JP5391680B2 - Compound, 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, and further, molding resin, casting resin, stereolithography resin, sealant, dental polymerization resin, printing ink, inkjet ink, paint, photosensitive for printing plate Resin, Color proof for printing, Resist for color filter, Resist for black matrix, Photo spacer for liquid crystal, Screen material for rear projection, Optical fiber, Rib material for plasma display, Dry film resist, Resist for printed circuit board, Solder resist, For semiconductor Photoresist for microelectronics Resist, etching resist, microlens array, insulation material, hologram material, optical switch, waveguide material, overcoat agent, powder coating, adhesive, adhesive, release agent, optical recording medium , Adhesives, release coating agents, compositions for image recording materials using microcapsules, novel radical polymerization initiators and polymerizations to obtain polymers with good physical properties in various fields such as devices The present invention relates to a polymerizable composition and a method for producing a polymer 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 examples thereof include α-aminoacetophenone derivatives (Patent Document 1). When the derivative has a substituent containing a sulfur atom or an oxygen atom at the 4-position of the phenyl group, the derivative is used as a photocuring photoinitiator containing a pigment such as, for example, 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 shows 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.

  In recent years, α-aminoacetophenone having a carbazole skeleton has been proposed to further increase sensitivity (Patent Documents 8 and 9). However, there is still no material that satisfies other properties at a high level, such as low yellowing, high solubility in various solvents and monomers, and odor reduction while achieving high sensitivity. Development is still needed.

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 JP 2006-206799 A JP 2008-38089 A

  An object of the present invention is to provide a novel α-aminoacetophenone capable of efficiently generating active radicals upon irradiation with energy rays, particularly light, and functioning as a highly sensitive radical polymerization initiator capable of polymerizing radically polymerizable compounds in a short time. The object is to propose a compound and a curable composition using the compound. Another object is to provide a radical polymerization initiator having a low odor and a high solubility, and excellent in low yellowing, and a polymerization composition using the same, in order to reduce not only the sensitivity but also the work load.

  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 compound represented by the following general formula (1).

General formula (1)

(Wherein R ^{1 to} R ¹¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, trifluoromethyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, (Represents a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)

  The present invention also relates to a radical polymerization initiator comprising the above compound.

  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 compound of the present invention is an α-aminoacetophenone compound having an arylcarbonyl group and a carbazole group substituted by an ethoxyethyl group, and has good absorption characteristics in energy rays, particularly in a wavelength region of 250 nm to 450 nm. And active radicals are efficiently generated in response to light irradiation in the wavelength region. Therefore, the compound which has a remarkably favorable effect as a radical polymerization initiator was able to be provided. Therefore, if the compound of the present invention is used, it becomes possible to reliably realize a polymerization reaction utilizing a radical generated from a polymerization initiator of a conventionally known α-aminoacetophenone derivative, a crosslinking reaction, etc. in a shorter time. As a result, it has become possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. Further, by using the compound of the present invention as the radical polymerization initiator (A), it is possible to provide a curable composition having good characteristics, for example, ink, paint, photosensitive printing plate, proof material, To provide industrially practical oligomers and polymers in the fields of photoresists, hologram materials, sealants, overcoat materials, stereolithography resins, adhesives, etc., and to obtain cured products with good characteristics It was possible to provide a radical polymerization initiator and a polymerizable composition using the same.

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

  First, the radical polymerization initiator (A) of the present invention will be described. The radical polymerization initiator (A) of the present invention is characterized by having an α-aminoacetophenone structure represented by the general formula (1) and having a carbazole group substituted by an arylcarbonyl group and an ethoxyethyl group. In addition, by introducing a carbazole group substituted by an arylcarbonyl group, the compound of the present invention can have light absorption characteristics suitable for a wavelength region of 250 nm to 450 nm. Since it decomposes very efficiently with respect to light irradiation, it can function as a highly sensitive material that efficiently generates a large amount of radicals.

  Furthermore, by having an ethoxyethyl group, it can have high solubility in various solvents and monomers.

General formula (1)

(Wherein R ^{1 to} R ¹¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, trifluoromethyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, (Represents a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)
One specific example of the radical polymerization initiator (A) of the present invention is shown as compound (1).

Compound (1)

  The absorption spectrum of compound (1) in acetonitrile is shown in FIG. Further, the absorption spectrum of a conventional α-aminoacetophenone derivative and compound (2) as a comparative compound is also shown in FIG.

Compound (2)

  As can be seen from FIG. 1, the compound (1) has even absorption characteristics in the wavelength region of 250 to 450 nm as compared with the compound (2). Therefore, compound (1) can absorb more irradiation light in the wavelength region of 250 to 450 nm than compound (2).

  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 4900 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 (2) 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 process from excitation to radical generation is performed with higher efficiency than known α-aminoacetophenone derivatives. That is. The second point is the absorption characteristic of the compound of the present invention. We believe that it can absorb a large amount of light energy necessary to generate radicals, because it has absorption characteristics evenly in the wavelength range of the light source that irradiates light.

  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 have slightly different absorption characteristics 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 (A) of the present invention will be described in detail.

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

The substituents R ¹ to R ¹¹ in the general formula (1) are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Alkoxyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted It represents a heterocyclic oxy group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

Here, examples of the halogen atom in the substituents R ¹ to R ¹¹ include fluorine, chlorine, bromine, and iodine.

The substituted or unsubstituted alkyl group in the substituents R ¹ to R ¹¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a case having 2 to 18 carbon atoms Includes linear, branched, monocyclic or condensed polycyclic alkyl groups interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _{2 -CH 2 -O-CH 2 -CH} 3, -CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, - (CH 2 -CH 2 -O) n -CH 3 ( wherein n is 1 to 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH _2. Examples include —CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _2, but are not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The substituted or unsubstituted alkoxyl group in the substituents R ¹ to R ¹¹ is a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or fused polycyclic alkoxyl groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , — O—CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O—CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O— (CH ₂ —CH ₂ —O) _n — CH ₃ (where n is 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —O—CH _{2 -CH (CH 3) -O-CH} 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include, but are not limited to: Is not to be done.

Examples of the alkylthio group in the substituents R ¹ to R ¹¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group, an ethylthio group, Examples thereof include, but are not limited to, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group.

Examples of the substituted or unsubstituted aryl group in the substituents R ¹ to R ¹¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, 2 -Naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1 -Acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group P-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p Examples thereof include, but are not limited to, bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like. Is not to be done.

Examples of the substituted or unsubstituted aryloxy group in the substituents R ¹ to R ¹¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyl group Although an oxy group, 9-fluorenyloxy group, etc. can be mentioned, it is not limited to these. In addition, the aryl group and the oxygen atom may be bonded at positions other than the above, and these are also included in the category of the substituent represented by R ¹ , R ² and R ³ of the present invention.

Examples of the arylthio group in the substituents R ¹ to R ¹¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms. Specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, 9 -Anthrylthio group, 9-phenanthrylthio group and the like can be mentioned, but are not limited thereto.

Examples of the substituted or unsubstituted heterocyclic group in the substituents R ¹ to R ¹¹ include an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzo Furanyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H- Indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizini Group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group Group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl Group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxyl group Ntoriru group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

The substituted or unsubstituted heterocyclic oxy group in the substituents R ¹ to R ¹¹ is a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2- Examples thereof include, but are not limited to, a carbazolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the heterocyclic thio group in the substituents R ¹ to R ¹¹ include a monocyclic or condensed polycyclic heterocyclic thio group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group, etc. However, it is not limited to these.

Examples of the substituted or unsubstituted alkenyl group in the substituents R ¹ to R ¹¹ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, and there are a plurality of them in the structure. Specific examples of the carbon-carbon double bond may include a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1- Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

As the substituted or unsubstituted acyl group in the substituents R ¹ to R ¹¹ , a carbonyl group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, Alternatively, a monocyclic or condensed polycyclic heterocycle having 4 to 18 carbon atoms, including a carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded. A carbonyl group to which a group is bonded, which may have an unsaturated bond in the structure, and specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl Group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbono group Group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group , 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted amino group in the substituents R ¹ to R ¹¹ include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an 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, cyclododecylamino group, 1-adapter N-amino group, 2-adamantamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group Group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group Group, piperazino 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-biphenyl Nylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group, diphenylamino group, ditolylamino group, N-phenyl-1-naphthylamino group, N-phenyl-2 -Naphtylamino group, N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N-ethylanilino Group, N-methyl-1-naphthylamino group and the like, but are not limited thereto.

  Furthermore, the above-mentioned alkyl group, alkoxyl group, alkylthio group, aryl group, aryloxy group, arylthio group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, alkenyl group, acyl group, amino group are further substituted. It may be substituted with a group.

  Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxyl groups such as methoxy group, ethoxy group and tert-butoxy group, aryl such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylthio group such as methylthio group and tert-butylthio group, arylthio group such as phenylthio group and p-tolylthio group, methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, Amino group such as holino group, piperidino group, phenylamino group, p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group In addition to aryl groups such as naphthyl group, anthryl group, phenanthryl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, Examples thereof include a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumum group, a dimethylsulfoniumum group, and a triphenylphenacylphosphoniumyl group.

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

  The synthesis method for obtaining the compound represented by the general formula (1) and the radical polymerization initiator (A) of the present invention is not particularly limited, and conventionally known chemical reaction, post-treatment method, purification method and analysis method are appropriately selected. By combining them, it is possible to easily synthesize and confirm the structure. Examples of methods for synthesizing α-aminoacetophenone derivatives include the methods described in European Patent Application No. 3002, Japanese Patent Application Laid-Open No. 58-157805, Japanese Patent Application Laid-Open No. 63-264560, and the like. The radical polymerization initiator of the present invention can be synthesized by appropriately replacing the raw materials used.

  Since the radical polymerization initiator (A) 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 It is possible to realize a polymerization reaction using a polymerization initiator, a crosslinking reaction, etc. in a shorter period of 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. It becomes possible. The method for using the radical polymerization initiator of the present invention will be described below.

  The polymerizable 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 the wavelength region of 250 nm to 450 nm. It can be used as a polymerizable composition capable of obtaining a cured product having various characteristics.

  The radical polymerizable compound (B) used in the polymerizable composition of the present invention will be described. The radical polymerizable compound (B) in the present invention means a compound having at least one skeleton capable of radical polymerization in the molecule. These have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and 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 radical 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 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, tricyclodecane dimethylol 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 product 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 Nippon Kayaku Co., Ltd. “Acrylic acid / methacrylic acid ester monomer” series manufactured by Nippon Shokubai Co., Ltd., Nippon Synthetic Chemical Industry Co., Ltd. Made in "Nichigo-UV Shiko urethane acrylate oligomer" series, Shin-Etsu vinyl acetate Co., Ltd. "carboxylic vinyl ester monomers" series include Co. Kohjin Co. "functional monomer" series, and the like.

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

Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, 3169 (1979), vinylcyclopropanes, Macromolecular Chemie Rapid Communication (Makromol. Chem. Rapid Commun.), Volume 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed.), 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. 21), 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (1985) Mounting No 2,3-vinyl oxirane.

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.), Vol. 21, 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) 2) described in Macromolecular Chemie, 183, 1913 (1982) and Macromolecular Chem., 186, 1543 (1985). -Methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, polymer described in Macromolecules, Vol. 15, page 1711 (1982) -5,6-benzo-2-methylene-1,3-diosepane described in Polypre. Preprints, Vol. 34, page 154 (1985).

  Further, 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), Kiyoto Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Association, 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 an arbitrary ratio in order to improve desired properties.

  The radical 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).

  In the polymerizable composition of the present invention, a sensitizer (C) can be added for the purpose of further promoting polymerization. The sensitizer increases the activity with respect to light from the ultraviolet region to the near-infrared region. Therefore, it is preferable to add a sensitizer when it is necessary to promote polymerization.

  Sensitizers (C) that can be used in combination with the polymerizable composition of the present invention include benzophenones, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives Polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin Conductor, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, Examples include tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes. Other specific examples include Ogahara Shin et al., “Dye Handbook” (1986, Kodansha). ), Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special functional materials” (1986, CMC). However, it is not limited to these, and other examples include dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region, and these may be two or more in any ratio as necessary. You can use it. 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. Coumarins can include coumarin 1, coumarin 338, coumarin 102 and the like. Ketocoumarins can include 3,3′-carbonylbis (7-diethylaminocouma). Emissions) and the like, but not limited thereto.

  The sensitizer (C) of the present invention is preferably used in the range of 1 to 10000 parts by weight, more preferably in the range of 2 to 5000 parts by weight with respect to 100 parts by weight of the radical polymerization initiator (A). More preferably, it is in the range of 5 to 3000 parts.

  Furthermore, the polymerizable composition of the present invention may be used by adding a carboxyl group-containing polymer (D) 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 (D) has solubility in an aqueous alkali 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 aqueous alkali solution. It is possible to form a resist pattern. Here, the carboxyl group-containing polymer (D) is a copolymer of acrylic acid ester or methacrylic acid ester and acrylic acid, 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 carboxyl group-containing polymer (D) is preferably used in the range of 10 to 1000 parts by weight, more preferably in the range of 10 to 500 parts by weight, relative to 100 parts by weight of the radical polymerizable compound (B). .

Further, the polymerizable composition of the present invention can be used in combination with other radical polymerization initiators for the purpose of further improving sensitivity.
Other radical polymerization initiators that can be used in combination with the polymerizable composition of the present invention include triazines described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Derivatives, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and US Pat. No. 3,567,453, diazonium compound publications, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37- No. 13109, Japanese Examined Publication No. 38-18015 and Japanese Examined Publication No. 45-9610 The ortho-quinonediazides described in JP-B-55-39162, JP-A-59-140203, and “MACROMOLECULES”, Vol. 10, page 1307 (1977) are used. Various onium compounds including azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging” "Science (J.IMAG.SCI.)", Volume 30, page 174 (1986), metal allene complexes, titanocenes described in JP-A No. 61-151197, "Coordination chemistry review (COORDINATION CHEMISTRY REVIEW), Vol. 84, pages 85 to 277 (1988) and JP-A-2- Transition metal complexes containing transition metals such as ruthenium described in 82701, Aluminate complexes described in JP-A-3-209477, Borate compounds described in JP-A-2-157760, JP-A-55-127550 And 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5-255347. Sulfonium complexes or oxosulfonium complexes described in JP-A No. 54-99185, aminoketone compounds described in JP-A No. 54-99185 and JP-A No. 63-264560, JP-A No. 2001-264530, JP-A No. 2001-261661, JP 2000-80068, JP 2001-233842, Special Table Examples include the oxime ester compounds described in 2004-534797, USP3558309 (1971), USP4202697 (1980), and JP-A-61-245858.

  These radical polymerization initiators are preferably contained in an amount of 10 parts by weight or less based on 100 parts by weight of the radical polymerization initiator (A) of the present invention.

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

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

  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).

  In the polymerizable composition of the present invention, a polymerization accelerator represented by amine, thiol, disulfide or the like or a chain transfer catalyst can be added for the purpose of further promoting the polymerization. The addition of a chain transfer agent suppresses the inhibition of polymerization by oxygen and promotes a uniform photocuring reaction even under high light shielding. Therefore, the addition of a chain transfer agent is preferred when it is necessary to promote 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, and are not particularly limited, but thiol compounds are preferable, and polyfunctional thiol compounds are particularly preferable.

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

  Particularly preferred polyfunctional thiol compounds include compounds having two or more thiol groups, such as hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, 1,4-butanediolbis (3-mercaptopropio 1, 4-butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylol Propane tris (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis ( -Mercaptoethylbenzene), bis (1-mercaptoethyl ester) phthalate, bis (2-mercaptopropyl ester) phthalate, bis (3-mercaptobutyl ester) phthalate, bis (3-mercaptoisobutyl ester) phthalate, ethylene Glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3-mercaptobutyrate), 1,3- Butanediol bis (3-mercaptobutyrate), 1,2-butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), di Pentaerythritol hexakis ( -Mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), 1,4-butanediol bis (2 -Mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol tetrakis (2-mercaptoisobutyrate), ethylene glycol bis (3 -Mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), 1,4-butanediol bis (3-mercaptoisobutyrate), trimethylol Propanetris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), 1,8-octanediol bis (3-mercaptobutyrate) ) 1,8-octanediol bis (2-mercaptopropionate), 1,8-octanediol bis (3-mercaptoisobutyrate), 2,4,6-trimercapto-S-triazine, 2- ( N, N-dibutylamino) -4,6-dimercapto-S-triazine and the like, but are not limited thereto.

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

  In addition, the polymerizable composition of the present invention further comprises an oxygen scavenger such as phosphine, phosphonate, phosphite, a reducing agent, a polymerization accelerator, an antifoggant, an antifading agent, an antihalation agent, a fluorescent whitening, depending on the purpose. Agents, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, UV absorbers, foaming agents, fungicides, thermal polymerization inhibitors, antistatic agents, dyes, organic and inorganic pigments, pigments You may mix and use a precursor, a magnetic body, and the additive which provides various other characteristics.

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

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

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

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

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In addition, unless otherwise indicated, a part shows a weight part in an example.

  First, the compounds used in Examples and Comparative Examples are shown in Table 1, and synthesis examples of the compounds (1) and (3) to (20) of the present invention are shown.

Table 1

Example 1
Synthesis of Compound (1) Synthesis of N- (2-ethoxyethyl) -carbazole 206.2 g of carbazole, 200.0 g of 1-bromo-2-ethoxyethane, 800 g of 40% NaOH aqueous solution, trimethylbenzylammonium chloride 4 g was added, heated to 85 ° C. and stirred for 2 hours. Thereafter, the reaction solution was cooled to room temperature and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off to obtain 295.0 g (yield 99%) of N- (2-ethoxyethyl) -carbazole.

Synthesis of N- (2-ethoxyethyl) -3-benzoyl-carbazole N- (2-ethoxyethyl) dissolved in 120 ml of chloroform with addition of 960 ml of chloroform and 295.58 g of aluminum chloride and stirring at 0 ° C. -After adding 295.0 g of carbazole, 173.3 g of benzoyl chloride dissolved in 1500 ml of chloroform was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 3 hours, and then the reaction solution was poured into 4000 g of ice water and stirred for 1 hour. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was purified by silica gel column chromatography using chloroform / ethyl acetate = 20/1 as a developing solvent. 338.6 g (yield 80%) of N- (2-ethoxyethyl) -3-benzoyl-carbazole was obtained.

Synthesis of N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-bromobutanoyl) -carbazole 560 ml of chloroform and 210.92 g of aluminum chloride were added and stirred at 0 ° C. to 280 ml of chloroform. After adding 135.8 g of N- (2-ethoxyethyl) -3-benzoyl-carbazole dissolved in this manner, 100.0 g of 2-bromo-n-butyryl bromide dissolved in 560 ml of chloroform was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 25 ° C. for 3 hours, and then the reaction solution was poured into 2000 g of ice water and stirred for 1 hour. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was purified by silica gel column chromatography using chloroform as a developing solvent, whereby N- (2-ethoxy 182 g (93% yield) of ethyl) -3-benzoyl-3 ′-(2-bromobutanoyl) -carbazole was obtained.

Synthesis of N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-dimethylaminobutanoyl) -carbazole N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-bromobutanoyl ) -Carbazole (181.8 g), tetrahydrofuran (250 ml) and dimethylamine in a 2 mol / l tetrahydrofuran solution (700 ml) were added, and the mixture was stirred at 60 ° C. for 6 hours. The precipitated solid was removed by furnace and the solvent was distilled off, and then the residue was dissolved in 800 ml of toluene. The toluene solution was washed with ion-exchanged water, the organic layer was dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and N- (2-ethoxyethyl) -3-benzoyl-3 ′ 167 g (99% yield) of-(2-dimethylaminobutanoyl) -carbazole was obtained.

Synthesis of N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-allyldimethylammonium bromidebutanoyl) -carbazole N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-dimethyl) To the place where 167 g of aminobutanoyl) -carbazole and 630 ml of acetonitrile were stirred at 25 ° C., 80 g of allyl bromide was added and stirred at 65 ° C. for 4 hours. Thereafter, the solvent was distilled off until the volume reached about 200 ml, and then this solution was dropped into 2500 ml of diethyl ether over 30 minutes. After completion of the dropwise addition, the precipitate was collected by filtration to obtain 176 g (yield 83%) of N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-allyldimethylammonium bromidebutanoyl) -carbazole. It was.

Synthesis of Compound (1) 161 g of N- (2-ethoxyethyl) -3-benzoyl-3 ′-(2-allyldimethylammonium bromidebutanoyl) -carbazole, 1000 ml of tetrahydrofuran and 75 g of 30% NaOH aqueous solution were added. , And stirred at 65 ° C. for 4 hours. Thereafter, 200 ml of toluene was added and stirred for 30 minutes. This toluene / tetrahydrofuran solution was washed with ion-exchanged water, the organic layer was dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was toluene / ethyl acetate = 10/1. 99.9 g (yield 71%) of compound (1) was obtained by purification by alumina column chromatography using a developing solvent.

Example 2
Synthesis of Compound (3) The target compound (3) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with o-toluoyl chloride.

Example 3
Synthesis of Compound (4) The target compound (4) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with p-toluoyl chloride.

Example 4
Synthesis of Compound (5) The target compound (5) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with p-methoxybenzoyl chloride.

Example 5
Synthesis of Compound (6) The target compound (6) was obtained in the same manner as in Synthesis Example 1, except that p-fluorobenzoyl chloride was replaced with p-fluorobenzoyl chloride.

Example 6
Synthesis of Compound (7) The target compound (7) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with p-phenylbenzoyl chloride.

Example 7
Synthesis of Compound (8) The target compound (8) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 1-naphthoyl chloride.

Example 8
Synthesis of Compound (9) The target compound (9) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with p- (n-butyl) benzoyl chloride.

Example 9
Synthesis of Compound (10) The target compound (10) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 3,5-dimethylbenzoyl chloride.

Example 10
Synthesis of Compound (11) The target compound (11) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 2,4,6-trimethylbenzoyl chloride.

Example 11
Synthesis of Compound (12) The target compound (12) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 3,5-dimethoxybenzoyl chloride.

Example 12
Synthesis of Compound (13) The target compound (13) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with p-cyanobenzoyl chloride.

Example 13
Synthesis of Compound (14) The target compound (14) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with p-nitrobenzoyl chloride.

Example 14
Synthesis of Compound (15) The target compound (15) was synthesized in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 2,3,4,5,6-pentafluorobenzoyl chloride. Obtained.

Example 15
Synthesis of Compound (16) The target compound (16) was obtained in the same manner as in Synthesis Example 1 except that o-nitrobenzoyl chloride was replaced with o-nitrobenzoyl chloride in Synthesis Example 1.

Example 16
Synthesis of Compound (17) The target compound (17) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 3,4,5-trimethoxybenzoyl chloride.

Example 17
Synthesis of Compound (18) The target compound (18) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 3-trifluoromethylbenzoyl chloride.

Example 18
Synthesis of Compound (19) The target compound (19) was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride in Synthesis Example 1 was replaced with 3-trifluoromethoxybenzoyl chloride.

Example 19
Synthesis of Compound (20) The target compound (20) was obtained in the same manner as in Synthesis Example 1 except that the benzoyl chloride in Synthesis Example 1 was replaced with 2-nitro-6-methylbenzoyl chloride.

  Table 2 shows the results of elemental analysis of the compounds of the present invention synthesized in Examples 1 to 19 described above.

Table 2

  Next, Examples using the compound of the present invention as a photopolymerization initiator (A) are shown.

(1) Curability: Examples 20 to 38, Comparative Examples 1 to 16
3 parts by weight of the radical polymerization initiator (A), 10 parts by weight of Daptot DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as the radical polymerizable compound (B), 85 parts by weight of ditrimethylolpropane tetraacrylate, A sensitizer (C) was blended with 0 or 1 part by weight and heated and melted to prepare a coating solution. Table 3 shows the radical polymerization initiator (A) and sensitizer (C) used. This coating solution was applied onto a pet film using a bar coater (# 3). The coated material was irradiated with ultraviolet rays (high pressure mercury lamp 160 W / cm1 lamp), and then rubbed with a cotton cloth and judged at a conveyor speed at which the film was not damaged. The results are shown in Table 3. In addition, curability is so good that the number of the conveyor speed (m / min) of an ultraviolet irradiation device is large.

Table 3

  The photopolymerizable composition using the compound of the present invention as a radical polymerization initiator has higher curability than a photopolymerizable composition using a generally used radical polymerization initiator. (Examples 20 to 38, Comparative Examples 1 and 2). Moreover, it became clear that it has high curability compared with the photopolymerizable composition which used the compound similar to this invention as a radical polymerization initiator (Comparative Examples 3-10). Furthermore, when the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is used as a radical polymerization initiator in combination with a commonly used radical polymerization initiator and a sensitizer. It became clear that it has higher curability than (Comparative Examples 11 to 16).

(2) Yellowing: Examples 39 to 57, Comparative Examples 17 to 32
5 parts by weight of the radical polymerization initiator (A), 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as the radical polymerizable compound (B), 85 parts by weight of ditrimethylolpropane tetraacrylate, A sensitizer (C) was blended with 0 or 1 part by weight and heated and melted to prepare a coating solution. Table 4 shows the radical polymerization initiator (A) and sensitizer (C) used. This coating solution was applied onto a pet film using a bar coater (# 3). Cut the coated material cured under the same conditions as the curability, 30 panelists relatively determined the yellowing of the coated material, evaluated in five stages from 1 (bad) to 5 (good) did. The results are shown in Table 4.

Table 4

  It is clear that the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is excellent in yellowing compared with a photopolymerizable composition using a commonly used radical polymerization initiator. It became. Furthermore, when the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is used as a radical polymerization initiator in combination with a commonly used radical polymerization initiator and a sensitizer. It became clear that it was excellent in yellowing.

(3) Odor: Examples 58 to 76, Comparative Examples 33 to 48
5 parts by weight of the radical polymerization initiator (A), 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as the radical polymerizable compound (B), 85 parts by weight of ditrimethylolpropane tetraacrylate, A sensitizer (C) was blended with 0 or 1 part by weight and heated and melted to prepare a coating solution. Table 5 shows the radical polymerization initiator (A) and sensitizer (C) used. This coating solution was applied onto a pet film using a bar coater (# 3). The coated material cured under the same conditions as the curability is finely cut and packed in glass bottles to collect odors. 30 panelists relatively determine the odor properties, and 5 from 1 (bad) to 5 (good). Rated by stage. The results are shown in Table 5.

Table 5

  It is clear that the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is superior in odor compared with a photopolymerizable composition using a commonly used radical polymerization initiator. It became. It is presumed that the reason why the photopolymerizable composition of the present invention is excellent in odor is because there is little volatilization of a radical polymerization initiator after curing or its decomposition product.

(4) Solubility: Examples 77-95, Comparative Examples 49-58
10 parts by weight of the radical polymerization initiator (A) and 90 parts by weight of dipentaerythritol hexaacrylate were blended and heated and melted at 80 ° C. for 24 hours. After this melt was stored at 22 ° C. for 1 week, it was visually confirmed whether or not the radical polymerization initiator (A) was precipitated. The results and the radical polymerization initiator (A) and sensitizer (C) used are shown in Table 6.

Table 6

  It became clear that the compound of this invention is a compound excellent in the solubility with respect to the acrylic monomer.

(5) Comprehensive evaluation Table 7 shows a comprehensive evaluation on curability, yellowing, odor, and solubility.

The evaluation criteria for each evaluation item are shown below.
(1) Curability ○: Conveyor speed (m / min) is 40 or more.
X: Conveyor speed (m / min) is less than 40.
(2) Yellowing ○: The relative judgment value is 4 or more.
X: The relative judgment value is 3 or less.
(3) Odor ○: Relative judgment value is 5.
X: The relative judgment value is 4 or less.
(4) Solubility ○: No precipitate.
X: There is a precipitate.

Table 7

  A photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is a generally used radical polymerization initiator or a photopolymerizable composition in which a radical polymerization initiator and a sensitizer are used in combination. It became clear that it was excellent in curability compared with. In addition, the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator can suppress coloring and odor after curing of the polymerizable composition compared to a general photopolymerizable composition, It became clear that all the requirements of high curability, low yellowing, low odor, high solubility, which were difficult with a photopolymerizable composition using a conventional radical polymerization initiator, were satisfied. Furthermore, it has become clear that even if a compound having a structure similar to that of the compound of the present invention is used, all of these requirements cannot be satisfied.

  The compound of the present invention is an α-aminoacetophenone compound having an arylcarbonyl group and a carbazole group substituted by an ethoxyethyl group, and has good absorption characteristics in energy rays, particularly in a wavelength region of 250 nm to 450 nm. And active radicals are efficiently generated in response to light irradiation in the wavelength region. Therefore, the compound which has a remarkably favorable effect as a radical polymerization initiator was able to be provided. Therefore, if the compound of the present invention is used, it becomes possible to reliably realize a polymerization reaction utilizing a radical generated from a polymerization initiator of a conventionally known α-aminoacetophenone derivative, a crosslinking reaction, etc. in a shorter time. As a result, it has become possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Ink-jet ink, paint, photosensitive resin for printing plates, color proof for printing, resist for color filters, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display, dry film resist, Resist for printed circuit boards, solder resist, photoresist for semiconductor, resist for microelectronics, resist for micromachine parts manufacturing, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat Agent, powder coatings, adhesives, pressure-sensitive adhesives, release agents, optical recording media, adhesive, release coat agent composition for image recording materials using microcapsules, and various devices and the like.

FIG. 1 is an absorption spectrum in acetonitrile of the compound (1) of the present invention and the compound (2) which is a conventional α-aminoacetophenone derivative.

Claims (5)

A compound represented by the following general formula (1).
General formula (1)

(Wherein R ^{1 to} R ¹¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, trifluoromethyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, Represents a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)   A radical polymerization initiator (A) comprising the compound according to claim 1.   A polymerizable composition comprising the radical polymerization initiator (A) according to claim 2 and a radical polymerizable compound (B).   The polymerizable composition according to claim 3, further comprising a sensitizer (C).   A method for producing a polymer, wherein the polymerizable composition according to claim 4 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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