JP2004196775A - Photocationic polymerization initiator composition and photocationically polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocationic polymerization initiator composition having high sensitivity to visual light, useful for dental use and developing sufficiently high curing rate and cure depth by the light irradiation for a short period. <P>SOLUTION: The initiator composition contains (A) a photo-acid generator generating an acid by light irradiation such as a diaryl iodonium salt compound, a sulfonium salt compound, a sulfonic acid ester compound and a halomethyl-substituted-s-triazine derivative and (B) a condensed polycyclic aromatic compound having a molecular structure containing a non-aromatic ring condensed to the condensed polycyclic aromatic ring, provided that at least one of atoms constituting the non-aromatic ring directly bonded to an atom shared by the condensed polycyclic aromatic ring and the non-aromatic ring is a saturated carbon atom having at least one hydrogen atom, such as 1,2,3,4-tetrahydronaphthacene and 1,2-dihydroaceanthrylene. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a novel photopolymerization initiator suitably used for a photoresist material, a printing plate-making material, a hologram material, a dental material, and the like, and a photopolymerization composition containing the photopolymerization initiator.

  Various proposals have been made for a cationic photopolymerization initiator that generates a Bronsted acid or a Lewis acid by light irradiation and polymerizes a cationically polymerizable compound such as an epoxide or a vinyl ether.

  One example of such a cationic photopolymerization initiator is a photoacid generator such as an iodonium salt compound or a sulfonium salt compound. However, these photoacid generators usually do not absorb near-ultraviolet light, and thus cannot excite the polymerization reaction even with a normal light source (370 to 550 nm) such as a halogen lamp. Therefore, a polycyclic aromatic compound substituted with an alkoxy group, an aralkyloxy group, an acyloxy group, or the like is used as a sensitizer and used as a photocationic polymerization initiator in combination with the photoacid generator (for example, Non-Patent Documents 1 to 3 and Patent Documents 1 to 4). Furthermore, there is an example in which these substituted fused polycyclic aromatic compounds are used in combination with a thioxanthone conductor.

  In addition, photoacid generators whose compounds themselves have absorption in the near ultraviolet to visible light region are also known, and include, for example, cyclopentadienyl-iron-arene complexes, and diazonium salt compounds (for example, Non-Patent Documents) 1).

  On the other hand, in the field of dental materials, radical polymerization systems using (meth) acrylate-based polymerizable monomers have hitherto been widely adopted and applied to various products. For such dental uses, polymerization using visible light is the mainstream in consideration of harmful effects on living organisms, and polymerization initiator systems composed of α-dicarbonyl compounds and aromatic amines and acylphosphines are used. Polymerization initiators and the like composed of oxides have been put to practical use.

  However, the radical polymerization system has a problem that polymerization is inhibited by oxygen and polymerization shrinkage is large. Paste-type dental restoration materials such as composite resins and compomers used for restoration of caries and fractures of natural teeth are directly filled and shaped into the cavity of the tooth and then cured. An unpolymerized layer or a low-polymerized layer is formed due to polymerization inhibition by oxygen in the medium. As a result, it is necessary to polish the surface after curing. If not polished, there is a problem of coloring or discoloration of the cured product over time. In addition, since the shrinkage during polymerization is large, a gap is likely to be formed at the interface between the hardened body and the dentin, which causes the restoration to fall off or bacteria enter the gap to cause secondary caries. Or occur.

  In that the polymerization is not inhibited by oxygen, cationic polymerization is superior to radical polymerization.Particularly, when a compound that performs ring-opening polymerization is used as a polymerizable monomer, the problem of polymerization shrinkage also occurs. It is greatly reduced.

  However, in the system composed of the photoacid generator and the sensitizing dye as described above, the polymerization rate is low and the curing depth is not sufficient. However, it is not sufficient as a polymerization initiator for dental applications requiring

  In addition, the cyclopentadienyl-iron-arene complex is strongly colored after curing, and the diazonium salt compound generates bubbles, so that it is also difficult to use the compound for dental use.

  In order to remedy such drawbacks, several cationic polymerization initiator systems which can be used for dental use have been proposed in recent years. For example, it is known that an α-dicarbonyl compound known as a radical polymerization initiator can be combined with an iodonium salt compound to cure a mixture of an epoxide and a hydroxy compound with visible light irradiation, and to give an improved cure depth. (For example, see Patent Document 6). It has also been reported that the curing rate can be further improved by further combining an aromatic amine with the α-dicarbonyl compound-iodonium salt compound (for example, see Patent Documents 7 and 8). However, these are not sufficient in terms of polymerization activity, and have not yet been put to practical use.

Ao Yamaoka, Mototaro Matsunaga, "Photopolymer Technology", Nikkan Kogyo Shimbun, p. 38-46 The Society of Polymer Science, Japan, “Polymer Synthesis and Reaction (1) Synthesis of Addition Polymer”, Kyoritsu Publishing Co., Ltd., p. 400-404 Kazuhiko Morio, Hiroshi Tsuchiya, Tsuyoshi Endo, "Recent Advances in Photoinitiated Cationic Polymerization", Functional Materials, CMC Corporation, October 1985, p. 5-13 JP-A-11-199681 JP-A-11-329552 JP 2000-7716 A JP 2001-81290 A JP-A-11-263804 Japanese Patent Publication No. Hei 10-508067 JP-A-11-130945 Japanese Unexamined Patent Publication No. 2002-500172

  The present invention has high sensitivity to light irradiation, particularly visible light useful for dental use, and furthermore, with short-time light irradiation, a photocationic polymerization initiator composition having a sufficient curing speed and curing depth, and It is an object of the present invention to provide a cationic photopolymerizable composition using the cationic photopolymerization initiator composition, which is not subject to polymerization inhibition by oxygen and has a small polymerization shrinkage.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, a composition containing a photoacid generator and a specific condensed polycyclic aromatic compound as a novel photopolymerization initiator capable of achieving the above object. The present invention was found to be useful, and the present invention was completed.

  That is, the present invention is a photocationic polymerization initiator composition comprising (A) a photoacid generator and (B) a condensed polycyclic aromatic compound, wherein the condensed polycyclic aromatic compound is It has a molecular structure in which a non-aromatic ring is further fused to a condensed polycyclic aromatic ring, and is directly bonded to an atom shared by the fused polycyclic aromatic ring and the non-aromatic ring. Wherein at least one of the non-aromatic ring constituting atoms is a saturated carbon atom, and the saturated carbon atom has at least one hydrogen atom. is there.

  Since the cationic photopolymerization initiator composition of the present invention has sufficient sensitivity to wavelengths in the visible light region, even when using a visible light irradiator used for dentistry or the like, short-time light irradiation is possible. And a deep effect depth can be obtained, and a polymer cured product having excellent mechanical properties can be obtained.

  Further, since it is possible to polymerize and cure a cationically polymerizable monomer that is not subject to polymerization inhibition by oxygen, a photopolymerizable composition containing the cationic photopolymerization initiator and the cationically polymerizable monomer of the present invention was used. In this case, a cured product having no surface unpolymerized layer can be obtained without using a special means for blocking oxygen. Therefore, even when polymerizing and curing in a place where oxygen blocking measures are difficult, such as in the oral cavity, it is easy to obtain good physical properties without performing surface polishing or the like for removing an unpolymerized layer.

  Further, the ring-opening polymerizable cationic polymerizable monomer has less polymerization shrinkage when polymerized than the radical polymerizable monomer, and uses such a ring-opening polymerizable cationic polymerizable monomer. By adding a filler, it is possible to further reduce polymerization shrinkage, so when such a polymerizable composition is used as a dental composite resin, a gap is generated at the interface between the composite resin and the tooth during polymerization. Very little sealing can be obtained, and the risk of bacteria invading through the gap after treatment and causing secondary caries is thus greatly reduced.

  The photoacid generator (A) used in the photocationic polymerization initiator of the present invention is a compound capable of directly generating a Bronsted acid or a Lewis acid upon irradiation with ultraviolet light or the like, and known compounds are used without any limitation.

  Such photoacid generators are variously described in each of the above-mentioned prior art documents. Specifically, diaryliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, and halomethyl-substituted -s- And triazine-containing conductors.

  In the present invention, among the photoacid generators, diaryliodonium salt-based photoacid generators are excellent in that the polymerization activity is particularly high.

  A typical diaryliodonium salt-based compound is represented by the following general formula (1)

(In the above _formulas, the R _1, R 2, _{R 3} and _{R 4} are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group or a nitro group, M ^- Are halide ions, p-toluenesulfonate ions, perfluoroalkylsulfonate ions, tetrafluoroborate ions, tetrakis (pentafluorophenyl) borate ions, tetrakis (pentafluorophenyl) gallate ions, hexafluorophosphate ions, hexafluorophosphate Arsenate ion and hexafluoroantimonate ion.)
And a diaryliodonium salt compound represented by the formula:

  Specific examples of the diaryliodonium salt compound represented by the general formula (1) include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, and p-isopropyl. Phenyl-p-methylphenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyloxyphenylphenyliodonium, cations such as p-phenoxyphenylphenyliodonium and chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pe And salts of anions such as (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) gallate, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate.

  Among these aryliodonium salts, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) are preferred from the viewpoint of solubility in cationically polymerizable monomers. Gallate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate salts are preferred, and from the viewpoint of stability when stored in the same package as the cationic polymerizable monomer because of low nucleophilicity, Fluoroantimonates, tetrakis (pentafluorophenyl) borate, and tetrakis (pentafluorophenyl) gallate salts are particularly preferred.

  Further, specific examples of the photoacid generator other than the above-mentioned aryl borate salt suitably used in the present invention include, as a sulfonium salt compound, dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium. Dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8-dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, diphenyl- Chlorides such as 4-phenylthiophenylsulfonium, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluoro Examples include phenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate salts.

  Specific examples of the sulfonic acid ester compound include benzoin tosylate, α-methylol benzoin tosylate, o-nitrobenzyl p-toluenesulfonate, p-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate and the like. And specific examples of halomethyl-substituted-S-triazine conductors include 2,4,6-tris (trichloromethyl) -S-triazine and 2-methyl-4,6-bis (trichloromethyl) -S- Triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (tribromomethyl) -S-triazine and the like can be mentioned.

  In the present invention, these photoacid generators may be used alone or in combination of two or more.

  The amount of the photoacid generator to be used is not particularly limited as long as it can initiate polymerization by light irradiation, but the polymerization proceeds at an appropriate rate and various physical properties of the obtained cured product (for example, weather resistance). In order to achieve both of the above-mentioned properties, the amount is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the cationic polymerizable monomer described below.

  The second component in the cationic photopolymerization initiator composition of the present invention is (B) a condensed polycyclic aromatic compound. The fused polycyclic aromatic compound has a molecular structure in which a non-aromatic ring is further fused to the fused polycyclic aromatic ring, and the fused polycyclic aromatic ring and the non-aromatic At least one of the non-aromatic ring-constituting atoms directly bonded to the atom shared by the ring is a saturated carbon atom, and the saturated carbon atom must have at least one hydrogen atom .

  The effect of the present invention cannot be obtained with a compound in which the condensed polycyclic aromatic compound is not condensed with a non-aromatic ring and is entirely composed of only aromatic rings. Further, even when condensed with a non-aromatic ring, among the atoms constituting the non-aromatic ring, an atom (condensed atom) shared by the non-aromatic ring and the condensed polycyclic aromatic ring The effect of the present invention can be obtained when all of the bonding atoms (hereinafter sometimes simply referred to as condensed atom adjacent atoms) have no hydrogen atoms or are other than saturated carbon atoms. Absent. That is, when all adjacent atoms of the condensed atom are saturated carbon atoms substituted so as to have no hydrogen atom such as a dichloromethylene group or a dimethylmethylene group, or a part of a double bond or a part of a triple bond The effect of the present invention cannot be obtained when the carbon atom is an unsaturated carbon atom constituting the following formula, or when the atom is an atom other than a carbon atom such as an oxygen atom and a nitrogen atom.

  On the other hand, the condensed polycyclic aromatic compound in the present invention has two or more condensed atom adjacent atoms, except when the non-aromatic ring is a three-membered ring, and all of them have at least one hydrogen atom. Need not be a saturated carbon atom having the formula Except for one of the plurality of condensed carbon adjacent atoms, it is an atom other than the above-described carbon atom, a carbon atom having no hydrogen atom, or an unsaturated carbon atom. Is also good. In addition, atoms constituting a non-aromatic ring other than adjacent atoms of a condensed atom (excluding an atom shared with a condensed polycyclic aromatic ring) are not limited to the above, and may be atoms of any kind or state. There may be.

  The condensed polycyclic aromatic ring moiety in the condensed polycyclic aromatic compound (B) in the present invention may have any known structure, but from the viewpoint of polymerization activity and ease of synthesis or availability, 2 to 6 benzenes It is preferably a condensed polycyclic aromatic hydrocarbon ring in which the rings are condensed. Specific examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring obtained by condensing two benzene rings, an anthracene ring or a phenanthrene ring obtained by condensing three benzene rings, and four benzene rings. Are condensed, a naphthacene ring, a 1,2-benzanthracene ring, a chrysene ring or a pyrene ring, and the benzo (a) pyrene ring, benzo (e) pyrene ring, benzo ( g) A pyrene ring, a benzo (h) pyrene ring, a benzo (i) pyrene ring, a perylene ring, a pentacene ring, a pentaphene ring or a picene ring, and a hexaphene ring, a hexacene ring and the like are exemplified as a condensed six benzene rings. Is done.

  On the other hand, a non-condensed aromatic ring such as a single benzene ring cannot improve the polymerization activity, so that the effects of the present invention cannot be obtained.

  In the fused polycyclic aromatic compound (B) in the present invention, a non-aromatic ring is further fused to the fused polycyclic aromatic ring as described above. That is, the condensed polycyclic aromatic compound of the present invention has a total of three or more rings of at least two rings exhibiting aromaticity (fused with each other) and at least one non-aromatic ring. It has a condensed structure. The form in which the non-aromatic ring is condensed with the condensed polycyclic aromatic ring is not particularly limited, and ortho-type in which one side of the condensed polycyclic aromatic ring and the non-aromatic ring is shared It may be condensed, or ortho-peri-condensation in which two or more sides of a condensed polycyclic aromatic ring and a non-aromatic ring are shared. For example, 1,2,3,4-tetrahydrophenanthrene, which corresponds to a compound obtained by condensing cyclohexane with the a-side of naphthalene, corresponds to the former, and 2,2, which corresponds to a compound obtained by condensing cyclohexane with two sides d and e of naphthalene. 3-Dihydrophenalene corresponds to the latter.

  As the non-aromatic ring condensed to such a condensed polycyclic aromatic compound, at least one of the atoms bonded to a condensed atom shared by the non-aromatic ring and the condensed polycyclic aromatic ring, The ring is not particularly limited as long as it is a saturated carbon atom ring having at least one hydrogen atom, and may be any known non-aromatic ring. Further, the non-aromatic ring may be further condensed with another aromatic ring or non-aromatic ring, or may have various substituents.

  Furthermore, in the condensed polycyclic aromatic compound in the present invention, a plurality of non-aromatic rings may be condensed, and further a non-cyclic substituent may be substituted.

  The compound which can be preferably used as the condensed polycyclic aromatic compound of the present invention includes the following general formula (2)

(In the above equation, the following equation (3)

Is a (m + 2) -valent condensed polycyclic aromatic hydrocarbon ring group in which 2 to 6 benzene rings are condensed, and has the following formula (4)

Is shared with the condensed polycyclic aromatic hydrocarbon ring among the non-aromatic rings condensed with the condensed polycyclic aromatic hydrocarbon ring represented by the above formula (3). R ₅ is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group or a monovalent organic residue having 1 to 10 carbon atoms, and R ₆ is a halogen atom, a hydroxyl group, a mercapto group, or a 1 carbon atom. It may be a monovalent organic residue of 10 to 10, or R ₆ may be bonded to each other to form a non-aromatic ring, m is an integer of 0 to 6, and R ₆ is plural. In each case or when there are a plurality of non-aromatic rings formed by bonding R _{6 s} , they may be the same or different. )).

  In the above equation (2)

Represents a (m + 2) -valent polycyclic aromatic hydrocarbon group in which 2 to 6 benzene rings are condensed. Specific examples of the polycyclic aromatic hydrocarbon group include (m + 2) -valent groups derived from those exemplified as the condensed polycyclic hydrogen ring.

  The partial structure is represented by the above formula (4) (the remainder is shared with the condensed polycyclic aromatic hydrocarbon ring represented by the above formula (3)). The aromatic ring is not particularly limited, and at least three carbon atoms (at least two of which are shared with the condensed polycyclic aromatic hydrocarbon ring and at least one is a saturated carbon atom bonded to the condensed carbon atom) Any non-aromatic ring having an atom (having as at least one hydrogen atom) may be used, but the ring preferably has 5 to 7 atoms (condensed polycyclic aromatic hydrocarbon). (Including an atom shared with a ring). Further, the non-aromatic ring may be a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like as a ring-constituting atom.

Specific examples of the non-aromatic ring fused to the condensed polycyclic aromatic hydrocarbon ring include a saturated hydrocarbon having 4 to 7 ring-constituting atoms such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. Rings; partially unsaturated hydrocarbon rings having 4 to 7 ring atoms such as cyclopentene ring, cyclohexene ring, cycloheptene ring and 1,2-cycloheptadiene ring; oxygen-containing saturated heterocycles such as oxetane ring and tetrahydrofuran ring Rings; nitrogen-containing saturated heterocycles such as azetidine ring, tetrahydropyran ring, pyrrolidine ring, piperazine ring; sulfur-containing saturated heterocycles such as trimethylene sulfide ring, tetrahydrothiophene ring, tetramethylene sulfide ring; γ-butyrolactone ring , Δ-valerolactone ring, ε-caprolactone ring, γ-butyrolactam ring, δ-valerolactam ring, ε Unsaturated heterocycles such as caprolactam ring; or ring structure such as 1,2,3,4,5,6,7,8-octahydronaphthalene ring, benzocyclopentane ring, benzocyclohexane ring, benzocycloheptane ring, etc. Examples thereof include a condensed polycyclic ring having 7 to 12 carbon atoms in which another ring is condensed to a hydrocarbon ring having 4 to 7 atoms. (The names of these rings are based on the nomenclature when they are not condensed with a condensed polycyclic aromatic hydrocarbon ring, and the condensed rings change their names as rings.)
These rings may have, as R ₅ in the above formula, a hydroxyl group, a mercapto group, a halogen atom, or a monovalent organic residue having 1 to 10 carbon atoms as a substituent. May have, as a substituent, a hydroxyl group, a mercapto group, a halogen atom, a monovalent organic residue having 1 to 10 carbon atoms, or the like. Furthermore, other aromatic and / or non-aromatic rings may be condensed.

In R ₅ in the above formula, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The monovalent organic residue having 1 to 10 carbon atoms is not particularly limited, and may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted group. , A substituted or unsubstituted alkylthio group, a substituted or unsubstituted aryl group, a dialkylamino group and the like. Examples of the unsubstituted alkyl group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t-butyl group, a pentyl group, an isopentyl group, and a hexyl group. Is exemplified.

  The substituent in the substituted alkyl group is not particularly limited, and may be an alkoxy group such as a methoxy group and an ethoxy group; an aryl group such as a phenyl group and a tolyl group; a 1-alkenyl group such as a vinyl group and a 1-propenyl group. A hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an acyloxy group such as an acetyloxy group and a benzoyloxy group; an alkylthio group such as an ethylthio group and a butylthio group; and a mercapto group.

  Examples of the substituted or unsubstituted alkenyl group include an unsubstituted alkenyl group such as a vinyl group and a 1-propenyl group, and a group in which these are substituted with the same substituent as the above-mentioned alkyl group. Examples of the substituted acyloxy group include an unsubstituted acyloxy group such as an acetyloxy group, a propionyloxy group, and a benzoyloxy group, and a group in which these are substituted with the same substituents as the above-described alkyl group.

  Examples of the substituted or unsubstituted alkoxy group and the substituted or unsubstituted alkylthio group include an alkoxy group and an alkylthio group derived from the above substituted or unsubstituted alkyl group.

  Examples of the substituted or unsubstituted aryl group include a phenyl group and a tolyl group, and examples of the dialkylamino group include a dimethylamino group and a diethylamino group.

R ₅ is particularly preferably a hydrogen atom, and further preferably has no substituent at other positions on the non-aromatic ring. The condensed non-aromatic ring is preferably a saturated or partially unsaturated hydrocarbon ring from the viewpoint of easy synthesis and availability. Most preferably, a hydrocarbon ring having 5 to 7 atoms (including an atom shared with a condensed polycyclic aromatic hydrocarbon ring) constituting the ring, or a carbon obtained by further condensing a hydrocarbon ring with the hydrocarbon ring It is a fused polycyclic hydrocarbon ring of Formulas 8 to 12.

  These substituted or unsubstituted non-aromatic rings are fused with the condensed polycyclic aromatic hydrocarbon ring to share a plurality of carbon atoms, and the condensed polycyclic aromatic compound according to the present invention. Is formed. The number of carbon atoms to be shared is not particularly limited, but is preferably an ortho-condensation or an ortho-peri-condensation in which two or three carbon atoms are shared. Needless to say, when these non-aromatic rings are condensed with a condensed polycyclic aromatic hydrocarbon ring, they are the constituent atoms of the non-aromatic ring and are condensed to the condensed polycyclic aromatic ring. At least one of the directly bonded atoms is a saturated carbon atom having at least one hydrogen atom, that is, the following formula in the general formula (2):

Must be condensed so as to be directly bonded to the condensed polycyclic aromatic hydrocarbon ring represented by the formula (3).

In the above formula (2), R ₆ is a hydroxyl group, a mercapto group, a halogen atom or a monovalent organic residue having 1 to 10 carbon atoms, or R ₆ bonds to each other to form a non-aromatic ring. ing. The halogen atom, the monovalent organic residue having 1 to 10 carbon atoms include the same ones which are specifically exemplified as the above R _5. When a non-aromatic ring is formed, the ring may have a form in which a ring similar to the non-aromatic ring whose partial structure is represented by the above formula (4) is condensed. Further, in this case, at least atoms constituting the non-aromatic ring, which are bonded to a condensed atom shared by the non-aromatic ring formed by the bonding of R ₆ and the condensed polycyclic aromatic ring, It does not need to be a saturated carbon atom having one hydrogen atom. That is, in the non-aromatic ring formed by the bond between R ₆ , all of the atoms bonded to the condensed atom shared by the non-aromatic ring and the condensed polycyclic aromatic ring are atoms other than carbon atoms. And it may be an unsaturated carbon atom, or a saturated carbon atom substituted with a halogen atom or an alkyl group so as not to leave a hydrogen atom.

Moreover, none if the non-aromatic ring which case or is R ₆ together are formed by combining R ₆ is more there are multiple, they may each be the same or different.

  Furthermore, when considering dental applications, it is necessary for the dental light irradiator to have high activity in visible light, and therefore, among the condensed polycyclic aromatic compounds represented by the above formula, the maximum absorption wavelength is 350 nm or more. Are preferred. Generally, by using a compound in which three or more benzene rings are linearly condensed as the polycyclic aromatic hydrocarbon group represented by the formula (3), the maximum absorption wavelength becomes 350 nm or more.

  Illustrative examples of the (B) condensed polycyclic aromatic compound suitably used include:

And the like.

  These condensed polycyclic aromatic compounds can be used alone or as a mixture of two or more.

  The amount of addition varies depending on other components to be combined and the type of the polymerizable monomer. However, the amount of the condensed polycyclic aromatic compound is usually 0.001 to 20 per 1 mol of the photoacid generator (A). Mol, preferably 0.005 to 10 mol.

  The cationic photopolymerization initiator of the present invention comprising the above-mentioned (A) photoacid generator and (B) condensed polycyclic aromatic compound is blended with a cationically polymerizable monomer to form a cationically photopolymerizable composition. used. As the cationic polymerizable monomer, known monomers known to undergo cationic polymerization can be used without any limitation, and such compounds are described in the above-mentioned prior art documents, and various documents cited therein. It is described in detail. Specific examples of typical cationic polymerization monomers include a vinyl ether compound, an epoxy compound, an oxetane compound, an aziridine compound, an azetidine compound, an episulfide compound, a cyclic acetal, a bicyclo ortho ester, a spiro ortho ester, a spiro ortho carbonate, Tetrahydrofuran and the like. In particular, in consideration of dental applications, oxetane compounds and epoxy compounds are particularly preferably used because they are easily available, have small volume shrinkage, and have a fast polymerization reaction.

  Specific examples of the oxetane compound include trimethylene oxide, 3-methyl-3-oxetanylmethanol, 3-ethyl-3-oxetanylmethanol, 3-ethyl-3-phenoxymethyloxetane, 3,3-diethyloxetane, One having one oxetane ring such as 3-ethyl-3- (2-ethylhexyloxy) oxetane, 1,4-bis (3-ethyl-3-oxetanylmethyloxy) benzene, 4,4'-bis (3 -Ethyl-3-oxetanylmethyloxy) biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethyloxymethyl) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, (3-ethyl-3-oxetanylmethyl) Jifenoeto, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, or a compound shown below

And the like having two or more oxatan rings.

  Particularly, from the viewpoint of the physical properties of the obtained cured product, those having two or more oxetane rings in one molecule of the monomer are preferably used.

  Specific examples of preferably used epoxy compounds include diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, and sorbitol poly. Glycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ester , O-phthalic acid diglycidyl ester, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 4,4′-bis (2,3- (Oxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis [4-glycidyloxyphenyl] propane, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, ethylene Glycol-bis (3,4-epoxycyclohexanecarboxylate) and the like.

  These cationically polymerizable monomers can be used alone or in combination of two or more.

  Various cationic polymerization initiators other than those described above can be added to the cationic photopolymerizable composition of the present invention. There is no limitation on other cationic polymerization initiators used in combination, specifically, boron trifluoride etherate, titanium tetrachloride, aluminum trichloride, p-toluenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, Perchloric acid, iodine, iodine bromide, triphenylmethylhexafluoroantimonate and the like can be mentioned.

  Furthermore, in addition to the cationically polymerizable monomer, a radically polymerizable monomer can be blended in the photocationically polymerizable composition of the present invention.

  Examples of suitably usable radical polymerizable monomers include methyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Dipropylene glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxyethoxyethoxy Cyphenyl] propane, 2,2-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 1,4-butanediol di (meth) acrylate, 1,3-hexanediol di ( (Meth) acrylate monomers such as meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane di (meth) acrylate; fumarate ester monomers such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; styrene And styrene such as divinylbenzene, α-methylstyrene and α-methylstyrene dimer; and conductors of α-methylstyrene; and allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate and allyl diglycol carbonate. These radically polymerizable monomers can be used alone or in combination of two or more.

  The amount of the above-mentioned radical polymerizable monomer may be selected according to the purpose, but is preferably used in the range of 0 to 200 parts by mass with respect to 100 parts by mass of the above-mentioned cationic polymerizable monomer. When compounding the radical polymerizable monomer, it is preferable to separately compound a radical polymerization initiator, particularly, a photoradical polymerization initiator.

  As the photoradical polymerization initiator, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether, α-diketones such as camphorquinone and benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Acylphosphon oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are exemplified. In addition, although these α-diketones and acylphosphonic oxides alone show photopolymerization activity, they are used in combination with amine compounds such as ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, and dimethylaminoethyl methacrylate. Is preferable because higher activity can be obtained.

  Further, an aryl borate compound / dye / photoacid generator-based photoradical polymerization initiator described in JP-A-9-3109 and the like can also be suitably used.

  When the photoradical polymerization initiator is blended, a known amount may be used, and specifically 0.01 to 20 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the radical polymerizable monomer. It is about parts by mass.

  Examples of the radical polymerization initiator other than the photoradical polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and tert-butylperoxy as thermal radical polymerization initiators. Peroxides such as dicarbonate and diisopropyl peroxydicarbonate; azides such as azobisisobutyronitrile; tributyl borane; tributyl borane partial oxide; sodium tetraphenylborate; sodium tetrakis (p-fluorophenyl) borate And boron compounds such as potassium tetrakis (p-chlorophenyl) borate.

  The above radical polymerization initiators can be added alone or in combination of two or more as needed.

  The photopolymerizable composition of the present invention itself is useful as a surface coating material or an adhesive, but by further adding a filler, polymerization shrinkage becomes extremely small, and a dental material, particularly a dental filling and restoration material. (Composite resin).

  As the filler, a known filler that can be used for a general dental composite resin is used without any particular limitation. Such fillers are generally roughly classified into organic fillers and inorganic fillers.

  Specific examples of typical organic fillers that can be suitably used include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, and ethylene-vinyl acetate. Copolymers, styrene-butadiene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene copolymers, and the like can be used, and these can be used alone or as a mixture of two or more.

  Specific examples of typical inorganic fillers include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass, and various cation-eluting fillers. Examples of the cation-eluting filler include hydroxides such as calcium hydroxide and strontium hydroxide, and oxides such as zinc oxide, silicate glass, and fluoroaluminosilicate glass. These inorganic fillers may be used alone or in combination of two or more. It should be noted that the use of an inorganic filler containing a heavy metal such as zirconia can impart X-ray contrast.

  Further, a particulate organic-inorganic composite filler obtained by adding a polymerizable monomer to these inorganic fillers in advance, forming a paste, polymerizing and pulverizing the paste, may be used.

  Further, the organic filler, the inorganic filler and the organic-inorganic composite filler can be used in an appropriate combination.

  The particle size and shape of these fillers are not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm, which are generally used as dental materials, can be appropriately used according to the purpose. Also, the refractive index of the filler is not particularly limited, and those having a range of 1.4 to 1.7 that a general dental filler has can be used without limitation.

  The mixing ratio of these fillers may be appropriately determined in consideration of the viscosity (operability) when mixed with the polymerizable monomer and the mechanical properties of the cured product, depending on the purpose of use. Is used in the range of 50 to 1500 parts by mass, preferably 70 to 1000 parts by mass, based on 100 parts by mass of the polymerizable monomer in the present invention.

  Known additives can be further added to the photopolymerizable composition of the present invention, if necessary. Examples of such additives include a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a dye, an antistatic agent, a pigment, and a fragrance.

  Furthermore, it is also possible to add an organic solvent, a thickener and the like as needed. Examples of the organic solvent include hexane, heptane, octane, toluene, dichloromethane, methanol, ethanol, and ethyl acetate. Examples of the thickener include polymer compounds such as polyvinylpyrrolidone, carboxymethylcellulose, and polyvinyl alcohol.

  The production method and packaging form of the cationically polymerizable composition of the present invention may be appropriately determined in consideration of storage stability, and are preferably a photoacid generator, a condensed polycyclic aromatic compound, and a cationically polymerizable monomer. After weighing a predetermined amount of an optional component such as a monomer and a filler, etc. in a dark place, and mixing the mixture to form a liquid or paste-like composition, and storing the composition in a light-shielded state What is necessary is just to fill in a possible container etc.

  As a means for curing the photopolymerizable composition of the present invention, a light source such as a carbon arc, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp, sunlight, a helium cadmium laser, and an argon laser is used without any limitation. The irradiation time varies depending on the wavelength of the light source, the intensity, the shape and the material of the cured body, and may be determined in advance by preliminary experiments, but generally, the irradiation time is in a range of about 5 to 60 seconds. It is preferable to adjust the mixing ratio of various components.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. The compounds used in the text and in the examples and their abbreviations are shown.

  (A) Photoacid generator

  (B) condensed polycyclic aromatic compound

(Note: DOXAn, TCHAn, An, BAn, Pery and DOAn are not condensed polycyclic aromatic compounds used as components of the photocationic polymerization initiator composition of the present invention.)
(C) Cationic polymerizable monomer

(D) Other CQ; camphorquinone DMBE; ethyl N, N-dimethylaminobenzoate The methods for evaluating the physical properties of the materials shown in the text and in the examples are as follows.

(1) Gelation time A cationic polymerizable monomer solution containing the photocationic polymerization initiator composition of the present invention was placed in a sample tube bottle having a capacity of 6 ml and an inner diameter of 1.6 cm so that the cured thick film became 10 mm. (About 1.5-1.6 g). Then, light irradiation was performed from a position 0.5 cm away from the solution surface using a dental light irradiator (TOKUSO POWER LITE, manufactured by Tokuyama Corporation). At this time, the time when the fluidity of the monomer disappeared was defined as the gelation time.

(2) Curability In the same manner as described above, 1.6 g of the solution was placed in a 6 ml sample tube bottle, and the hardness of the cured body after light irradiation for 2 minutes and the presence or absence of an unpolymerized portion were evaluated in four steps. That is, those having sufficient hardness and having no unpolymerized portions (liquid, jelly-like or rubber-like portions) at all ◎, those having unpolymerized portions but having a partially cured depth of at least 10 mm. (Circle), the thing which hardened partially, but the hardening depth did not reach 10 mm was set to (triangle | delta), and the thing which gelated partially but was mostly liquid, or what hardly hardens at all was x.

(3) Depth of cure In the same manner as described above, 1.6 g of the solution was placed in a 6 ml sample tube bottle, and irradiated with light for 2 minutes. After the light irradiation, the cured sample was taken out by breaking the sample tube bottle, and the shallowest part of the cured depth was measured and defined as the cured depth.

(4) Flexural Strength / Flexural Modulus The curable composition was filled in a mold of 2 × 2 × 25 mm and irradiated with light for 1.5 minutes with a light irradiator to be cured. After storing the cured product at 37 ° C. overnight, using an autograph (manufactured by Shimadzu Corporation), the three-point bending strength and the bending elastic modulus were each five at a distance between supports of 20 mm and a crosshead speed of 0.5 mm / min. Was measured and the average value was calculated.

(5) Polymerization Shrinkage A SUS plunger having a diameter of 3 mm and a height of 4 mm was charged into a SUS split mold having a hole having a diameter of 3 mm and a height of 7 mm to make the height of the hole 3 mm. This was filled with the curable composition and pressed with a polypropylene film from above. The film surface was placed downward on a glass table equipped with a dental irradiator, and a short needle capable of measuring the movement of a minute needle was contacted from above a SUS plunger. Polymerization and curing were performed using a dental irradiator, and the shrinkage [%] 10 minutes after the start of irradiation was calculated from the vertical movement distance of the short hand.

(6) Surface unpolymerized The curable composition was placed in a state of contact with air, and irradiated with a dental irradiator for 1 minute. If the surface of the obtained cured product had stickiness due to unpolymerization, it was evaluated as x, and if there was no stickiness, it was evaluated as ○.

Examples 1 to 19
To 100 parts by mass of the cationic polymerizable monomer shown in Table 1, 0.2 parts by mass of the photoacid generator shown in Table 1 and 0.05 parts by mass of the condensed polycyclic aromatic compound were added, and the mixture was added to a dark place. Dissolved below. Table 1 shows the results of the gelation time, curability, and curing depth of this solution. In all of the examples, gelling quickly occurred and good curability was selected.

Comparative Examples 1 and 2
0.2 parts by mass of the photoacid generator shown in Table 1 and 0.05 parts by mass of the condensed polycyclic aromatic compound were added to 100 parts by mass of OX-1, and dissolved in a dark place. -19. Table 1 shows the results of the gelation time, curability, and curing depth.

  In Comparative Examples 1 and 2, instead of the condensed polycyclic aromatic compound of the component (B) in the essential components of the present invention, a condensed atom shared by a non-aromatic ring and a condensed polycyclic aromatic ring was used. The bonded atoms are those using a condensed polycyclic aromatic compound which is not a saturated carbon atom having a hydrogen atom, and in all Examples, a long irradiation of light is required until gelation, and a sufficient curing depth is required. Could not get.

Comparative Examples 3 to 5
0.2 parts by mass of the photoacid generator shown in Table 1 and 0.05 parts by mass of the condensed polycyclic aromatic compound were added to 100 parts by mass of OX-1, and dissolved in a dark place. -19. Table 1 shows the results of the gelation time, curability, and curing depth.

  Comparative Examples 3 to 5 used unsubstituted condensed polycyclic aromatic compounds instead of the condensed polycyclic aromatic compounds of component (B) in the essential components of the present invention. In the above method, long-time light irradiation was required until gelation, and a further sufficient curing depth could not be obtained.

Comparative Example 6
0.2 parts by mass of the photoacid generator shown in Table 1 and 0.05 parts by mass of the condensed polycyclic aromatic compound were added to 100 parts by mass of OX-1, and dissolved in a dark place. -19. Table 1 shows the results of the gelation time, curability, and curing depth.

  In Comparative Example 6, a condensed polycyclic aromatic compound substituted with an alkoxy group was used instead of the condensed polycyclic aromatic compound as the component (B) in the essential components of the present invention. Time light irradiation was required, and a sufficient curing depth could not be obtained.

Comparative Example 7
0.2 parts by mass of DPISb, 0.05 parts by mass of CQ, and 0.05 parts by mass of DMBE were added to 100 parts by mass of OX-1, and dissolved in a dark place, and carried out in the same manner as in Examples 1 to 19. did. Table 1 shows the results of the gelation time, curability, and curing depth.

  Comparative Example 7 is a case where CQ as a sensitizing dye and DMBE as an electron donor were used instead of the condensed polycyclic aromatic compound. Under the conditions of this example, a curing depth of 10 mm or more was obtained. Could not.

Comparative Example 8
0.05 parts by mass of DPP was added to 100 parts by mass of OX-1, dissolved in a dark place, and carried out in the same manner as in Examples 1 to 19. Table 1 shows the results of the gelation time, curability, and curing depth.

  Comparative Example 8 is an example in which only a condensed polycyclic aromatic compound was used without using a photoacid generator. In this case, no curing behavior was exhibited.

Examples 20 to 25
0.8 parts by weight of DPISb and 0.2 parts by weight of DPP were dissolved in 100 parts by weight of a mixture having a weight ratio of OX-2 / EP-1 = 95/5 to obtain a solution A in a dark place. Similarly, a solution prepared using a mixture of OX-2 / EP-2 = 95/5 was a solution B, and a solution prepared using a mixture of OX-2 / DV = 95/5 was a solution C, BOE / EP- Solution D was prepared using a 2 = 50/50 mixture.

  20 g of quartz powder (particle size: 5 μm) was suspended in 80 ml of an aqueous acetic acid solution adjusted to pH 4.0, and 0.8 g of 3-glycidyloxypropyltrimethoxysilane was added dropwise with stirring. After stirring for 1 hour, water was distilled off with an evaporator, and the obtained solid was pulverized in a mortar and dried at 80 ° C. under reduced pressure for 15 hours. After drying, the obtained powder was used as the inorganic filler F1.

  Similarly, the mixture is treated with 3-glycidyloxypropyltrimethoxysilane to obtain spherical silica (particle diameter 0.2 to 2 μm) from F2, spherical silica-zirconia (particle diameter 0.4 μm) from F3, and spherical silica-zirconia (particle diameter). F4 from 0.2 μm), F5 from spherical silica-titania (particle diameter 0.1 μm), and F6 from ground silica-zirconia (particle diameter 5 μm).

  The prepared inorganic filler and the solution were mixed in an agate mortar, and the mixture was defoamed under vacuum to remove air bubbles to obtain a curable composition. Further, the filler content relative to the curable composition was represented by a weight ratio, and was defined as a filling rate (%).

  Table 2 shows the composition, flexural strength, flexural modulus, polymerization shrinkage, and unpolymerized surface of the curable composition.

Claims (4)

A cationic photopolymerization initiator composition comprising (A) a photoacid generator and (B) a condensed polycyclic aromatic compound, wherein the condensed polycyclic aromatic compound is a condensed polycyclic aromatic compound. The non-aromatic ring has a molecular structure in which a non-aromatic ring is further condensed to the ring, and the non-aromatic property is directly bonded to an atom shared by the condensed polycyclic aromatic ring and the non-aromatic ring. A cationic photopolymerization initiator composition, wherein at least one of the ring-constituting atoms is a saturated carbon atom, and the saturated carbon atom has at least one hydrogen atom. The cationic photopolymerization initiator composition according to claim 1, wherein (A) the photoacid generator is a diaryliodonium salt compound. A cationic photopolymerizable composition comprising the cationic photopolymerization initiator composition according to claim 1. The cationic photopolymerizable composition according to claim 3, which is for dental use.