of the present invention are known (containing two functional groups in the same molecule) α-aminoacetophenone. It is clearly more sensitive than the derivative. From Comparative Examples 7 to 12, even when carbazole or phenoxathiin is used in combination as a sensitizer, the results are significantly inferior to the sensitizer-integrated radical polymerization initiator as in the present invention. Therefore, the radical polymerization initiator of the present invention is highly effective.

  It can be seen that when the radical polymerization initiator of the present invention is used, the sensitivity is improved as compared with the case where a known α-aminoacetophenone derivative is used as the polymerization initiator. Moreover, it turns out that a sensitivity is improving rather than the case where a well-known alpha-amino acetophenone derivative is used together with a sensitizer as a polymerization initiator.

  The present invention provides a radical polymerization initiator that functions as a radical generator very sensitive to irradiation with energy rays, particularly irradiation with light of 250 to 450 nm. Therefore, the radical polymerization initiator of the present invention can rapidly and surely proceed polymerization and crosslinking reaction using radicals generated by irradiation of energy rays, which have 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, Paints, photosensitive resins for printing plates, color proofs for printing, resists for color filters, resists for black matrices, photo spacers for liquid crystals, screen materials for rear projection, optical fibers, ribs for plasma displays, dry film resists, for printed circuit boards Resist, solder resist, semiconductor photoresist, microelectronic resist, micromachine component manufacturing resist, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat agent, powder coating Adhesives, adhesives, release agents, optical recording media, adhesive, release coat agent composition for image recording materials using microcapsules, and various devices and the like.

Absorption spectrum of compound (1) and compound (16) (acetonitrile)

Claims (4)

A radical polymerization initiator represented by the following general formula (1).
General formula (1)

Wherein A represents a group represented by the following general formula (2), general formula (3), general formula (4), or general formula (5), and Ar ¹ represents a group

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, acyl group, alkoxy group, aryloxy group. , An acyloxy group, an alkoxycarbonyloxy group, an alkylthio group, an arylthio group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, or a halogen atom, and R ^{5 to} R ⁹ are , And together may form an aromatic ring)
R ¹ is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group,
R ² is either the same meanings as R ^1, or a substituted or unsubstituted together with R ^1, an alkylene group or carbon atoms 3 to 9, consisting of 2 to 8 carbon atoms, oxaalkylene groups Or represents an azaalkylene group,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or COR ¹⁰ , or together they have 2 carbon atoms Represents an alkylene group of ˜6, an oxaalkylene group, a thiaalkylene group or an azaalkylene group having 2 to 6 carbon atoms,
R ¹⁰ represents a substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkoxy group, or aryloxy group. ]
General formula (2)

General formula (3)

General formula (4)

General formula (5)

[ Wherein Y represents —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═ CH— or a direct bond,
Z is —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, Or a direct bond,
U represents —O—, —S—, or —N (R ¹¹ ) —;
V represents a nitrogen atom,
W represents a nitrogen atom,
R ¹¹ represents a substituted or unsubstituted alkyl group, alkenyl group, or alkoxy group. ] A is a radical polymerization initiator according to claim 1, which is a general formula (2). A polymerizable composition comprising the radical polymerization initiator (A) according to claim 1 or 2 and a radical polymerizable compound (B). A method for producing a polymer, wherein the polymerizable composition according to claim 3 is polymerized by irradiating it with an energy ray containing light in a wavelength region of 250 nm to 450 nm.

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