JP5481856B2 - Photopolymerization initiator, polymerizable composition, and method for producing polymer - Google Patents

Description

The present invention relates to a novel photopolymerization 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 coatings, compositions for image recording materials using microcapsules, novel photopolymerization initiators and polymerization to obtain polymers with good physical properties in various 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). The polymerizable composition containing the α-aminoacetophenone derivative is
It is known that it is a highly sensitive polymerizable composition that can be cured with a small amount of light irradiation. But,
From the viewpoint of cost reduction and productivity improvement in recent years, the α-aminoacetophenone derivative is preferably used in a highly sensitive polymerizable composition that can be cured in a shorter time and with a smaller amount of light irradiation. Even the system using a combination of a photosensitizer and an aromatic carbonyl compound was not sensitive enough to cope with various newly proposed processes. Therefore, 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, as a highly sensitive photoinitiator, α containing two functional groups in the same molecule
-Aminoacetophenone derivatives have also been proposed. Α- containing two functional groups in the same molecule
It is known that aminoacetophenone derivatives not only exhibit high activity but also do 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.

On the other hand, when a conventional photoinitiator is used, various problems occur in addition to the curable surface of the polymerizable composition. Among them, the problem of volatilization and odor of a photopolymerization initiator that occurs from a polymerizable composition cured after light irradiation has been a major problem in recent years. The problem of volatilization and odor of the photopolymerization initiator that occurs from the polymerizable composition cured after light irradiation not only affects the coated product, but also the environment of the coated site, and further degrades the performance of the coated product. Therefore, improvement is needed. Then, the photoinitiator which aimed at the volatilization and odor improvement of the photoinitiator after polymeric composition hardening was also proposed (patent document 7, 8, 9). However, even in a polymerizable composition using these photopolymerization initiators, suppression of volatilization and odor of the photopolymerization initiator that occurs from the polymerizable composition after further curing is desired.
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-T-2006-525399 Special table 2007-525573

The polymerizable composition containing these conventionally known 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 is required. In addition, the volatilization and odor generation of the photopolymerization initiator and photopolymerization initiator decomposition products that occur from the polymerizable composition after curing may damage the environment of the coated product and the coating site, and may deteriorate the performance of the coated product. Therefore, improvement is required. In the polymerizable composition, it is difficult to satisfy all the requirements regarding curability and volatilization and odor of the photopolymerization initiator generated from the polymerizable composition. Accordingly, an object of the present invention is to provide a novel photopolymerization initiator and a polymerizable composition using the photopolymerization initiator for satisfying all these requirements.

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

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group. R ³ and R ⁴ may be combined to form a ring.
R ⁵ to R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, or a substituted or unsubstituted aryl group. Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted Arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, substituted Or an unsubstituted acyl group, substituted or unsubstituted A substituted alkyloxycarbonyl group or a substituted or unsubstituted aryloxycarbonyl group is represented.
R ^{12 to} R ¹⁶ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkyl sulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, represents a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group, a R ¹² to R ¹⁶ At least one is a halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted aryl Sulfonyl group, substituted or Unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, and is either substituted or unsubstituted aryloxycarbonyl group. )

The present invention, at least one of R ¹² to R ^16, a nitro group, and to the photopolymerization initiator is either a substituted or unsubstituted acyl group.

The present invention, at least one of R ¹² to R ^16, relates to the photopolymerization initiator is lower following general formula (2).
General formula (2)

(Wherein R ^{17 to} R ²¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, A substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group is represented.)
The present invention further relates to a polymerizable composition comprising the photopolymerization initiator (A) and the radical polymerizable compound (B).

Furthermore, this invention relates to the manufacturing method of a polymer which irradiates and polymerizes the said polymeric composition by the energy ray containing the light of the wavelength range of 250 nm to 450 nm.

The photopolymerization initiator of the present invention is characterized by having a phenylcarbazole group in the central skeleton, and has good absorption characteristics in energy rays, particularly in the wavelength region of 250 nm to 450 nm, and light in this wavelength region. It is possible to function as a highly sensitive photo radical generator without using a sensitizer in combination with irradiation. Therefore, if the polymerization initiator of the present invention is used, it becomes possible to realize a polymerization reaction and a crosslinking reaction using radicals generated from a polymerization initiator of a conventionally known α-aminoketone derivative in a shorter time. As a result, it is possible to realize a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. Further, since the photopolymerization initiator of the present invention has its specific structure, in the polymerizable composition containing the photopolymerization initiator, volatilization and odor of the photopolymerization initiator that occurs from the cured polymerizable composition. Can be suppressed.

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

First, the photopolymerization initiator (A) of the present invention will be described. The photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1) and is characterized by having an N-phenylcarbazole group in the central skeleton. Further, by introducing this N-phenylcarbazole group, the compound of the present invention can have light absorption characteristics suitable for a wavelength region of 250 nm to 450 nm. 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
General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group. R ³ and R ⁴ may be combined to form a ring.

R ⁵ to R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, or a substituted or unsubstituted aryl group. Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted Arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, substituted Or an unsubstituted acyl group, substituted or unsubstituted A substituted alkyloxycarbonyl group or a substituted or unsubstituted aryloxycarbonyl group is represented.
R ^{12 to} R ¹⁶ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkyl sulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, represents a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group, a R ¹² to R ¹⁶ At least one is a halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted aryl Sulfonyl group, substituted or Unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, and is either substituted or unsubstituted aryloxycarbonyl group. ) One specific example of the photopolymerization initiator (A) of the present invention is shown as compound (a).
Compound (a)

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

As can be seen from FIG. 1, the compound (a) is 250 to 450 n in comparison with the compound (b).
It has absorption characteristics evenly in the wavelength region of m. Therefore, compound (a) is compound (b)
As compared with the above, more irradiation light in the wavelength region of 250 to 450 nm can be absorbed.

Further, the compound (a) which is the 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 exceeds the case where the α-aminoacetophenone derivative (b) 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, excitation ~
That is, the radical generation process is performed more efficiently than known α-aminoacetophenone derivatives. 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 dominant 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,
Examples include, but are not limited to, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulse emission xenon lamps. Also, deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-
A laser having an emission wavelength in a wavelength region of 250 nm to 450 nm, such as a Cd laser, a nitrogen laser, a Xe-Cl excimer laser, a Xe-F excimer laser, and a semiconductor excitation solid laser, can also be used as a suitable energy ray source. The polymerization initiator (A
) All have suitable absorption in the wavelength region of 250 nm to 450 nm, and the absorption characteristics are slightly different depending on the substituent, but function as a very sensitive radical polymerization initiator by appropriately selecting the above light source. Is possible. 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 has a general formula (
As shown in 1), various substituents can be introduced. By introducing substituents,
The radical polymerization initiator (A) of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as absorption maximum wavelength and transmittance, and the solubility in the resin or solvent used together.

The substituents R ¹ and R ² in the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group. Represents an alkenyl group. R ¹ and R ² may be integrated to form a ring.

Here, the substituted or unsubstituted alkyl group is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1
Examples include a linear, branched, monocyclic or condensed polycyclic alkyl group 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. In addition, the number of carbon atoms is 2 to 18, and in some cases-
Specific examples of linear and branched alkyl groups 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), - (C
H ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH
₃ ) —O—CH ₂ —CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like can be mentioned, 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,
It is not limited to these.

Examples of the substituted or unsubstituted aryl group include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 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-
Azulenyl 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,
Examples thereof include p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, etc. It is not limited to.

Examples of the substituted or unsubstituted heterocyclic group 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, a 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group,
2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group,
Pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-
Indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, 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, 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, morpholinidyl group Thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-coumarinyl group, etc. Not intended to be.

Examples of the substituted or unsubstituted alkenyl group include straight-chain, branched-chain having 1 to 18 carbon atoms,
A monocyclic or condensed 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, an 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-
Examples thereof include a hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a cyclopentenyl group, a cyclohexenyl group, a 1,3-butadienyl group, a cyclohexadienyl group, and a cyclopentadienyl group. However, it is not limited to these.

R ¹ and R ² may be bonded to the carbon atom of the general formula (1) at substitution positions other than those described above, and these are also the substituents represented by R ¹ and R ² of the present invention. Included in the category.

R ¹ and R ² may be integrated to form a ring.

When R ¹ and R ² are combined to form a ring, the formed site has 2 carbon atoms.
A substituted or unsubstituted alkylene group having 8 to 8 carbon atoms, a substituted or unsubstituted oxaalkylene group having 3 to 9 carbon atoms, or a substituted or unsubstituted azaalkylene group having 3 to 9 carbon atoms.

Here, as a ring formed when the substituted or unsubstituted alkylene group is an alkylene group having 2 to 8 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring,
Although a cyclohexane ring, a cycloheptane ring, a cyclooctane ring etc. can be mentioned, It is not limited to these.

A substituted or unsubstituted oxaalkylene group having 3 to 9 carbon atoms,
Examples of the ring formed when the substituted or unsubstituted azaalkylene group is an azaalkylene group having 3 to 9 carbon atoms include a tetrahydrofuran ring, a pyrrolidine ring, a piperidine ring, and the like. Is not to be done.

Of the above substituents, R ¹ is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group in terms of the difficulty of synthesis and sensitivity as a radical generator. Is particularly preferably a methyl group, an ethyl group, a benzyl group, a p-methylbenzyl group, or a 2-propenyl group.

The substituents R ³ and R ⁴ in the general formula (1) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group,
It represents a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group.

The substituted or unsubstituted alkyl group for R ³ and R ⁴ has the same meaning as the substituted or unsubstituted alkyl group for R ¹ and R ² described above.

The substituted or unsubstituted alkyloxy group for R ³ and R ⁴ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. There may be mentioned linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group,
Examples thereof include, but are not limited to, a cyclohexyloxy group, an adamantyloxy group, a norbornyloxy group, a boronyloxy group, and a 4-decylcyclohexyloxy group. Specific examples of the linear or branched alkyloxy 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 ( wherein m is 5 _{1), - O-CH 2} -CH (C
_{H 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 alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

The substituted or unsubstituted aryl group for R ³ and R ⁴ has the same meaning as the substituted or unsubstituted aryl group for R ¹ and R ² described above.

R ^3, and examples of the substituted or unsubstituted aryloxy group in R ^4,. 4 to carbon atoms
18 monocyclic or condensed polycyclic aryloxy groups are mentioned, and specific examples thereof include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1- A pyrenyloxy group, a 5-naphthacenyloxy group, a 1-indenyloxy group, a 2-azurenyloxy group, a 1-acenaphthyloxy group, a 9-fluorenyloxy group, and the like can be mentioned, but are not limited thereto. It is not a thing. In addition, the aryl group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ³ , R ⁴ , R ⁷ and R ⁸ of the present invention.

The substituted or unsubstituted heterocyclic group for R ³ and R ⁴ has the same meaning as the substituted or unsubstituted heterocyclic group for R ¹ and R ² described above.

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

The substituted or unsubstituted alkenyl group for R ³ and R ⁴ has the same meaning as the substituted or unsubstituted alkenyl group for R ¹ and R ² described above.

As the substituted or unsubstituted acyl group in R ³ and R ⁴ , 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, A monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded. 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, Examples include crotonoyl group, oleoyl group, cinnamoyl group benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group and isonicotinoyl group. However, it is not limited to these. In addition, the aryl group and the carbonyl group, the heterocyclic group and the carbonyl group may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ³ and R ⁴ of the present invention. It is.

R ³ and R ⁴ may be combined to form a ring.

When R ³ and R ⁴ are combined to form a ring, the formed site has 2 carbon atoms.
A substituted or unsubstituted alkylene group having 6 to 6 carbon atoms, a substituted or unsubstituted oxaalkylene group having 2 to 6 carbon atoms, a substituted or unsubstituted thiaalkylene group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms And a substituted or unsubstituted azaalkylene group.

Here, as a ring formed when the substituted or unsubstituted alkylene group is an alkylene group having 2 to 6 carbon atoms, a propyleneimine ring, a pyrrolidine ring, a piperidine ring, a pipecoline ring, or the like is formed. Examples can be given, but the present invention is not limited to these examples.

A substituted or unsubstituted oxaalkylene group having 2 to 6 carbon atoms,
As the ring formed when the substituted or unsubstituted thiaalkylene group is a thiaalkylene group having 2 to 6 carbon atoms, or the substituted or unsubstituted azaalkylene group is an azaalkylene group having 2 to 6 carbon atoms, , Morpholine ring, thiomorpholine ring, thiazolidine ring, piperazine ring, or homopiperazine ring can be mentioned as an example,
It is not limited to these.

Among the above-mentioned substituents, R ³ and R ⁴ are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, R in view of synthesis difficulty and sensitivity as radical generators. ^{When 3} and R ⁴ are combined to form a ring, a substituted or unsubstituted alkylene group, a substituted or unsubstituted oxaalkylene group, a substituted or unsubstituted thiaalkylene group, a substituted or unsubstituted aza An alkylene group is preferable, and —NR ³ (R ⁴ ) is, for example, dimethylamino group, diethylamino group, bis-2-methyloxyethylamino group, morpholino group, thiomorpholino group, prolidino group, piperidino group, piperazino group, or 1 −
A methylpiperazino group is particularly preferred.

The substituents R ^{5 to} R ¹⁶ in the general formula (1) are each independently a hydrogen atom, a halogen atom,
Nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic ring A group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group,
Substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted An amino group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group is represented.

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

Examples of the haloalkyl group include alkyl having 1 to 15 carbon atoms in which all the substituents are substituted with the halogen atoms described above, and specific examples include a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, Iodomethyl, pentafluoroethyl, pentapentachloroethyl, pentabromoethyl, pentaiodoethyl, trifluorodibromoethyl, tribromodiiodoethyl, heptafluoropropyl, heptachloropropyl, heptabromo Propyl group, nonafluorobutyl group, nonachlorobutyl group,
Nonabromobutyl group, undecafluoropentyl group, undecachloropentyl group, undecabromopentyl group, tridecafluorohexyl group, tridecachlorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, nonadecafluorononyl group ,
Examples thereof include, but are not limited to, henicosafluorodecyl group, tricosafluoroundecyl group, pentacosafluorododecyl group, and the like.

The substituted or unsubstituted alkyl group in R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted alkyl group in R ¹ and R ² described above.

The substituted or unsubstituted alkyloxy group in R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted alkyloxy group in R ³ and R ⁴ described above.

The substituted or unsubstituted aryl group in R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted aryl group in R ³ and R ⁴ described above.

The substituted or unsubstituted aryloxy group for R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted aryloxy group for R ³ and R ⁴ described above.

The substituted or unsubstituted heterocyclic group in R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted heterocyclic group in R ³ and R ⁴ described above.

The substituted or unsubstituted heterocyclic oxy group in R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted heterocyclic oxy group in R ³ and R ⁴ described above.

The substituted or unsubstituted alkenyl group for R ⁵ to R ¹¹ has the same meaning as the substituted or unsubstituted alkenyl group for R ¹ and R ² described above.

As the substituted or unsubstituted alkylsulfanyl group, a straight chain having 1 to 18 carbon atoms,
Examples include branched, monocyclic or condensed polycyclic alkylthio groups. Specific examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio. Examples include, but are not limited to, groups.

Examples of the substituted or unsubstituted arylsulfanyl group include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group and the like, but are not limited thereto.

The substituted or unsubstituted alkylsulfinyl group is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. Specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group,
Hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2
-Ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group and the like may be mentioned, but not limited thereto.

As the substituted or unsubstituted arylsulfinyl group, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group Group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfinyl group § sulfonyl phenylsulfinyl group, 4-dimethylaminophenyl sulfinyl but Le group and the like, but is not limited thereto.

The substituted or unsubstituted alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, and a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, and the like. Is not to be done.

As the substituted or unsubstituted arylsulfonyl group, an arylsulfonyl group having 6 to 30 carbon atoms is preferable. Specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl Group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4- Although such methylamino phenylsulfonyl group,
It is not limited to these.
Examples of the substituted or unsubstituted amino group include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, 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, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, 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.

As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

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

The substituted or unsubstituted acyl group for R ^{5 to} R ¹⁶ has the same meaning as the substituted or unsubstituted acyl group for R ¹ and R ² described above.

Examples of the substituted or unsubstituted alkyloxycarbonyl group include an alkyloxy group having 2 to 20 carbon atoms. Specific examples include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, Examples include, but are not limited to, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, a trifluoromethyloxycarbonyl group, and the like.

Examples of the substituted or unsubstituted aryloxycarbonyl group include aryloxy groups having a carbon number of ~, and specific examples thereof include a phenyloxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, and 2-methyl. Phenyloxycarbonyl group, 2-methyloxyphenyloxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 2-dimethylaminophenyloxycarbonyl group, 2-fluorophenyloxycarbonyl group, 2-nitrophenyloxycarbonyl group, 4- Methylphenyloxycarbonyl group, 4-methyloxyphenyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4
-Phenyloxyphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-nitrophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3- Examples thereof include, but are not limited to, a cyanophenyloxycarbonyl group and a 3-trifluoromethylphenyloxycarbonyl group.

Here, at least one of R ^{12 to} R ¹⁶ is a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted group. acyl group, Ri substituted or unsubstituted alkyloxycarbonyl group or a substituted or unsubstituted aryloxycarbonyl group der, preferably, at least one, a nitro group, or a substituted or unsubstituted acyl group, particularly preferably Is at least one of the following general formula (2).
General formula (2)

R ^{17 to} R ²¹ in the general formula (2) are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl Represents a sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group .

R ^{17 to} R ²¹ halogen atom, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted amino group, substituted Or an unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group is a halogen atom, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group in R ⁵ and R ¹⁶ Unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group , Substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group.

Examples of the substituent that the substituent in R ¹ and R ² , R ³ and R ⁴ , R ^{5 to} R ¹⁶ , or R ^{17 to} R ²¹ may further include a hydroxyl group, a mercapto group, and a cyano group Nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkyloxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkyloxycarbonyl group, alkylsulfanyl group, arylsulfanyl group, complex Examples thereof include, but are not limited to, a ring sulfanyl group and an amino group.

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

The alkyl group is a straight chain, branched chain, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally interrupted by one or more —O—. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups. 1 to 1 carbon
Specific examples of 8 linear, branched, monocyclic or condensed polycyclic alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl groups. Decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group,
Isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, ter
Examples include t-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. It is not limited. 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 -C
H 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 —CH ₃ —,
Examples include —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,
It is not limited to these.

Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-
Examples include phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group, etc.
Is not to be done.

The heterocyclic group includes a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and has 4 to 18 carbon atoms.
A monocyclic or condensed polycyclic heterocyclic group, and specific examples thereof include 2-furanyl group, 2-thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, A 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, a 9-acridinyl group and the like can be mentioned, but the invention is not limited to these.

The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. A carbonyl group to which a cyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom,
Examples include a carbonyl group having a phosphorus atom and a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms bonded thereto, which may have an unsaturated bond in the structure.
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, oleoyl group, benzoyl group, 2-methylbenzoyl group 4-methyloxybenzoyl group, 1-naphthoyl group, 2
-Naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group,
Examples thereof include, but are not limited to, isonicotinoyl group, 9-anthroyl group, and 5-naphthacenoyl group.

Examples of the alkyloxy group include linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms. Or a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. 2 carbon atoms
Specific examples of linear or branched alkyloxy groups which are from 1 to 18 and are 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 (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3
(Where m is 5 _{1), - O-CH 2} -CH (CH 3) -O-CH 2 -CH 3 -, -
Examples thereof include, but are not limited to, O—CH ₂ —CH— (OCH ₃ ) ₂ .

Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-
An acenaphthyloxy group, a 9-fluorenyloxy group, etc. are mentioned, However, It is not limited to these.

The heterocyclic oxy group includes a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and has 4 carbon atoms.
To 18 monocyclic or condensed polycyclic heterocyclic oxy groups, and specific examples thereof include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzoyl group. Examples include a furyloxy group, a 2-benzothienyloxy group, a 2-carbazolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, a 9-acridinyloxy group, etc. It is not limited to.

The acyloxy group includes a hydrogen atom, a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or 6 to 1 carbon atoms.
A carbonyloxy group having a monocyclic or condensed polycyclic aryl group having 8 to 18 carbon atoms and a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. Specific examples include 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 group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1
-Naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group,
Examples thereof include, but are not limited to, a 9-anthroyloxy group and a 5-naphthacenoyloxy group.

Examples of the alkyloxycarbonyl group include an alkyloxycarbonyl group having 2 to 20 carbon atoms. Specific examples include a methyloxycarbonyl group, an ethyloxycarbonyl group,
Propyloxycarbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2- Naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-
Dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methyloxyphenyloxycarbonyl group, 2-butyloxyphenyloxycarbonyl group, 3- Examples include, but are not limited to, cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenoloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methyloxyphenyloxycarbonyl group and the like. It is not a thing.

Examples of the alkylsulfanyl group include linear, branched, monocyclic or condensed polycyclic alkylsulfanyl groups having 1 to 18 carbon atoms. Specific examples include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, Examples thereof include butylsulfanyl group, pentylsulfanyl group, hexylsulfanyl group, octylsulfanyl group, decylsulfanyl group, dodecylsulfanyl group, octadecylsulfanyl group and the like.

Examples of the arylsulfanyl group include monocyclic or condensed polycyclic arylsulfanyl groups having 6 to 18 carbon atoms, and specific examples thereof include phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 9-anthryl. Examples thereof include, but are not limited to, a sulfanyl group and a 9-phenanthrylsulfanyl group.

Examples of the heterocyclic sulfanyl group include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
Furyl group, 2-thienylsulfanyl group, 2-pyrrolylsulfanyl group, 6-indolylsulfanyl group, 2-benzofurylsulfanyl group, 2-benzothienylsulfanyl group, 2-carbazolylsulfanyl group, 3-carbazolyl Examples thereof include, but are not limited to, a sulfanyl group and a 4-carbazolylsulfanyl group.

The amino group is preferably an amino group of 0-50 carbon atoms, and specific examples, -NH ₂
, N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-
N-arylamino group, N, N-disulfonylamino group and the like can be mentioned. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-
Cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N
-Decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2-
Methyloxyphenylamino group, N-2-isopropyloxyphenylamino group, N-2
-(2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3
-Nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, N-4-methyloxyphenylamino group, N-4-cyanophenylamino group, N-4-tri Fluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N- Dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutyl Carbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N N- (di-butylsulfonyl) amino group, N, N- (diphenyl-sulfonyl) amino group, and the like, but not limited to Korara.

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

The synthesis method for obtaining the photopolymerization initiator (A) of the present invention is not particularly limited, and the structure can be easily synthesized by appropriately combining conventionally known chemical reactions, post-treatment methods, purification methods and analysis methods. It is possible to confirm. Methods for synthesizing α-aminoketone derivatives are disclosed in European Patent Application No. 3002, Japanese Patent Laid-Open No. 58-157805, Japanese Patent Laid-Open No. 63-264560.
The photopolymerization initiator (A) of the present invention can be synthesized by appropriately replacing the raw materials used in the synthesis described therein.

The photopolymerization initiator (A) of the present invention functions as a highly sensitive photopolymerization initiator by irradiation with energy rays, particularly in the wavelength region of 250 nm to 450 nm. It is possible to realize polymerization reactions and crosslinking reactions using initiators in a shorter period of time, and as a result, it is possible to achieve significant increases in sensitivity and improved properties for various applications using these reactions. It becomes. Below, the utilization method of the photoinitiator (A) of this invention is described.

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

The radical polymerizable compound (B) used 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-methyloxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butyloxyethyl acrylate, methyloxytriethylene glycol acrylate, methyloxypolyethylene glycol # 400 acrylate, methyloxydipropylene glycol acrylate, methyloxytripropylene glycol acrylate , Methyloxypolypropylene glycol acrylate, ethyloxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyester 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-acryloyloxypropyl tetrahydro phthalate.

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 # 4
00 diacrylate, polypropylene glycol # 700 diacrylate, neopentyl glycol diacrylate, neopentyl 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-acryloxypolyethyloxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A di Acrylate, 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, tricyclodecane dimethylol di Acrylate, 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-methyloxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butyloxyethyl methacrylate, methyloxytriethylene glycol methacrylate, methyloxypolyethylene glycol # 400 methacrylate, methyloxydipropylene glycol methacrylate, methyloxytripropylene glycol methacrylate , Methyloxypolypropylene glycol methacrylate, ethyloxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, cresyl polyethylene Glycol methacrylate, p- nonyl 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, neopentyl glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct 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-methacryloxy) Polyethyloxyphenyl) propane, bisphenol A dimethacrylate, EO-modified bisphenol A di Methacrylate, 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 trimethacrylate, 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-methyloxystyrene, pt-butyloxystyrene, pt-
Butyloxycarbonylstyrene, pt-butyloxycarbonyloxystyrene, 2
, 4-Diphenyl-4-methyl-1-pentene.

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

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

  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 Chemie Rapid Communication (Makromol)
Chem. Rapid Commun.), Volume 5, page 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.), Vol. 21, page 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (19
85)), 2,3-divinyloxiranes.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (
J. Polym. Sci. Polym. Chem. Ed.), 20, 3021 (1982) and Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym.
Lett. Ed.), Volume 21, p. 373 (1983), 2-methylene-1,3-dioxepane, Polymer Prepreprints, Volume 34, p. 152 (198).
5)) Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 20, 361 (1982), Macromolecular Chemromol., 183, 1913 (198)
2-methylene-4-phenyl-1,3-dioxepane, Macromolecules, described in Makromol. Chem., 186, 1543 (1985). Vol. 15, p. 1711 (1982) 4,7-dimethyl-2-methylene-1,3-dioxepane, polymer pre-print (Polym. Prep
rints), 34, 154 (1985).
, 3-Giosepan.

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 Group, Akamatsu Kiyoshi, “New Photosensitive Resin Technology” (1987, CMC), Endo Takeshi, “Thermosetting Polymer Refinement”, (1986, CMC) ),
Takiyama Shinichiro, “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 a film formed using the photopolymerizable composition of the present invention is partially cured,
It is possible to form a so-called negative resist pattern from the difference in solubility in an alkaline aqueous solution. 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,
Examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and isobornyl methacrylate.

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, 3-
Examples include tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

The photopolymerization initiator (A) of the present invention is 0% relative to 100 parts by weight of the radical polymerizable compound (B).
. It is preferably used in the range of 01 to 60 parts by weight. Also, carboxyl group-containing polymers (
C) is preferably used in the range of 20 to 500 parts by weight and more preferably in the range of 50 to 150 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B).

The 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, Polymers and copolymers such as polyvinyl esters are mentioned, and more specifically, polymethacrylate,
Polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenolic resin, epoxy resin, alkyd resin, etc., supervised by Kiyoshi Akamatsu, “Practical technology of new photosensitive resin” (see MC, 1987) and "10188 chemical products", 657-76.
An organic polymer known in the industry described on page 7 (Chemical Industry Daily, 1988) can be mentioned.

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.

The polymerizable composition of the present invention has sufficient sensitivity without using other sensitizers,
Furthermore, it can be used in combination with a sensitizer and other photopolymerization initiators for the purpose of improving sensitivity and improving film properties after curing.

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 Pigment, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative,
Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , Naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, etc. Edited by Nobu Okawara, "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemicals of Functional Dyes" (1 81, CMC), the dyes and sensitizers described in “Special Functional Materials” (1986, CMC) edited by Tadasaburo Ikemori et al. Examples include dyes and sensitizers that absorb light in the near-infrared region, and two or more of these may be used in any ratio as necessary.
Among the sensitizers, the thioxanthone derivatives include 2,4-diethylthioxanthone,
2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propyloxythioxanthone and the like can be mentioned. Examples of benzophenones include benzophenone, 4-methylbenzophenone, Examples include 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethyloxybenzophenone, 4,4′-bis (diethylamino) benzophenone, and examples of coumarins include coumarin 1 , Coumarin 338, Coumarin 102, and the like. Examples of ketocoumarins include 3,3′-
Examples thereof include, but are not limited to, carbonyl bis (7-diethylaminocoumarin).

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 3
69, IRGACURE 379, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 7
84, Irgacure 261, Irgacure OXE-01 (CGI124), CGI2
42 (Ciba Specialty Chemicals), Adeka optomer N1414, Adeka optomer N1717 (Asahi Denka), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621 Triazine derivatives described in JP-A-60-60104, JP-A-59-1504 and JP-A-61-243
Organic peroxide described in Japanese Patent No. 807, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-641
No. 3, Japanese Patent Publication No. 47-1604 and diazonium compound gazette described in USP 3,567,453, USP 2,848,328, USP 2,852,379 and USP 2,940,853, an organic azide compound, Shoko 36-
Ortho-quinonediazides described in JP-A-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-391.
No. 62, JP-A-59-140203, and “Macromolecules (MACROMOLE
CULES) ", Vol. 10, page 1307 (1977) and various onium compounds including azo compounds described in JP-A-59-142205, JP-A-1
-54440, European Patent No. 109851, European Patent No. 126
No. 712, “Journal of Imaging Science (J.IMAG. SCI.)”, Vol. 30, page 174 (1986), a metal allene complex described in JP-A No. 61-151197. Titanocene, “Coordination Chemistry Review (COORDINATIO
N CHEMISTRY REVIEW), 84, 85-277 (1988) and transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, 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 compounds described in JP-A-59-107344 Halogen compounds, JP-A-5-2138
No. 61, JP-A-5-255347, JP-A-5-255421, JP-A-6
JP-A-157623, JP-A-2000-344812, JP-A-2002-26551.
No. 2, Japanese Patent Application No. 2004-053009, and Japanese Patent Application No. 2004-263413, sulfonium complexes or oxosulfonium complexes, Japanese Patent Application Laid-Open No. 2001-26453
No. 0, JP-A No. 2001-261661, JP-A No. 2000-80068, JP-A No. 2001-233842, USP 3558309 (1971), USP
No. 4202697 (1980), Japanese Patent Application Laid-Open No. 61-24558, Special Table 2004
-534797 and oxime ester compounds described in JP-A No. 2004-359639, bifunctional photoinitiators described in JP-T-2002-530372, and the like. These polymerization initiators are radical polymerizable compounds ( B) It is preferable to contain in 0.01 to 40 weight part with respect to 100 weight part.

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-methyloxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The thermal 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, ethyl 4-dimethylaminobenzoate, N-phenylglycine, triethanolamine, N, N-diethylaniline and the like. Amines such as USP 4414312 and JP-A-6
Thiols described in JP-A-4-13144, disulfides described in JP-A-2-291561, thiones described in USP 3558322 and JP-A 64-17048, and described in JP-A-2-291560. O-acylthiohydroxamate and N-alkyloxypyridinethiones.

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 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. Xenon lamp, deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-
Various light sources such as a Cd laser, a nitrogen laser, a Xe-Cl excimer laser, a 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, 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.

The photopolymerization 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 photopolymerization initiator (A) of the present invention is a known α-
The reason why the sensitivity is higher than that of the aminoketone derivative is not clear so far, but 1
) When the photopolymerization initiator (A) of the present invention is irradiated with light in the ultraviolet region, the process of excitation to radical generation is performed more efficiently than known α-aminoketone derivatives, or
2) Since the photopolymerization initiator (A) of the present invention has absorption characteristics evenly in the wavelength region of the light source for light irradiation, it can absorb a large amount of light energy necessary for generating radicals 1) And / or 2).

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, compounds used in Examples and Comparative Examples are shown in Table 1, and compounds (1) to (4), (6), (8) to (12), and (14) that are photopolymerization initiators of the present invention. , (15), (17) to (20), (22) to (25), (27) to (33), (35), (36), (39), (41), (43) to (43) 45), (48) to (53), and (55) to (57) are synthesis examples.

Synthesis example (1)
Photoinitiator: Synthesis of Compound (1) Synthesis of Compound (A)

100 g of N- (4-benzoylphenyl) -carbazole was dissolved in 300 ml of benzene, 84.5 g of aluminum chloride was further added, and 79.4 g of 2-bromobutyryl bromide was dissolved in 500 ml of benzene with stirring at 0 ° C. The solution was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 3 L of benzene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using ethyl acetate / toluene = 1/2 as a developing solvent to obtain 128.0 g of compound (A). Obtained.

  Synthesis of compound (B)

100 g of compound (A) was dissolved in 500 ml of THF. The solution is cooled to 0 ° C. and 2M
-200 ml of dimethylamine was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 25 ° C. for 24 hours. Next, excess dimethylamine was removed at room temperature by blowing N ₂ at room temperature, and this suspension was poured into 500 ml of ice water and extracted with 300 ml of ethyl acetate. The organic layer is dried over magnesium sulfate, the desiccant is filtered off, the solvent is distilled off, and 87.2 g of compound (B) is removed.
Obtained.

Synthesis of Compound (1) 80.0 g of Compound (B) was dissolved in 500 ml of tetrahydrofuran, and allyl bromide 4
2.0 g was added dropwise over 1 hour. After stirring for 12 hours at 40 ° C., 30% into this solution
NaOH aqueous solution 58.0g was added, and also it stirred for 12 hours. This mixed solution was added to ice water 100
The mixture was poured into 0 ml and extracted with 500 ml of toluene. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by alumina column chromatography using ethyl acetate / toluene = 5/1 as a developing solvent to obtain 71.2 g of compound (1). It was.

Synthesis example (2)
Photoinitiator: Synthesis of Compound (2) Synthesis of Compound (C)

97.1 g of N- (4-nitrophenyl) -carbazole was dissolved in 500 ml of chloroform, and 101.8 g of aluminum chloride was further added, and 95.7 g of 2-bromoisobutyl bromide was dissolved in 500 ml of chloroform with stirring at 0 ° C. The solution was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 3000 g of ice water and extracted with 3 L of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was purified by silica gel column chromatography using chloroform / toluene = 1/10 as a developing solvent to obtain 106.3 g of compound (C). It was.

Synthesis of Compound (2) 90 g of Compound (C) was dissolved in 500 ml of tetrahydrofuran, and 41.7 g of sodium methoxide (28% methanol solution) was added dropwise over 10 minutes under heating and stirring in a nitrogen atmosphere at 60 ° C. After completion of dropping, the mixture was stirred at 60 ° C. for 3 hours. Volatile components of the reaction solution were distilled off under reduced pressure. The residue was dissolved in 300 ml of toluene and washed three times with 500 ml of ion exchange water.
The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the volatile component was distilled off under reduced pressure.

The residue is dissolved in 300 ml of acetonitrile and 358.6 g of morpholine in a nitrogen atmosphere.
Then, 121.6 g of lithium perchlorate was added and stirred at 60 ° C. for 8 hours. Volatile components of the reaction solution are distilled off under reduced pressure, dissolved in 300 ml of toluene, and washed with 500 ml of ion-exchanged water.
Performed once. The organic layer was dried over magnesium sulfate, and the desiccant was filtered off. The residue was purified by silica gel column chromatography using chloroform / toluene = 1/5 as a developing solvent, and 85.7 g of compound (2) was obtained. Obtained.

Synthesis Example (3) to Synthesis Example (57)
By applying the methods of Synthesis Example (1) and Synthesis Example (2) described above, compounds (3) , (4), (6), (8) to (12) which are photopolymerization initiators of the present invention. , (14), (15), (17) to (20), (22) to (25), (27) to (33), (35), (36), (39), (41), ( 43) to (45), (48) to (53), and (55) to (57) could be obtained.

The obtained compounds (1) to (4), (6), (8) to (12), (14), (15), (17) to (20), (22) to (25), (27 )-(33), (35), (36), (39), (41), (43)-(45), (48)-(53), (55)- (57), EI-MS The structure was confirmed with (PolarisQ manufactured by Thermo). The results are shown in Table 2.

(1) Curability : Examples 1 to 4, 6, 8 to 12, 14, 15, 17 to 20, 22 to 25, 27 to 33, 35, 36, 39, 41, 43 to 45, 48 to 53, 55-57 , Comparative Examples 1-12
4 parts by weight of photopolymerization initiator (A), 0 or 1 part by weight of photosensitizer, 10 parts by weight of Daptot DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as radical polymerizable compound (B), ditrimethylolpropanetetra 85 parts by weight of acrylate was blended and melted by heating to prepare a coating solution. Table 3 shows the photopolymerization initiator and photosensitizer 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 130 W / cm1 lamp), then rubbed with a cotton cloth and judged at a conveyor speed at which the film was not damaged. The results are shown in Table 3. In addition, the larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability.
Table 3

Photopolymerizable composition using the photopolymerization initiator (A) of the present invention (Examples 1-4, 6, 8-12, 14, 15, 17-20, 22-25, 27-33, 35, 36) 39, 41, 43 to 45, 48 to 53, 55 to 57) have higher curability than the photopolymerizable composition (Comparative Examples 1 to 4) using a conventionally known photopolymerization initiator. It became clear that Furthermore, the photopolymerizable composition (Examples 1-4, 6, 8-12, 14, 15, 17-20, 22-25, 27-33 using the photoinitiator (A) of this invention , 35, 36, 39, 41, 43 to 45, 48 to 53, 55 to 57), when a conventionally known photopolymerization initiator and a photosensitizer are used in combination as a photopolymerization initiator (Comparative Example) It became clear that it has higher curability than 5-12).

Although not clarified detailed reason, at least one of R ¹² to R ^16, a halogen atom, a nitro group, a cyano group, a haloalkyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, The electronic effect of substitution by an electron-withdrawing substituent, which is one of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, contributes to the light absorption of a compound and the efficiency of photolysis after light absorption. This is presumed to have had a positive effect.
(3) Odor: Examples 58-62, 64-67 , 69, 70 , 72-74, 80 , Comparative Examples 13-20
5 parts by weight of photopolymerization initiator (A), 0 or 1 part by weight of photosensitizer, 10 parts by weight of Aronix M215 (manufactured by Toagosei Co., Ltd.) as radical polymerizable compound (B), 80 parts by weight of fanoxyethyl acrylate Were mixed and heated and melted to prepare a coating solution. Table 5 shows the photopolymerization initiator and photosensitizer used. This coating solution was applied onto a pet film using a bar coater (# 3). After irradiating this coated material with ultraviolet rays (high pressure mercury lamp 130W / cm1 light), the coated material is cut finely and packed in a glass bottle to collect odors. The evaluation was made in five stages from 1 (bad) to 5 (good). The results are shown in Table 5.
Table 4

The photopolymerizable composition using the photopolymerization initiator of the present invention (Examples 58 to 62, 64 to 67, 69, 70, 72 to 74, 80 ) was subjected to photopolymerization using a conventionally known photopolymerization initiator. It was found that the composition was superior in odor compared with the composition (Comparative Examples 13 to 20). The reason why the photopolymerizable composition of the present invention is excellent in odor is that there is little volatilization of the photopolymerization initiator after curing and its decomposition product, and it is more cured at the same light irradiation amount. It is speculated that there is an effect of suppressing volatile materials.

It is clear that the photopolymerizable composition using the photopolymerization initiator of the present invention is excellent in curability even when compared with a photopolymerizable composition using a conventional photopolymerization initiator and a photosensitizer in combination. It became. Also,
The photopolymerizable composition using the photopolymerization initiator of the present invention can suppress odor after curing of the polymerizable composition as compared with a general photopolymerizable composition, and is a conventional photopolymerization initiator. It became clear that all these requirements which were difficult with the photopolymerizable composition which used this were satisfy | filled.

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, crosslinking reaction, etc. using radicals generated by irradiation of energy rays that have been conventionally used as a catalyst,
As a result, it can be expected that the sensitivity to energy rays for various applications will be enhanced, or that the characteristics of various applications will be improved due to sufficient progress of the reaction. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Ink-jet ink, paint, photosensitive resin for printing plates, color proof for printing, resist for color filters, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display, dry film resist, Resist for printed circuit boards, solder resist, photoresist for semiconductor, resist for microelectronics, resist for 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 shows absorption spectra in acetonitrile of a compound (a) which is a photopolymerization initiator of the present invention and a compound (b) which is an α-aminoacetophenone derivative which is a conventional photopolymerization initiator.

Claims (5)

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

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted acyl group. R ³ and R ⁴ may be combined to form a ring.
R ⁵ to R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, or a substituted or unsubstituted aryl group. Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted Arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, substituted Or an unsubstituted acyl group, substituted or unsubstituted A substituted alkyloxycarbonyl group or a substituted or unsubstituted aryloxycarbonyl group is represented.
R ^{12 to} R ¹⁶ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkyl sulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, represents a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group, a R ¹² to R ¹⁶ At least one is a halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted aryl Sulfonyl group, substituted or Unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, and is either substituted or unsubstituted aryloxycarbonyl group. ) R ¹² at least one of to R ^16, a nitro group, and claim 1, wherein the photopolymerization initiator is either a substituted or unsubstituted acyl group (A). At least one of R ¹² to R ^16, but a photopolymerization initiator according to claim 2, wherein a lower following general formula (2) (A).


General formula (2)

(Wherein R ^{17 to} R ²¹ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, A substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyloxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group is represented.) A polymerizable composition comprising the photopolymerization initiator (A) according to any one of claims 1 to 3 and a radically polymerizable compound (B). 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.

Images