JP2006077137A - Radical polymerization initiator, polymerizable composition, and method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radical polymerization initiator usable for various applications without combinedly using a sensitizer. <P>SOLUTION: The invention relates to the radical polymerization initiator expressed by general formula (1). And the invention relates to the polymerizable composition comprising the radical polymerization initiator (A) and a radically polymerizable compound (B). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

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

  In recent years, researches on photopolymerization initiators having higher sensitivity than those of commercially available photopolymerization initiators have been actively conducted, and examples thereof include sulfonium borate complexes (Non-Patent Documents 1 to 5, Patent Documents). 1, 2). It is said that when these sulfonium borate complexes and sensitizers such as Michler's ketone, thioxanthone, and ketocoumarin are irradiated with light, free radicals are generated from both the sulfonium cation and borate anion, indicating high sensitivity (Patent Literature). 3 to 5).

  In addition, as an example that can function as a polymerization initiator without using a sensitizer because it has absorption near 365 nm, a sulfonium ion type polymerization initiator having a coumarin structure or a naphthalene structure introduced in the molecule has been proposed. (See Patent Documents 6 and 7). Further, a sulfonium ion type polymerization initiator into which a benzothienyl group or a benzofuryl group is introduced has been proposed (see Patent Document 8).

Furthermore, as an example of a highly sensitive sulfonium ion type polymerization initiator, a polymerizable composition containing a sulfonium ion type polymerization initiator characterized by containing a sulfonium cation having a phenacyl group in which the benzene ring is substituted with an amino group has been reported. (See Patent Document 9).
Journal of Chemical Society, Chemical Communication, 1977, 675-676 Macromolecules, 1998, 31, 6022-6029 Journal of Photoscience, 1998, 5, 63-67 Macromolecules, 1999, 32, 6545-6551 Journal of Photopolymer Science and Technology, 1999, 12, 115-120 JP-A-5-213861 JP-A-5-255347 JP-A-5-255421 JP-A-6-157623 JP 2000-344812 A Japanese Patent Laid-Open No. 2001-213909 JP 2002-293816 A JP 2001-261728 A JP 2002-265512 A

  The polymerizable composition containing these polymerization initiators can be used in various applications. However, from the viewpoint of cost reduction and productivity improvement, a material that can be cured with a small addition amount and a small amount of light irradiation energy, that is, a highly sensitive material has been required, and these radical polymerization initiators are not necessarily sufficient. In other words, a more sensitive polymerization initiator is required.

  Various irradiation wavelengths are used in the field to which the photocuring technology is applied, but the wavelength region of 300 nm to 450 nm as typified by metal halide lamps and mercury lamps is most often used. In order to express high polymerization sensitivity with respect to these irradiation wavelengths, it is required that the polymerization initiator and sensitizer contained in the polymerizable composition have suitable absorption in the wavelength region of 300 nm to 450 nm. . However, known materials having suitable absorption in this irradiation wavelength region often have absorption up to around 400 nm or longer wavelength side, and are colored yellow. Conversely, a material with little coloration often has low polymerization sensitivity because it does not have suitable absorption in the wavelength region of 300 nm to 450 nm. In order to achieve high sensitivity using a material that does not have such a suitable absorption in the polymerizable composition, the amount of polymerization initiator or sensitizer must be increased, resulting in coloring. In many cases, the addition of a large amount of a low molecular weight compound leads to a decrease in film properties.

  Since the known sulfonium borate type polymerization initiator described at the beginning of the background art has almost no absorption in the wavelength region of 300 nm to 450 nm, the optimum sensitizer is found from many sensitizers and the composition ratio is adjusted. Once determined, there was a complication that it was necessary to use them together. In addition, known sensitizers such as Michler's ketone, thioxanthone, and ketocoumarin are often colored, and some of the sensitizers used at the time of light irradiation are decomposed but are not completely decolored. Later coloring of the composition was inevitable.

  In addition, sulfonium ion polymerization initiators with a coumarin structure, naphthalene structure, benzothienyl group or benzofuryl group introduced into the molecule are less colored and absorb in the wavelength region of 300 nm to 450 nm without the use of a sensitizer. Therefore, it can function as a polymerization initiator. However, absorption in the wavelength region of 300 nm to 450 nm is very small, and a highly sensitive polymerizable composition that can be cured in a shorter time and with a smaller amount of light irradiation is required from the viewpoint of cost reduction and productivity improvement. However, the practical sensitivity was insufficient for the introduction of an expensive borate structure.

  In addition, a polymerizable composition including a sulfonium ion-type polymerization initiator, which is proposed as a highly sensitive polymerizable composition and includes a sulfonium cation having a phenacyl group in which a benzene ring is substituted with an amino group, Sensitivity is not sufficient to cope with various newly proposed processes represented by an increase in the area of the exposure region, and further enhancement of the sensitivity of the polymerization initiator is required.

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

(Wherein R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, An acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, or a halogen atom is represented.
Provided that one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ is

And at least one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ is

Represents.
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
R ₃₁ represents an alkyl group or an aryl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₂₁ , and R ₂₂ are integrated. A ring may be formed.
X ⁻ represents an arbitrary anion. )

In the present invention, R ₀₃ or R ₀₈ is
It relates to the radical polymerization initiator.

Furthermore, this invention relates to the said polymerization initiator whose X < ^- > is the borate represented by following General formula (2).

General formula (2)

(However, in the formula, R ₅₁ , R ₅₂ , R ₅₃ , and R ₅₄ each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. A group selected from an alkenyl group that may be substituted, an alkynyl group that may have a substituent, or an alicyclic group that may have a substituent;

  Furthermore, the present invention relates to a polymerizable composition comprising the radical polymerization 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 300 nm to 450 nm.

  The radical polymerization initiator of the present invention replaces the benzene ring portion of a conventionally known phenacylsulfonium cation with a specific substituent, that is, a phenylthiophenyl group having an acyl group, thereby allowing energy rays, particularly wavelengths of 300 nm to 450 nm. It has good absorption characteristics in the region, and can function as a very sensitive photo radical generator without using a sensitizer for light irradiation in the wavelength region. . Therefore, by using the polymerization initiator of the present invention, it is possible to reliably realize a polymerization reaction and a crosslinking reaction using radicals generated from a conventionally known phenacylsulfonium salt-based polymerization initiator in a shorter time. As a result, it is possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions.

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

  First, the radical polymerization initiator of the present invention will be described. The radical polymerization initiator of the present invention is characterized by having a specific structure at the cation site, thereby realizing a significant increase in sensitivity to energy rays, particularly light irradiation in the wavelength region of 300 nm to 450 nm.

  The radical polymerization initiator of the present invention has a structure represented by the general formula (1), and has a characteristic structure in which the benzene ring portion of the phenacylsulfonium cation is replaced with a phenylthiophenyl group having an acyl group. Have. By introducing this substituent, light absorption characteristics suitable for a wavelength region of 300 nm to 450 nm can be imparted to the sulfonium cation. In addition, by having this structure, the sulfonium cation of the present invention decomposes very efficiently without using a sensitizer for light irradiation in the wavelength region. It is possible to function as a highly sensitive material that is generated automatically.

General formula (1)

(Wherein R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, An acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, or a halogen atom is represented.
Provided that one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ is

And at least one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ is

Represents.
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
R ₃₁ represents an alkyl group or an aryl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ may be combined to form a ring.
X ⁻ represents an arbitrary anion. )

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

Compound (1)

(In the above compound (1), Bu represents a butyl group and Ph represents a phenyl group. Hereinafter, the same notation will be used.)

  The absorption spectrum of compound (1) in acetonitrile is shown in FIG. In addition, the absorption spectrum of the conventional phenacylsulfonium compound (2) as a comparative compound is also shown in FIG.

Compound (2)

  As can be seen from FIG. 1, the compound (2) does not have a suitable absorption in the wavelength region of 300 nm or more, but the compound (1) has an absorption maximum with a molar extinction coefficient of 9900 at 350 nm and a wavelength of 300 to 450 nm. It has suitable absorption in the wavelength region.

  Further, the compound (1) which is the radical polymerization initiator of the present invention is a relatively transparent material having a molar extinction coefficient of about 2600 at 365 nm corresponding to one of the emission lines of a mercury lamp, for example. As a radical generator that greatly surpasses the case where the compound (2), which is a conventionally known phenacylsulfonium-based radical generator having the same anion, is used alone or in combination with a sensitizer. It is a material with innovative functions.

At present, details of the reaction mechanism of radical generation by light irradiation are not clear, but when the light in the ultraviolet region is irradiated to the radical polymerization initiator (A), sulfur in the structure represented by the general formula (3) It is considered that the bond between the atom and the carbon atom C ² is efficiently cleaved with high selectivity to generate a radical, and the generated radical attacks the radical polymerizable compound (B) to cause polymerization. Progress and cure.

General formula (3)

  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 300 nm to 450 nm that expresses particularly suitable sensitivity is preferable, Other energy rays may be emitted simultaneously with the light in the wavelength region. A particularly preferable light source is a light source having a main wavelength of light emission in a wavelength region of 300 nm to 450 nm. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high light source. Examples thereof include, but are not limited to, a power metal halide lamp, a xenon lamp, and a pulse emission xenon lamp. Also emits light in the wavelength range from 300 nm to 450 nm, such as deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excitation solid state laser A laser having a wavelength can also be used as a suitable energy ray source. All of the polymerization initiators (A) of the present invention have suitable absorption in the wavelength region of 300 nm to 450 nm, and the absorption characteristics are slightly different depending on the substituents. It can function as a sensitive radical polymerization initiator. In addition, these light sources can be appropriately irradiated through optical devices such as filters, mirrors, and lenses.

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

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

The substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) are each independently a hydrogen atom, alkyl group, aryl A group, an alkenyl group, an acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, or a halogen atom;

The alkyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) has 1 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 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-decyl , And the like Kurohekishiru group, but not limited thereto.

The aryl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) may contain a hetero atom. Examples thereof include monocyclic or condensed polycyclic aryl groups having 4 to 18 carbon atoms, and specific examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-furanyl group, 2-pyrrolyl group, 9-fluorenyl group, 2-furyl group, 2-thienyl group, 2-indolyl group, 3-indolyl group, 6-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 4-quinolinyl group, 4-isoquinolyl group, 2-carbazolyl group, 3-carbazolyl group , 4-carbazolyl group, 9-acridinyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-phenoxazinyl group, 3-thianthenyl group and the like, but are not limited thereto. .

The alkenyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) has 1 to 18 carbon atoms. Examples thereof include linear, branched, monocyclic or condensed polycyclic alkenyl groups, which may have a plurality of carbon-carbon double bonds in the structure. Specific examples thereof include a vinyl group, 1 -Propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2 -Hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclope , And the like Tajieniru group, but not limited thereto.

The acyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) is a hydrogen atom or a carbon number of 1 To a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group is bonded, or a monocyclic or condensed polycyclic aroma having 4 to 18 carbon atoms which may contain a hetero atom Carbonyl groups bonded to each other may be mentioned, and they may have an unsaturated bond in the structure. Specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group. Group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acrylo Group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, sulfonium group Examples of the acyl group having the following can include, but are not limited to:
In addition, it is particularly preferable that the following acyl group having a sulfonium group is substituted with R ₀₃ or R ₀₈ .

The alkoxyl group in the substituent R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) has 1 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkoxyl groups. Specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyl. Oxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert-pentyloxy group , Tert-octyloxy group, neopentyloxy group, cyclopropyloxy group Examples include cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, etc. However, it is not limited to these.

The aryloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) includes a hetero atom. Examples thereof include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, and a 9-phenanthryl. Oxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2- Thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazo Aryloxy group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl but oxy group, and the like, but is not limited thereto.

The acyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) is a hydrogen atom or a carbon number of 1 To a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group is bonded, or a monocyclic or condensed polycyclic group having 4 to 18 carbon atoms which may contain a hetero atom Examples include carbonyloxy groups to which aromatics are bonded. Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyl. Oxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexane Silcarbonyloxy 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, 9-anthroyloxy group, 5-naphthacenoyloxy group and the like, but are not limited thereto. It is not a thing.

The alkoxycarbonyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) has a carbon number of 1 12 carbonic acid ester groups, and specific examples include tert-butoxycarbonyloxy group, tert-pentyloxycarbonyloxy group, 1,1-diethylpropyloxycarbonyloxy group, 1-ethyl-2-cyclopentenyloxycarbonyloxy group. Group, 2-tetrahydropyranyloxycarbonyloxy group, 1-ethylcyclopentyloxycarbonyloxy group and the like, but are not limited thereto.

The substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) described above, an alkyl group, an aryl group, an alkenyl group, The acyl group, alkoxyl group, aryloxy group, acyloxy group, alkoxycarbonyloxy group may be further substituted with other substituents, such as hydroxyl group, mercapto group, cyano group. Nitro group, halogen atom, alkyl group, aryl group, acyl group, alkoxyl group, aryloxy group, acyloxy group, alkylthio group, arylthio group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, A tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like can be mentioned.

  Examples of the aryl group include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-furanyl group, 2-pyrrolyl group, 9-fluorenyl group, 2-furyl group 2-thienyl group, 2-indolyl group, 3-indolyl group, 6-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 4-quinolinyl group, 4-isoquinolyl group, 2-carbazolyl group, 3-carbazolyl group Group, 4-carbazolyl group, 9-acridinyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-phenoxazinyl group, 3-thiol Ntoreniru group, and the like.

  As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon atom which may contain a hetero atom is 4 carbon atoms. To 18 monocyclic or condensed polycyclic aromatic carbonyl groups, which may have an unsaturated bond in the structure. Specific examples thereof include formyl group, acetyl group, propionyl group, Butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group Benzoyl group, 1-naphthoyl group, 2-naphthoyl group, N'namoiru group, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru group, and the like 5 Nafutasenoiru group.

Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group Boronyl Alkoxy group, 4-decyl cyclohexyl group, 2-tetrahydrofuranyl group, and 2-tetrahydropyranyloxy group.
Examples of the aryloxy group include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, 9 -Anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluore Nyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like.

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples include a carbonyloxy group having 4 to 18 monocyclic or condensed polycyclic aromatics bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth A royloxy group, a 5-naphthacenoyloxy group, etc. can be mentioned.

Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.
Examples of the arylthio group include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3 -A carbazolylthio group, a 4-carbazolylthio group, etc. can be mentioned, However, It is not limited to these.

The halogen atom in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) includes a fluorine atom, a chlorine atom, A bromine atom and an iodine atom can be mentioned.

The substituents in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ in the general formula (1) are not necessarily the same. The above-mentioned substituents can be used in any combination. Substituents Particularly preferred substituents in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ are a hydrogen atom, an alkyl group, an alkoxyl group, Examples include groups selected from an aryloxy group and an acyloxy group. Two adjacent substituents selected from R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ are combined to form a cyclic structure. It may be formed.

Next, the substituent represented by the substituent —R ₃₁ in the general formula (1) will be described. As the alkyl group and aryl group in the substituent R _31, the alkyl group and aryl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ The same substituents as those exemplified above can be mentioned.

The alkyl group, aryl group, alkoxyl group and alkenyl group in the substituents R ₁₁ and R ₁₂ in the general formula (1), the alkyl group, aryl group and alkenyl group in R ₂₁ and R ₂₂ are the substituents R ₀₁ , R _The same substituents as those exemplified as the alkyl group, aryl group, alkoxyl group and alkenyl group in ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ may be mentioned. it can.

The substituents R ₂₁ and R ₂₂ may be R ₂₁ R _{22 to} each other, or R ₁₁ , R ₁₂ , R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and Any of R ₁₀ may be bonded to each other to form a ring structure. In addition, the substituents R ₁₁ and R ₁₂ are bonded to any of R ₂₁ , R ₂₂ , R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R _10. And a ring structure may be formed.

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

X < ^- > in General formula (1) represents arbitrary anions. Examples of such anions include nucleophilic anions such as F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , HSO ₃ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , and CH ₃ SO ₃ ^— . The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction.
Moreover, as X < ^- > in General formula (1), the alkylbenzenesulfonic acid ion represented by p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, and camphorsulfonic acid can also be used.
Further, as X ⁻ in the general formula (1), a non-nucleophilic anion can also be used. Examples of this include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₃ SO ₃ ^{— and the} like are exemplified, but not limited thereto. The borate anion represented by the general formula (2) is also included in the category of the anion X ⁻ of the present invention.

As X ⁻ in the general formula (1), a borate anion represented by the following general formula (2) can also be synthesized relatively easily, has higher sensitivity, high solubility, and high safety and health. It can be preferably used. R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ in the general formula (2) each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It represents a group selected from an alkenyl group that may be substituted, an alkynyl group that may have a substituent, and an alicyclic group that may have a substituent.

Examples of the alkyl group which may have such a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Octyl, decyl, dodecyl, octadecyl, etc.
As the aryl group which may have a substituent, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, 1-naphthyl group, 2-naphthyl group, mesityl group, cumenyl group, o-chlorophenyl group, m-fluorophenyl group, p-cyanophenyl group, etc.
Examples of the alkenyl group that may have a substituent include a vinyl group, a 1-propenyl group, an isopropenyl group, and a 1-butenyl group.
Examples of the alkynyl group which may have a substituent include ethynyl group, 1-hexynyl group and 1-propynyl group, and examples of the alicyclic group which may have a substituent include cyclohexyl group, cyclopentyl group and cyclohexenyl. Group, norbornyl group, bornyl group, menthyl group, pinanyl group, adamantyl group and the like.

  The hydrogen atom of these groups may be further substituted with other substituents. Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, methoxy group, tert group In addition to alkoxy groups such as butoxy group and phenoxy group, alkyl groups such as methyl group, tert-butyl group and dodecyl group, aryl groups such as phenyl group and p-tolyl group, mesyl group, p-toluenesulfonyl group, A trifluoromethyl group etc. are mentioned.

These substituents R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ are each independently preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or the like, and more preferably Examples include a methyl group, an ethyl group, a butyl group, a phenyl group, a mesityl group, a 4-methylphenyl group, and a 3-fluorophenyl group, but the present invention is not limited to these examples.
Of these four substituents bonded to boron, one is an alkyl group that may be substituted, and three are phenyl groups that may be substituted, which is preferable because radical generating ability may be improved.

  Therefore, as the structure of the borate anion represented by the general formula (2), specifically, tert-butyl triethyl borate, phenyl triethyl borate, tributyl benzyl borate, diethyl dibutyl borate, dibutyl diphenyl borate, methyl triphenyl borate, ethyl Triphenylborate, propyltriphenylborate, isopropyltriphenylborate, butyltriphenylborate, sec-butyltriphenylborate, tert-butyltriphenylborate, dodecyltriphenylborate, benzyltriphenylborate, vinyltriphenylborate, ethynyltri Phenylborate, butyltrimesitylborate, butyltris (p-methoxyphenyl) borate, butyltris (p-fluoropheny ) Borate, butyltris (p-bromophenyl) borate, sec-butyltris (p-methoxyphenyl) borate, sec-butyltris (p-fluorophenyl) borate, tert-butyltris (p-methoxyphenyl) borate, butyltris [3,5 -Bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, butyltri (m-fluorophenyl) borate, tetraphenylborate, pentafluorophenyltrifluoroborate, 3,5-bis (trifluoromethyl) phenyl Trifluoroborate, bis (pentafluorophenyl) difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, The [3,5-bis (trifluoromethyl) phenyl] fluoroborate, although tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and the like, but is not limited thereto.

  Of these, butyltriphenylborate is particularly preferable as the anion represented by the general formula (2).

  The radical polymerization initiator represented by the general formula (1) of the present invention is a combination of the sulfonium cation and various anions exemplified above.

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

However, X ⁻ in the above structural formula is Cl ⁻ , Br ⁻ , HSO ₃ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CH ₃ SO ₃ ⁻ p -toluenesulfonic acid, p-dodecylbenzenesulfonic acid, BF ₄ ^−. , PF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₃ SO ₃ ⁻ , tert-butyltriethylborate, phenyltriethylborate, tributylbenzylborate, diethyldibutylborate, dibutyldiphenyl Borate, methyl triphenyl borate, ethyl triphenyl borate, propyl triphenyl borate, isopropyl triphenyl borate, butyl triphenyl borate, sec-butyl triphenyl borate, tert-butyl triphenyl borate, dodecyl triphenyl borate, Diltriphenylborate, vinyltriphenylborate, ethynyltriphenylborate, butyltrimesitylborate, butyltris (p-methoxyphenyl) borate, butyltris (p-fluorophenyl) borate, butyltris (p-bromophenyl) borate, sec-butyltris (p-methoxyphenyl) borate, sec-butyltris (p-fluorophenyl) borate, tert-butyltris (p-methoxyphenyl) borate, butyltris [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluoro phenyl) borate, tetraphenylborate, SCN ^- although anions like are exemplified, the present invention is not limited to these examples.

  The synthesis method for obtaining the radical polymerization initiator of the present invention is not particularly limited, and the structure can be easily synthesized and confirmed by appropriately combining conventionally known chemical reactions, post-treatment methods, purification methods and analysis methods. Is possible. The synthesis method of phenacylsulfonium salt is described in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 38, 1433-1442 (2000), Macromolecules, Vol. 33, pages 825-832 (2000), etc. The energy-sensitive linear acid generator of the present invention can be synthesized by appropriately replacing the raw materials used in the synthesis described in these methods.

As an example of the synthesis method, an acetylphenyl sulfide derivative is synthesized as a starting material. When an acetylphenyl sulfide having an appropriate acyl group is not available, an acetylphenyl sulfide derivative having a corresponding acyl group can be obtained by acetylation by a Friedel-Crafts reaction on a phenyl sulfide derivative having an acyl group. The acetyl group of the acetylphenyl sulfide derivative having an acyl group described above is brominated with a bromination reagent such as bromine, and then this derivative is reacted with sulfide to correspond to the cation site of the radical polymerization initiator of the present invention. A sulfonium bromide salt can be obtained. Such sulfonium bromide salt obtained in the anion X ^- can be performed easily ion-exchanged with a metal salt having, it is possible to obtain a radical polymerization initiator of the present invention.

  Since the radical polymerization initiator of the present invention functions as a very sensitive radical polymerization initiator by irradiation with energy rays, particularly in the wavelength region of 300 nm to 450 nm, a conventionally known phenacylsulfonium salt-based radical polymerization initiator is used. The polymerization reaction, the crosslinking reaction, etc. to be used can be reliably realized in a shorter time, and as a result, it is possible to realize a significant increase in sensitivity and improvement in characteristics of various uses applying these reactions. The method for using the radical polymerization initiator of the present invention will be described below.

  The composition containing the radical polymerization initiator (A) and the radical polymerizable compound (B) of the present invention is cured quickly and reliably by irradiation with energy rays, particularly light in a wavelength region of 300 nm to 450 nm, and has good characteristics. It can be used as a polymerizable composition capable of obtaining a cured product having the above.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Moreover, the cyclic compound shown below is mention | raise | lifted as a radically polymerizable compound (B).
Examples of three-membered ring compounds:
Vinylcyclopropanes described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 17, p. 3169 (1979), Macromolecular Chemie. Rapid Communication (Makromol. Chem. Rapid Commun.), Vol. 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed., Vol. 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. ), Vol. 21, page 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 564 (1985) 2,3-di-vinyl oxiranes described.

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

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

  The radically polymerizable compound (B) of the present invention may be used alone or in a mixture of two or more at any ratio in order to improve desired properties. Moreover, it is preferable to use the polymerization initiator (A) of this invention in 0.01-60 weight part with respect to 100 weight part of radically polymerizable compounds (B). The carboxyl group-containing polymer (C) is preferably used in the range of 20 to 500 parts by weight, more preferably in the range of 50 to 150 parts by weight, based on 100 parts by weight of the radical polymerizable compound (B). .

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

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

  Furthermore, the polymerizable composition of the present invention may be used by adding the following carboxyl group-containing polymer for the purpose of using it as an alkali developing type photoresist material for image formation. Since the carboxyl group-containing polymer has solubility in an alkaline aqueous solution, if the film prepared using the photopolymerizable composition of the present invention is partially cured, a so-called negative resist pattern is formed due to the difference in solubility in the alkaline aqueous solution. Can be formed. Here, the carboxyl group-containing polymer includes 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. . These copolymers may be used alone or in combination of two or more.

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

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

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

  In addition, the polymerizable composition of the present invention has sufficient sensitivity without using other sensitizers, but for the purpose of further improving the sensitivity and improving the film properties after curing, other sensitizers and other sensitizers may be used. It can be used in combination with a photopolymerization initiator.

  Sensitizers that can be used in combination with the polymerizable composition of the present invention include benzophenones, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone 1 , 2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, etc. Pigment, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, Liarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline Derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and the like. Other specific examples include Ogahara Nobu et al., “Dye Handbook” (1986, Kodansha), The dyes and sensitizers described in Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Tadasaburo et al., “Special functional materials” (1986, CMC) However, it is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region, and two or more of these may be used in any ratio as necessary. It doesn't matter. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). ) And the like, but is not limited thereto.

  Other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include Irgacure 651, Irgacure 184, Darocur 1173 described in the Ciba Specialty Chemicals Photopolymerization Initiator General Catalog (issued in 1997), IRGACURE 500, IRGACURE 1000, IRGACURE 2959, IRGACURE 907, IRGACURE 369, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261 Triazine derivatives described in Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621 and Japanese Patent Publication No. 60-60104, Japanese Patent Publication No. 59-1504 and Japanese Patent Publication No. 61-243807. Peroxides, diazonium compound gazettes described in JP-B 43-23684, JP-B 44-6413, JP-B 47-1604 and USP 3567453, USP 2848328, USP 2852379 And an organic azide compound described in US Pat. No. 2,940,853, ortho described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015, and JP-B 45-9610 -Quinonediazides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203, and "Macromolecules", Vol. 10, page 1307 (1977) Various onium compounds, JP-A-59-142205 Azo compounds described, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Volume 30 174 (1986), titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, 85-277. (1988) and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, aluminate complexes described in JP-A-3-209477, and boric acid described in JP-A-2-157760. 2, 4 of the salt compound described in JP-A-55-127550 and JP-A-60-202437 , 5-triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, carbon tetrabromide and JP Organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068 Oxime ester compounds described in JP-A-2001-233842, USP3558309 (1971), USP4202697 (1980), and JP-A-61-25585, etc. The agent is a compound having an ethylenically unsaturated bond capable of radical polymerization of 100 weight. Preferably contained in the range of 0.01 to 10 parts by weight relative to.

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

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

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

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

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

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of energy such as ultraviolet rays, visible light, near infrared rays, electron beams, etc. to obtain a desired polymer, As the light source, a light source having a dominant wavelength of light emission in a wavelength region of 300 nm to 400 nm is preferable. Examples of light sources having a dominant wavelength of light emission in the wavelength region of 300 nm to 400 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. Examples of the light source include xenon lamps, deuterium lamps, fluorescent lamps, Nd-YAG triple wave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, and semiconductor-excited solid lasers. The definitions of ultraviolet rays, near-ultraviolet rays, visible light, near-infrared rays, infrared rays, and the like referred to in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

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

(Function)
The radical polymerization initiator (A) of the present invention functions as a radical polymerization initiator that is sensitive to irradiation light in a wavelength region of 300 to 450 nm. The reaction mechanism is considered as follows. Since the sulfonium structure in the radical polymerization initiator (A) itself has a suitable absorption in the irradiation light region of a wavelength region of 300 to 450 nm, it functions as a radical polymerization initiator having a sensitizing function. . That is, when excited by ultraviolet light or near-ultraviolet light, efficient electron transfer or energy transfer occurs in the molecule, and it is possible to generate radicals by photolysis very quickly. It is thought that it functions as an agent. Moreover, since the sulfonium ion in the radical polymerization initiator (A) has a high electron accepting property, it is not only decomposed itself when photoexcited, but more efficiently decomposed when the counter anion has an electron donating property. It is thought to progress. When the anion Y ⁻ in the general formula (1) is a borate anion represented by the general formula (2), the borate anion not only has a high electron donating property but also decomposes itself to generate a free radical. To do. Therefore, in this case, since the free radical is generated from both the sulfonium cation and the borate anion, extremely high sensitivity can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In addition, unless otherwise indicated, a part shows a weight part in an example. First, prior to the examples, some of the synthesis examples of the above-described radical polymerization initiator (A) of the present invention are shown.

Synthesis example (1)
Synthesis of compound (1)

Synthesis of 4-benzoyl-diphenyl sulfide Dissolve 80.0 g of diphenyl sulfide in 450 ml of carbon disulfide, add 57.3 g of aluminum chloride, and stir at 0 ° C. to 60.0 g of benzoyl chloride to 150 ml of carbon disulfide. The dissolved solution was added over 2 hours. After completion of the addition, the mixture was stirred at 25 ° C. for 3 hours. The reaction solution was poured into 1500 g of ice water and extracted with 800 ml of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was recrystallized from chloroform-hexane to obtain 109.2 g of 4-benzoyl-diphenyl sulfide (yield 88). %).

Synthesis of 4′-benzoyl-4-bromoacetyl diphenyl sulfide 94.3 g of 4-benzoyl-diphenyl sulfide was dissolved in 400 ml of dichloromethane, 95.2 g of aluminum chloride was further added, and bromoacetyl bromide 72 was added with stirring at 0 ° C. A solution of 1 g dissolved in 50 ml dichloromethane was added over 1 hour. After completion of the addition, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 1000 ml of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was recrystallized from chloroform-hexane to obtain 125.8 g of 4′-benzoyl-4-bromoacetyldiphenyl sulfide. (94% yield).

Synthesis of dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium bromide 60.0 g of 4′-benzoyl-4-bromoacetyldiphenyl sulfide was dissolved in 250 ml of dichloromethane, 18.1 g of sulfide was added and stirred at room temperature for 12 hours. The crystals precipitated in the solution were filtered, and the obtained crystals were washed with chloroform and then dried to give dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] as white crystals. 62.9 g of sulfonium bromide was obtained (yield 91%).

Synthesis of dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium butyltriphenylborate (compound (1)) Dimethyl [2- (4′-benzoyl-diphenylsulfide-4) -Yl) -2-oxoethyl] sulfonium bromide 18.0 g was dissolved in a mixed solvent consisting of 900 ml of ion-exchanged water and 3600 ml of methanol, and 54.79 g of an aqueous solution of lithium butyltriphenylborate (weight concentration 20.82%) was room temperature. The mixture was added dropwise over 80 minutes and stirred at room temperature for 1 hour after the completion of the addition. 3600 ml of ion-exchanged water was added to the reaction solution, and further stirred for 90 minutes. The precipitate was filtered, and the resulting solid was dissolved in 1200 ml of methyl isobutyl ketone and extracted and washed with water. The organic layer was dried over magnesium sulfate, the desiccant was removed, and the resulting solution was added dropwise into 2000 ml of hexane cooled to 0 ° C. The produced crystals are filtered, washed with hexane, and dried to obtain dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium · butyltriphenylborate (compound (1)). 23.7 g of white crystals were obtained (yield 92%).

(Synthesis Example 2)
Synthesis of compound (3)

Synthesis of dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium hexafluoroantimonate (compound (3)) 15.0 g of 4′-benzoyl-4-bromoacetyldiphenyl sulfide was dissolved in 200 ml of acetone, 2.5 g of dimethyl sulfide was added, and the mixture was cooled to 0 ° C. Left 0 ° C., to this solution, AgSbF ₆ and 12.5 g (silver salt of hexafluoroantimonate) was added dropwise over 1 hour a solution prepared by adding acetone 100 ml, was warmed up to room temperature, stirred remains shielding 24 hours did. The produced solid was removed by filtration, and the solvent of the obtained solution was distilled off to obtain a solid. This solid was reprecipitated with acetone-hexane, and dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium hexafluoroantimonate (compound (3)) was obtained as white crystals. 12.6 g was obtained (55% yield).

(Synthesis Example 3)
Synthesis of compound (4)

Synthesis of dimethyl {2- [4 '-(o-toluoyl) -diphenyl sulfide-4-yl] -2-oxoethyl} sulfonium hexafluorophosphate (Compound (4)) This is a starting material for Synthesis Example 1 4 '-(o-toluoyl) -4-bromoacetyldiphenyl sulfide can be obtained in a good yield in substantially the same manner as in (Synthesis Example 1) except that benzoyl chloride is replaced with o-toluoyl chloride. did it. After dissolving 15.0 g of this 4 ′-(o-toluoyl) -4-bromoacetyl diphenyl sulfide in 200 ml of dichloromethane, 3.8 g of diethyl ethyl sulfide was added and cooled to 0 ° C. A solution obtained by adding 8.9 g of AgPF ₆ (hexafluorophosphate silver salt) to 100 ml of acetone was added dropwise to this solution over 1 hour while keeping the temperature at 0 ° C., and the mixture was warmed to room temperature and then stirred for 24 hours while being shielded from light. did. The produced solid was removed by filtration, and the solvent of the obtained solution was distilled off to obtain a solid. This solid was reprecipitated with acetone-hexane, and 12.3 g of dimethyl {2- [4 '-(o-toluoyl) -diphenylsulfide-4-yl] -2-oxoethyl} sulfonium hexafluorophosphate as white crystals. (Compound (4)) was obtained (yield 60%).

(Synthesis Example 4)
Synthesis of compound (6)

Synthesis of dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium perfluorobutanesulfonate (compound (6)) Dimethyl [2 synthesized in the synthesis section of compound (1) -(4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium bromide (8.7 g) was dissolved in a mixed solvent consisting of 4000 ml of ion-exchanged water and 300 ml of acetone, and perfluorobutane was stirred at room temperature. A solution prepared by dissolving 6.2 g of potassium sulfonate in 300 ml of ion-exchanged water was added dropwise over 30 minutes. The solution after completion of dropping was further stirred at room temperature for 6 hours, and the precipitated crystals were filtered and washed thoroughly with ion-exchanged water. This crystal is dissolved in 600 ml of methyl isobutyl ketone, extracted and washed in ion-exchanged water, the organic layer is dried over magnesium sulfate, the desiccant is removed, and 2400 ml of hexane is added dropwise at room temperature, and the resulting crystal is filtered. And washed with hexane and dried to obtain 7.5 g of dimethyl [2- (4′-benzoyl-diphenylsulfide-4-yl) -2-oxoethyl] sulfonium perfluorobutanesulfonate (compound (6)). Obtained (yield 59%).

(Synthesis Example 5)
Synthesis of Compound (8) Synthesis of Dimethyl {2- [4 ′-(o-Toluoyl) -diphenylsulfide-4-yl] -2-oxoethyl} sulfonium tetraphenylborate (Compound (8)) (Synthesis Example 1) 4 ′-(o-toluoyl) -4-bromoacetyldiphenyl sulfide was obtained in a similar manner as in (Synthesis Example 1) except that o-toluoyl chloride was replaced with o-toluoyl chloride. Could get at rate. After 10.0 g of this 4 ′-(o-toluoyl) -4-bromoacetyldiphenyl sulfide was dissolved in 200 ml of dichloromethane, 2.5 g of diethyl sulfide was added and stirred at about 35 ° C. for 48 hours. 200 ml of ether was added to this solution, and the resulting crystals were filtered, washed with dichloromethane and dried to give dimethyl {2- [4 ′-(o-toluoyl) -diphenylsulfide-4-yl] -2. -Oxoethyl} sulfonium bromide 4.2 g was obtained (yield 35%).

  Dissolve 5.2 g of this dimethyl {2- [4 '-(o-toluoyl) -diphenyl sulfide-4-yl] -2-oxoethyl} sulfonium bromide in a mixed solvent consisting of 300 ml of ion-exchanged water and 500 ml of dimethyl sulfoxide. 34.5 g of an aqueous sodium tetraphenylborate solution (weight concentration 10%) was added dropwise at room temperature over 30 minutes. The precipitate was extracted with 100 ml of methyl isobutyl ketone, and this organic layer was further extracted and washed with ion exchange water. The organic layer was dried over magnesium sulfate and the desiccant was filtered, and then 500 ml of hexane was added dropwise at room temperature to obtain white crystals. The crystals were filtered, washed with hexane, dried, and dimethyl {2- [4 '-(o-toluoyl) -diphenylsulfide-4-yl] -2-oxoethyl} sulfonium tetraphenylborate (compound) as white crystals. 4.6 g of (8)) was obtained (yield 60%).

(Synthesis Example 6 and Synthesis Example 7)
By applying the methods of Synthesis Example 1 to Synthesis Example 5 described above, compounds (5) and (7), which are radical polymerization initiators of the present invention, were also obtained.

The results of elemental analysis of the radical polymerization initiator of the present invention synthesized in Synthesis Example 1 to Synthesis Example 8 are shown in Table 1.

Example 1
From 6 parts by weight of the compound (1) which is a radical polymerization initiator of the present invention, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 100 parts by weight of polymethyl methacrylate as a binder, and 1600 parts by weight of cyclohexanone as a solvent The resulting polymerizable composition was blended with the composition shown in Table 5 to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. The coating film was irradiated with light from a high-pressure mercury lamp through a bandpass filter that selectively transmits only 365 nm light, thereby giving an energy of 300 mJ / cm ² . The absorption intensity at 810 cm ⁻¹ corresponding to the characteristic absorption of the acrylic group of the coating film on the stainless steel plate after the light irradiation was monitored using a reflective IR. When the acrylic monomer consumption rate after the light irradiation was calculated based on the intensity of the above characteristic absorption before the light irradiation, the acrylic monomer consumption rate was 23%.

(Example 2 to Example 6 and Comparative Example 1 to Comparative Example 9)
The experiment was carried out in exactly the same manner as in Example 1, except that 6 parts by weight of the compound (1) as the radical polymerization initiator (A) in Example 1 was replaced with 6 parts by weight of the radical polymerization initiator shown in Table 3. The consumption rate of the acrylic monomer was calculated. The results are also shown in Table 2.

  In the present invention (Examples 1 to 6), irradiation with light of 365 nm generates radicals involved in polymerization without using a sensitizer and consumes acrylic groups. On the other hand, Comparative Examples 1 to 6 are not involved in the polymerization even when irradiated with 365 nm light. From Comparative Examples 6 to 9, having absorption at 365 nm does not necessarily lead to improvement in sensitivity. From Comparative Examples 1 to 9, when comparing radical polymerization initiators having the same anion, the radical polymerization initiator having a cation of the present invention has higher polymerization ability in any case.

(Examples 7 to 10 and Comparative Examples 10 to 29)
From 6 parts by weight of the compound (1) which is a radical polymerization initiator of the present invention, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 100 parts by weight of polymethyl methacrylate as a binder, and 1600 parts by weight of cyclohexanone as a solvent The resulting polymerizable composition was blended with the composition shown in Table 5 to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. The coating film was irradiated with light from a high-pressure mercury lamp at an intensity of 10.0 mW / cm ² through a band-pass filter that selectively transmits only 365 nm light and an ND filter for light intensity adjustment. During this light irradiation, a reflection IR was used to monitor an absorption intensity of 810 cm ⁻¹ corresponding to the characteristic absorption of the acrylic group of the coating film on the stainless steel plate. From this time-dependent change in absorption intensity, the acrylic monomer consumption rate was calculated based on the intensity of the above characteristic absorption before light irradiation. After 10 seconds of light irradiation, the acrylic monomer consumption rate was 19%, and after 30 seconds of light irradiation. The consumption rate was 23%.

In the present invention (Examples 7 to 10), irradiation with light of 365 nm generates radicals involved in polymerization without using a sensitizer and consumes acrylic groups. On the other hand, from Comparative Examples 10 to 14, the radical polymerization initiators other than the present invention are significantly inferior in sensitivity to the 365 nm light irradiation as compared with the radical polymerization initiator of the present invention. From Comparative Examples 11 to 14, having absorption does not necessarily lead to an improvement in sensitivity. From Comparative Examples 15 to 24, radical polymerization can be confirmed by using a sensitizer, but this is far from the present invention. Further, from Comparative Examples 25 to 29, even when diphenyl sulfide is used as a sensitizer, the results are remarkably inferior compared with the sensitizer-integrated radical polymerization initiator as in the present invention. Therefore, the radical polymerization initiator of the present invention is highly effective.

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

  The present invention provides a radical polymerization initiator that functions as a radical generator very sensitive to irradiation with energy rays, particularly irradiation with light of 300 to 450 nm. Therefore, the radical polymerization initiator of the present invention can rapidly and surely proceed polymerization and crosslinking reaction using radicals generated by irradiation of energy rays, which have been conventionally used, as a result. It can be expected to increase the sensitivity to energy rays or to improve the characteristics of various applications by sufficiently proceeding the reaction. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Paints, photosensitive resins for printing plates, color proofs for printing, resists for color filters, resists for black matrices, photo spacers for liquid crystals, screen materials for rear projection, optical fibers, ribs for plasma displays, dry film resists, for printed circuit boards Resist, Photoresist for semiconductor, Resist for microelectronics, Resist for manufacturing micro machine parts, Insulating material, Hologram material, Waveguide material, Overcoat agent, Adhesive, Adhesive, Release agent, Optical recording medium, Adhesive Examples thereof include an adhesive, a release coating agent, and various devices.

Absorption spectra of compound (1) and compound (2) (acetonitrile, 10 ⁻⁵ M)

Claims (5)

A radical polymerization initiator represented by the following general formula (1).
General formula (1)
(Wherein R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, An acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, or a halogen atom is represented.
Provided that one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ is
And at least one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ and R ₁₀ is
Represents.
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
R ₃₁ represents an alkyl group or an aryl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₂₁ , and R ₂₂ are integrated. A ring may be formed.
X ⁻ represents an arbitrary anion. ) R ₀₃ or R ₀₈ is
(R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₀₇ , R ₀₈ , R ₀₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₂₁ , and R ₂₂ are integrated. A ring may be formed. )
The radical polymerization initiator according to claim 1, wherein Wherein X ^-, a radical polymerization initiator according to claim 1 or 2, wherein the borate is denoted by the following general formula (2).
General formula (2)
(However, in the formula, R ₅₁ , R ₅₂ , R ₅₃ , and R ₅₄ each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. And a group selected from an alkenyl group that may be substituted, an alkynyl group that may have a substituent, or an alicyclic group that may have a substituent.   A polymerizable composition comprising the radical polymerization initiator (A) according to any one of claims 1 to 3 and a radical polymerizable compound (B).   A method for producing a polymer, wherein the polymerizable composition according to claim 4 is polymerized by irradiation with an energy ray containing light in a wavelength region of 300 nm to 450 nm.