WO2017154983A1 - 光重合開始剤及び光硬化性組成物 - Google Patents
光重合開始剤及び光硬化性組成物 Download PDFInfo
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- WO2017154983A1 WO2017154983A1 PCT/JP2017/009248 JP2017009248W WO2017154983A1 WO 2017154983 A1 WO2017154983 A1 WO 2017154983A1 JP 2017009248 W JP2017009248 W JP 2017009248W WO 2017154983 A1 WO2017154983 A1 WO 2017154983A1
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- Prior art keywords
- light
- photopolymerization initiator
- tertiary amine
- mass
- parts
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- 239000001016 thiazine dye Substances 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/62—Photochemical radical initiators
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/79—Initiators
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
Definitions
- the present invention relates to a photopolymerization initiator useful for applications such as dental materials, photoresist materials, printing plate materials, hologram materials and the like, particularly for dental materials, and a photocurable composition containing the photopolymerization initiator.
- Photopolymerization initiators that generate radical or ionic species by light irradiation are used in various applications as a photocurable composition in combination with a polymerizable unsaturated compound or a polymerizable cyclic compound.
- a photosensitizer that generates energy by absorbing light and generates a polymerization active species by the generated energy is used, but in combination with the photosensitizer, polymerization is performed.
- a reducing agent (electron donor) having an accelerating function is also used.
- acyl phosphine oxide compounds and ⁇ -diketone compounds are known, and in particular, ⁇ -diketone compounds exhibit radical generating ability in the visible light wavelength region which has little influence on the human body.
- ⁇ -diketone compounds exhibit radical generating ability in the visible light wavelength region which has little influence on the human body.
- camphor quinone which is a representative compound of ⁇ -diketone
- various dyes are also known as photosensitizers.
- an amine compound is representative, and in particular, a tertiary amine is widely used in combination with the above-mentioned ⁇ -diketone.
- the photopolymerization initiator as described above is incorporated in a paste-like composition (referred to as a composite resin) mainly composed of a polymerizable monomer and a filler, whereby a composite is obtained.
- the resin is provided with photopolymerizability.
- the said composite resin is shape
- light to be irradiated for polymerization and curing may be referred to as "activation light".
- such active light is about 10 mm or less using a light source having an output light intensity of about 100 to 1500 mW / cm 2 in a wavelength range of about 360 to 500 nm (which is the main absorption range of ⁇ -diketone compounds). Irradiated from a distance.
- the composite resin is filled into the cavity of the tooth to be repaired and formed into a tooth shape, and then it is irradiated with actinic light using a dedicated light irradiator to cure and cure the tooth. It has been done.
- the composite resin is built up in the shape of a tooth to be repaired on a plaster model, and this is polymerized and cured by light irradiation, and then the cured product obtained in a dental clinic is used with a dental adhesive. Bonding to dentin also results in tooth restoration.
- the photopolymerization initiator contains a combination of a photosensitizer such as an ⁇ -diketone compound and a tertiary amine compound, it is possible that the operation such as filling or building up is performed. There is a problem that the viscosity of the composite resin (paste) increases and the operation becomes difficult.
- ambient light emitted from a dental light or a room light (for example, a fluorescent lamp) illuminating the inside of the oral cavity.
- white light emitted from a dental light or a room light (for example, a fluorescent lamp) illuminating the inside of the oral cavity.
- ambient light General ambient light is adjusted to about 500 to 10000 lux in consideration of visibility and the like.
- the light intensity of ambient light in the main absorption region (360 to 500 nm) of the ⁇ -diketone compound is 1 mW / cm 2 or less, and less than a few percent of the active light.
- a polymerization initiator consisting of a combination of an ⁇ -diketone compound and a tertiary amine compound has good polymerization activity to light in the visible range, and because of its good polymerization activity, the environment as described above Sensitive to light, curing starts. Therefore, when working under environmental light which is essential for operations such as filling and building up, the height of this polymerization activity works adversely and the curing progresses gradually, causing the above problems. It is a thing.
- the phenomenon of an increase in the viscosity of the paste during operations such as filling and buildup can be avoided by reducing the amount of the photopolymerization initiator used or increasing the amount of the polymerization inhibitor added.
- the strength of the resulting cured product is reduced without sufficient curing occurring even when irradiated with active light for the same time as in the prior art, and a large amount of unpolymerized monomer is present near the surface of the cured product. Problems often occur such as being left behind. For this reason, it is necessary to lengthen irradiation time of active light in order to advance polymerization curing sufficiently.
- the composite resin is often used in the oral cavity of a patient, and taking a long irradiation time not only takes time for operation but also imposes a great burden on the patient. At present, there is a demand for shortening of the curing time.
- the energy saving of the active light source is also progressing, and a light irradiator that irradiates light with an intensity of about 20 to 100 mW / cm 2 using a laser diode or the like is becoming widespread. That is, in the method of reducing the addition amount of the photopolymerization initiator, etc., when a light irradiator such as a laser diode is used, the curing time can not be shortened and the strength of the cured product can not be improved. Without curing, it is difficult to accelerate polymerization and curing quickly and sufficiently.
- the composite resin containing the conventional photopolymerization initiator is excellent in the stability to the environmental light without impairing the reaction activity to the active light, and at the same time the strong light by the light irradiator for dental use etc. No composite resin has been obtained which has the property of curing rapidly when irradiated.
- Patent Document 1 proposes a photopolymerization initiator comprising an aryliodonium salt, a sensitizing compound and an electron donor compound.
- An object of the present invention is photopolymerization that exhibits excellent sensitivity to actinic light, can rapidly complete the polymerization and curing of a polymerizable monomer, and can ensure stability to ambient light.
- An object of the present invention is to provide a photocurable composition containing an initiator and the photopolymerization initiator.
- Another object of the present invention is to provide a photocurable composition suitably used as a dental composite resin.
- the inventors selected a specific aryliodonium salt as a result of conducting many experiments and examining the reactivity of the photopolymerization initiator with respect to the active light, and this aryliodonium salt was used as a photosensitizer and a tertiary amine. By using it in combination with a compound, the sensitivity to active light is significantly improved, and it has been found that the stability of the photocurable composition to ambient light can be secured by utilizing such characteristics, based on such a finding.
- the present invention has been completed.
- a photoinitiator comprising (a) a photosensitizer, (b) a tertiary amine compound and (c) an aryliodonium salt
- the aryliodonium salt (c) one that generates an acid having a dissociation constant of ⁇ 3.0 or more in water at 25 ° C. is selected, and a photopolymerization initiator is provided.
- the aryliodonium salt (c) is diphenyliodonium 2-carboxylate monohydrate.
- the photosensitizer (a) is an ⁇ -diketone.
- the tertiary amine compound (b) contains an aromatic tertiary amine (b1).
- the tertiary amine compound (b) contains an aromatic tertiary amine (b1) and an aliphatic tertiary amine (b2).
- the aryliodonium salt (c) is contained in an amount of 10 to 80% by mass based on the total amount of the tertiary amine compound (b) and the aryliodonium salt (c).
- a photocurable composition comprising the above photopolymerization initiator and a polymerizable monomer.
- a radically polymerizable monomer is used as the polymerizable monomer
- the photopolymerization initiator is compounded in such an amount that the amount of the photosensitizer (a) in the photopolymerization initiator is 0.01 to 10 parts by mass per 100 parts by mass of the polymerizable monomer. is being done, (3) It further contains a filler and is used as a dental composite resin, Is preferred.
- the photopolymerization initiator of the present invention comprises (a) a photosensitizer, (b) a tertiary amine compound and (c) an aryliodonium salt, but the particularly important features are (c) an aryliodonium salt It has an important feature in that a compound which generates an acid having a dissociation constant of -3.0 or more in water at 25 ° C. is used. That is, although the aryliodonium salt is a compound known as a photoacid generator, the specific aryliodonium salt used in the present invention has the acidity of the acid generated upon the cleavage reaction (polymerization reaction) by light irradiation.
- the photocurable composition containing the photopolymerization initiator of the present invention has improved sensitivity (sensitivity to active light) to a halogen lamp, a xenon lamp, or an irradiator equipped with a laser diode, and the curing thereof Very fast.
- the high sensitivity to the above-mentioned active light can be ensured because the acidity of the acid generated from the aryliodonium salt is low, so neutralization with the tertiary amine compound (b) is possible. It is considered that this is because the reaction is suppressed and the polymerization promoting property by the reducing property (electron donating property) possessed by this compound is sufficiently exhibited.
- the photopolymerization initiator exhibits high sensitivity to active light as described above means that the stability of the photocurable composition to ambient light can be easily secured. That is, by reducing the compounding amount of the photopolymerization initiator (particularly the photosensitizer), the stability to environmental light can be enhanced.
- the compounding amount of the photopolymerization initiator when the compounding amount is reduced Naturally, the sensitivity to active light is lowered, and it takes a long time for polymerization and curing.
- the photopolymerization initiator of the present invention has extremely high sensitivity to active light, so that even when the compounding amount is reduced, a decrease in polymerization curability due to irradiation with active light is effectively avoided, and a short time By light irradiation, polymerization and curing by irradiation with active light can be completed.
- the environment is such that the light intensity on the irradiated surface is 0.3 mW / cm 2
- the compounding amount of each component can be adjusted without lowering the polymerization curing property with respect to active light so that 85 seconds or more, particularly 90 seconds or more are required to start the polymerization.
- the photocurable composition of the present invention when used as, for example, a dental compound resin, it is possible to easily carry out operations such as filling the cavity of the tooth and building up the form of the tooth, and further, the activity By irradiation with light, a cured product having excellent properties such as strength can be formed in a short time, and the burden on the patient can be reduced.
- the photopolymerization initiator of the present invention contains (a) a photosensitizer, (b) a tertiary amine compound and (c) an aryliodonium salt as essential components, and further, the photopolymerization initiation characteristic is not impaired. In the range, suitable additives may be included.
- the photosensitizer (a) used in the present invention is a compound that generates energy by light absorption, and generates an active species effective for polymerization such as radicals by this energy transfer (or electron transfer), It has a maximum absorption wavelength of 350 to 700 nm.
- photosensitizers As such a photosensitizer (a), known photosensitizers can be used. For example, ketone compounds (particularly, ⁇ -diketone compounds), coumarin dyes, cyanine dyes, merocyanine dyes, thiazines Dyes, azine dyes, acridine dyes, xanthene dyes, squalium dyes, pyrylium salt dyes and the like can be used as the photosensitizer (a). Among the photosensitizers mentioned above, the following can be mentioned as specific examples of those suitably used.
- ketone compounds Camphorquinone 9,10-phenanthrenequinone, Benzyl diacetyl acetyl benzoyl 2,3-pentadione 2,3-octadione 4,4'-dimethoxybenzyl acenaphthene quinone 4,4-bis (dimethylamino) benzophenone 9-fluorenone 3,4-benzo-9-fluorenone 2-dimethylamino -9-fluorenone 2-methoxy-9-fluorenone 2-chloro-9-fluorenone 2,7-dichloro-9-fluorenone 2-nitro-9-fluorenone 2-acetoxy-9-fluorenone benzanthrone anthraquinone 2,4-dihydroxybenzophenone
- Examples of coumarin dyes 3-Thienoyl coumarin 3- (4-methoxybenzoyl) coumarin 3- (4-cyanobenzoyl) coumarin 3-thienoyl-7-methoxycoumarin 3-benzoyl-7-methoxycoumarin 5,7-dimethoxy-3- (4-) Methoxybenzoyl) coumarin 3-acetyl-7-dimethylaminocoumarin 7-diethylamino-3- (4-cyanobenzoyl) coumarin 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin 3-cinnamoyl-7-diethylaminocoumarin 3- Carboxy-7-diethylaminocoumarin 3- (4-carboxybenzoyl) -7-diethylaminocoumarin 3,3'-carbonylbis (7-diethylamino) coumarin 2,3,6,7-tetrahydro-1,1,7,7- Tetramethyl -10 -(Benz
- cyanine dyes 1,3,3,1 ', 3,3'-Hexamethyl-2,2'-indocyanine perchlorate 1,3'-diethyl-2,2'-quino-selenacyanine iodide 1,1'-diethyl- 2,4'-quinocyanine iodide 3,3'-diethyl-2,2'-thiazolinocarbocyanine iodide 3,3 ', 9-triethyl-5,5'-diphenyl-2,2'- Oxacarbocyanine iodide 3,3'-diethyl-2,2'-thiacarbocyanine iodide 1,1'-diethyl-2,4'-quinocarbocyanine iodide 3,3'-diethyl-2,2 ' -Oxadicarbocyanine iodide 3,3'-diethyl-2,2 '-(4,5,4', 5'-dibenzo
- merocyanine dyes 3-ethyl-5- [2- (3-methyl-2-thiazolidinylidene) Ethylidene] -2-thio-2,4-oxazolidinedione 3-carboxymethyl-5- [2- (3-ethyl-2-benzothiazolylidene) ethylidene] rhodanine 3-ethyl-5- [2- (3-ethyl- 4-Methyl-2-thiazolinylidene) ethylidene] rhodanine
- thiazine dyes Methylene blue thionine chloride
- acridine dyes 1-Aminoacridine 9- (2'-hydroxystyryl) acridine acrylic orange acridine yellow
- squalium dyes Dihydro-3- [2-hydroxy-3- (5-isopropyl-3,8) -Dimethyl-1-azirenyl) -4-oxo-2-cyclobutene-1 -Ylidene] -7-isopropyl-1,4-dimethylazlenium hydroxide
- pyrylium salt dyes Triphenylpyrylium perchlorate 2,6-Bis (4-methylphenyl) -4- (4-phenylthiochloroperclate)
- the above-described photosensitizers can be used alone or in combination of two or more. Further, among the photosensitizers exemplified above, camphorquinone, 9,10-phenanthrenequinone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, An ⁇ -diketone compound such as acenaphthene quinone is most preferably used.
- the tertiary amine compound (b) used in the present invention is a so-called reducing agent (or electron donor) and has a polymerization promoting function.
- a tertiary amine compound (b) an aromatic tertiary amine (b1) having an aromatic ring in the molecule, or an aliphatic tertiary amine having no aromatic ring in the molecule Any of (b2) can be used.
- R 1 and R 2 are each independently an alkyl group
- R 3 is an alkyl group, an aryl group, an alkenyl group, an alkoxy group or an alkyloxycarbonyl group.
- the alkyl group represented by R 1 , R 2 and R 3 is preferably an alkyl group having a carbon number of 1 to 6, and examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl and n- A hexyl group etc. can be mentioned. Moreover, these alkyl groups may, of course, have a substituent. Examples of such a substituent include a halogen atom such as a fluorine atom and a hydroxyl group.
- R 1 to R 3 may be a halogenoalkyl group such as a fluoromethyl group or 2-fluoroethyl group, or a hydroxyalkyl group such as 2-hydroxyethyl group.
- examples of the aryl group include those having 6 to 12 carbon atoms such as phenyl group, p-methoxyphenyl group, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group and the like .
- examples of the alkenyl group include those having 2 to 12 carbon atoms such as vinyl group, allyl group and 2-phenylethenyl group.
- Examples of the alkoxy group include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group.
- alkyloxycarbonyl group examples include those having 1 to 10 carbon atoms in the alkyloxy group moiety such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, amyloxycarbonyl group, isoamyloxycarbonyl group and the like.
- R 1 and R 2 are preferably an alkyl group having 1 to 6 carbon atoms, and in particular, an unsubstituted alkyl group having 1 to 3 carbon atoms For example, methyl group, ethyl group, n-propyl group), 2-hydroxyethyl group and the like are more preferable.
- R 3 is preferably an alkyloxycarbonyl group.
- the following compounds are most preferable as the aromatic tertiary amine represented by the above general formula (1).
- p-Dimethylaminobenzoate methyl p-dimethylaminoethylbenzoate p-dimethylaminopropylpropyl p-dimethylaminopropylbenzoate p-dimethylaminobenzoic acid isoamyl p-diethylaminobenzoate ethyl p-diethylaminobenzoate propyl
- N N-dimethylaniline, N, N-dibenzylaniline, N, N-Dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di ( ⁇ -hydroxyethyl) -p-toluidine
- aliphatic tertiary amine (b2) suitably used as the tertiary amine compound (b) in the present invention, the following can be mentioned.
- aromatic tertiary amine (b1) and the aliphatic tertiary amine (b2) described above can be used alone or in a combination of two or more.
- aromatic tertiary amines (b1) can be suitably used, they exhibit high polymerization activity, maintain polymerization curability in a short time by irradiation light, and yet have high curing properties.
- the aromatic tertiary amine (b1) and the aliphatic amine (b2) are used in combination in that physical properties are expressed and furthermore the coloring when the cured product is exposed to ultraviolet light such as sunlight is reduced. Is preferred.
- aromatic tertiary amine (b1) and aliphatic amine (b2) b1: b2 1: 99 to 99: 1
- such a tertiary amine compound (b) is generally used in an amount of 10 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the photosensitizer 1 (a). used.
- aryliodonium salts used in the present invention is a compound known as a so-called acid generator and has the property of generating an acid derived from an anion present in the molecule by a cleavage reaction by light irradiation. ing.
- aryliodonium salts (c) those having an acid dissociation constant of -3.0 or more in water (25.degree. C.) of the acid to be generated are selected in the present invention.
- Such aryliodonium salts are diaryl compounds, and the cleavage reaction by light irradiation generates an acid (HX) as shown in the following formula (2).
- R 4 and R 5 are each independently a hydrogen atom or an alkyl group.
- X ⁇ is a counter anion of aryliodonium salt
- HX is an acid generated in the cleavage reaction shown in the above formula (2).
- the aryliodonium salt (c) used in the present invention generates an acid having a low acidity (the acid dissociation constant in water is -3.0 or more) in the cleavage reaction represented by the above formula (2). . That is, the photocurable composition in which the aryliodonium salt (c) coexists with the photosensitizer (a) and the tertiary amine compound (b) described above is irradiated with active light to cause polymerization reaction.
- an acid derived from an aryl radical and a counter anion of an aryliodonium salt is generated.
- the aryliodonium salt used in the present invention has a low acidity of the acid generated by the above-mentioned cleavage reaction, which effectively suppresses the neutralization reaction between the acid and the tertiary amine compound,
- the aryl radical generated together with the compound effectively acts on the initiation of polymerization to exhibit extremely excellent polymerization activity.
- the aryliodonium salt (c) used in the present invention is an acid having a low acidity, specifically, an acid dissociation constant in water (25 ° C.) of -3.0 or more, especially -2.
- An acid of 0 to 10.0 is generated, and by using such a compound in combination with the photosensitizer (a) and the tertiary amine compound (b) described above, the polymerization activity to active light can be obtained. It can be greatly improved.
- the acid dissociation constants of various acids in water (25 ° C.) are as follows for reference. HCl: -3.7 HBr: -4.1 HNO 3 : -1.8 Chloroacetic acid: 2.9 Benzoic acid: 4.2 Phenol: 9.9
- any aryliodonium (c) which generates an acid having a low acidity any aryliodonium (cation) and a counter anion may be used as long as the acid dissociation constant of the generated acid in water is in the above range.
- the salt which consists of can be used, the following cation and counter anion can be mentioned as this suitable example.
- aryliodonium (cation); Diphenyliodonium Bis (p-chlorophenyl) iodonium Ditollioliodonium Bis (p-methoxyphenyl) iodonium Bis (p-tert-butylphenyl) iodonium p-isopropylphenyl-p-methylphenyliodonium bis (m-nitrophenyl) iodonium p- tert-Butylphenylphenyliodonium p-methoxyphenylphenyliodonium p-octyloxyphenylphenyliodonium p-phenoxyphenylphenyliodonium counteranion examples; Nitrate anion Acetate anion Chloroacetate anion Carboxylate anion Phenolate anion
- diphenyliodonium 2-carboxylate monohydrate is particularly preferable in view of easy availability and excellent curing rate.
- the aryliodonium salt (c) mentioned above is usually used in an amount of 10 to 2000 parts by weight, in particular 20 to 1000 parts by weight, most preferably 20 to 300 parts by weight, per 100 parts by weight of (a) photosensitizer Ru. Moreover, since such aryliodonium salt (c) does not bring about deterioration of the performance of the compound (b) by neutralizing the above-mentioned tertiary amine compound (b), the compound is compared with the compound (b) The curing rate can be increased upon irradiation with active light.
- the aryliodonium salt (c) is 10 to 80% by mass, in particular 15 to 70% by mass, and further 30 to 60% by mass based on the total amount of the tertiary amine compound (b) and the aryliodonium salt (c). It can be used in such an amount as to be% by mass.
- the photopolymerization initiator of the present invention comprising the above-described photosensitizer (a), tertiary amine compound (b) and aryliodonium salt (c) is combined with a polymerizable monomer to form a photocurable composition.
- the amount of photosensitizer (a) (particularly ⁇ -diketone) in this photopolymerization initiator is generally determined by the amount of polymerizable monomer (especially radical) in order to exert its performance sufficiently.
- the polymerizable monomer is preferably used in a proportion of 0.01 to 10 parts by mass, and more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the polymerizable monomer.
- the amount of the photosensitizer (a) used is preferably 1 part by mass or less per 100 parts by mass of the monomer.
- the polymerization curing is completed in about 20 seconds, for example Although depending on the amount of the filler, it is possible to obtain a cured product having a Vickers hardness of 30 or more and a bending strength of 140 MPa or more.
- the photocurable composition containing the above-mentioned photopolymerization initiator of the present invention has an adverse effect on the polymerizability with respect to active light and environmental light, in addition to the polymerizable monomer and the photopolymerization initiator of the present invention depending on its use.
- An appropriate combination agent can be added according to a use in the range which does not exert.
- this photocurable composition can be used for various uses such as dental materials, photoresist materials, printing plate making materials, hologram materials, etc. According to such uses, known compounding agents are appropriately blended. can do.
- the photocurable composition containing the photopolymerization initiator according to the present invention is excellent in the polymerization curing property to active light and can improve the stability to environmental light, so that it can be used for dental restoration. It is extremely useful as a composite resin.
- the various components mixed in this photocurable composition are demonstrated.
- Polymerizable monomer in the present invention, a radical polymerizable monomer or a polymerizable monomer other than this, such as a vinyl ether compound, an epoxy compound, an oxetane compound, an aziridine compound, an azetidine compound, an episulfide compound, cyclic
- cationically polymerizable monomers such as acetals, bicycloorthoesters, spiroorthoesters, spiroorthocarbonates, tetrahydrofuran and the like can also be used, in order to fully exhibit the performance of the photopolymerizable monomer of the present invention
- radically polymerizable monomers are preferably used.
- radically polymerizable monomers known radically polymerizable monomers may be used without any limitation, but in general, from the viewpoint of curing speed and mechanical properties of a cured product, (meth) acrylates
- the polymerizable monomer of the system is suitably used, and in particular, a polyfunctional (meth) acrylate type polymerizable monomer having a plurality of polymerizable functional groups is preferable.
- the polyfunctional (meth) acrylate polymerizable monomer known monomers can be used without particular limitation. Examples of those generally suitably used include those shown in the following (I) to (III).
- diisocyanate compound having an aromatic group diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate and the like are representative, and as a vinyl monomer having an OH mark, 2-hydroxyethyl methacrylate, Methacrylates such as 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates can be exemplified.
- (I-ii) Aliphatic compound based difunctional polymerizable monomer ethylene glycol dimethacrylate diethylene glycol dimethacrylate triethylene glycol dimethacrylate (hereinafter abbreviated as 3G) Tetraethylene glycol dimethacrylate neopentyl glycol dimethacrylate 1,3-butanediol dimethacrylate 1,4-butanediol dimethacrylate 1,6-hexanediol dimethacrylate Acrylate corresponding to the above various methacrylates 1,2-bis (3- A diaduct obtained by adding a vinyl monomer having an OH group to a methacryloyloxy-2-hydroxypropoxy) ethyl diisocyanate compound
- examples of the diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylene bis (4-cyclohexylisocyanate), etc.
- examples of the vinyl monomer having an OH group for example, examples are methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, and acrylates corresponding to these methacrylates.
- polyfunctional (meth) acrylate-based polymerizable monomers may be used in combination of two or more kinds, if necessary. Moreover, you may use a monofunctional (meth) acrylate type monomer as needed.
- the radically polymerizable monomers described above can be used singly or in combination of two or more, and as necessary, easiness of polymerization, adjustment of viscosity, or others
- these other polymerizable monomers the following can be mentioned in addition to the above-mentioned cationic polymerizable monomers.
- Fumaric acid esters such as monomethyl fumarate, diethyl fumarate, Diphenyl fumarate; Styrene or ⁇ -methylstyrene derivatives such as styrene, divinylbenzene, ⁇ -methylstyrene, ⁇ -methylstyrene dimers; Aryl compounds such as diaryl terephthalates, diaryl phthalates, diaryl diglycol carbonates;
- a typical example of a compounding agent appropriately blended in addition to the above-described photopolymerization initiator and polymerizable monomer is a filler, and the mechanical strength and the like of a cured product to be obtained can be improved by blending the filler.
- the following inorganic fillers are typical as such a filler.
- Metal simple substances such as Periodic group I, II, III, Group IV metals, transition metals; Oxides and complex oxides of the above metals;
- Metal oxides such as amorphous silica, quartz, alumina, titania, zirconia, barium oxide, yttrium oxide, lanthanum oxide, ytterbium oxide; Silica-based composite oxides such as silica-zirconia, silica-titania, Silica-titania-barium oxide, silica-titania-zirconia; Glass, such as borosilicate glass, aluminosilicate glass, fluoroaluminosilicate glass; Metal fluorides such as barium fluoride, strontium fluoride, yttrium fluoride, lanthanum fluoride, ytterbium fluoride; Inorganic carbonates such as calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate; Metal sulfates, such as magnesium sulfate, barium sulfate;
- particulate organic-inorganic composite fillers obtained by adding a polymerizable monomer to these inorganic fillers in advance and making them into a paste and then polymerizing and pulverizing may be used.
- An organic-inorganic composite filler may be used which is obtained by previously adding an anionic monomer and drying and then polymerizing.
- treating the above-mentioned filler with a surface treatment agent typified by a silane coupling agent improves the compatibility with the polymerizable monomer and can improve the mechanical strength and water resistance.
- a silane coupling agent typified by a silane coupling agent
- silica-zirconia, silica-titania, silica among the above-mentioned fillers, have strong X-ray contrast properties.
- -Titania-barium oxide, silica-titania-zirconia, and their surface treatments are preferred, with silica-zirconia being most preferred.
- each of the above-mentioned fillers can be used alone or in combination of two or more.
- an appropriate refractive index can be used.
- particle size adjustment is carried out to a suitable particle size, and it mixes.
- the refractive index of the filler is generally about 1.4 to 1.7, and the particle size thereof is 0.01
- the thickness is about 100 ⁇ m, particularly about 0.01 to 5 ⁇ m.
- the compounding amount of the filler described above 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.
- it is preferably used in an amount of 50 to 1,500 parts by mass, particularly 70 to 1,000 parts by mass, per 100 parts by mass of the polymerizable monomer described above.
- photocurable composition containing the photopolymerization initiator of the present invention known polymerization initiators such as organic peroxides may be added insofar as the polymerization curability to active light and the stability to environmental light are not impaired. It can also be blended.
- the organic solvent includes hexane, heptane, octane, toluene, dichloromethane, methanol, ethanol, ethyl acetate and the like
- the thickener includes high molecular weight compounds such as polyvinyl pyrrolidone, carboxymethyl cellulose, polyvinyl alcohol and highly dispersible silica. It is illustrated.
- the curing of the photocurable composition containing the photopolymerization initiator of the present invention may be carried out using the same known light source as that used for curing the ⁇ -diketone photopolymerization initiator, but with low strength.
- Carbon arc, xenon lamp, metal halide lamp in order to take advantage of the characteristics of the photopolymerization initiator of the present invention that it is relatively stable against light irradiation, and is rapidly cured by light irradiation of a certain intensity or more.
- Visible light sources such as tungsten lamps, LEDs, halogen lamps, helium cadmium lasers and argon lasers are used without any limitation.
- the irradiation time varies depending on the wavelength and intensity of the light source, and the shape and material of the cured product, and may be determined in advance by preliminary experiments.
- such a photocurable composition is excellent in environmental light stability and curability to active light, and therefore, a dental composite resin used to repair a tooth which has been lost due to caries and the like.
- a dental composite resin used to repair a tooth which has been lost due to caries and the like.
- a dental composite resin used to repair a tooth which has been lost due to caries and the like.
- a dental composite resin used to repair a tooth which has been lost due to caries and the like.
- Additives known as components of composite resins can be blended within a range that does not affect the effects of the present invention.
- Such a photopolymerizable composite resin can be prepared by weighing a predetermined amount of each component to be blended under light shielding and kneading until uniform.
- the photosensitizer (a), the tertiary amine compound (b), the aryliodonium salt (c), the polymerizable monomer and the various additives used in Examples and Comparative Examples of the present invention are as follows. It is.
- the preparation method of the photopolymerizable composite resin which is one use of a photocurable composition, the hardening characteristic (environmental light stability, hardening property, hardness), and the measurement of the mechanical strength of a hardening body used the following method. .
- Hardness of cured product (Vickers hardness) The hardness of the cured product was measured by the following method using the following dental light irradiator. That is, a photocurable composition is filled in a polytetrafluoroethylene mold having a hole of 6 mm ⁇ ⁇ 1.0 mm and pressure-contacted with a polypropylene film, and Toxo Power Light is used as a dental light irradiator, and the irradiator The film was adhered to a polypropylene film and irradiated for 20 seconds to prepare a cured product.
- the resulting cured product was determined using a Vickers indenter with a microhardness tester (MHT-1 manufactured by Matsuzawa Seiki) using the diagonal length of the indentation formed on the test piece with a load of 100 gf and a load holding time of 30 seconds ⁇ tok So power light: optical power density 700 mW / cm 2, light intensity 640 on the irradiated surface ⁇ 650 mW / cm 2, the light source is a halogen lamp, Tokuyama dental Co. ⁇ .
- the hardened body is arranged in a square column of 2 ⁇ 2 ⁇ 25 mm with # 800 water-resistant abrasive paper, and this sample piece is mounted on a testing machine (Autograph AG5000D manufactured by Shimadzu Corporation), the distance between supporting points is 20 mm, crosshead speed The three-point flexural strength was measured at 1 mm / min.
- the distance between the light source and the sample was set so that the surface of the paste-like photocurable composition sample would be 10000 lux.
- a dental light (light source: halogen light, manufactured by Takara Lemont) was used as a light source, and the distance between the sample and the light source was set such that the illuminance measured by the illuminance meter was the above illuminance.
- the light intensity on this irradiated surface was 0.3 mW / cm 2 .
- the prepared photocurable composition sample was weighed in 0.03 g of a polypropylene film and irradiated with the light of dental light for a predetermined time, and then the sample was crushed to measure the time when the inside of the sample started to solidify.
- the irradiation time was 5 seconds apart. As this time is longer, the environmental light stability is more excellent, and thus a good operation margin time can be obtained.
- a luminometer Tokyo Glass Instruments Co., Ltd., Digital Look Meter FLX-1330 was used. This luminometer has a sensitivity of 400 to 700 nm.
- Example 1 Each component was mixed in the dark according to the following formulation to prepare a uniform solution of the photocurable composition.
- Polymerizable monomer 100 parts by mass
- D-2.6E 70 parts by mass
- 3G 25 parts by mass
- UDMA 5 parts by mass
- Photopolymerization initiator 0.9 parts by mass
- CQ 0.3 parts by mass DMBE: 0.5 parts by mass
- DPICH 0.4 parts by mass
- Example 2 to 7 and Comparative Examples 1 to 6 A solution was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed to the combination described in Table 1. The Vickers hardness of the cured product prepared from these solutions was evaluated under the conditions described above. The results are shown in Table 1.
- the photosensitizer (a), the tertiary amine compound (b), and the acid dissociation constant of the acid generated by the cleavage reaction in water are -3.0 or more.
- the cured product obtained from the solution combined with an aryliodonium salt (c) exhibited high Vickers hardness.
- Comparative Examples 1 and 2 are the examples which do not mix
- Comparative Examples 5 and 6 use aryliodonium salts in which the acid dissociation constant in water (25 ° C.) of the acid generated by the cleavage reaction is less than ⁇ 3.0. In this case, although the Vickers hardness is higher than that of Comparative Example 1, the Vickers hardness is lower than that of the example.
- Example 8 A paste-like composition was prepared according to the following formulation. Polymerizable monomer (100 parts by mass); D-2.6E: 70 parts by mass 3G: 25 parts by mass UDMA: 5 parts by mass Filler (400 parts by mass); E-1: 160 parts by mass E-2: 240 parts by mass Polymerization inhibitor (HQME): 0.15 parts by mass Photopolymerization in which a photopolymerization initiator having the composition shown in Table 2 was further added to this paste-like composition Type composite resin was obtained. The Vickers hardness, flexural strength and environmental light stability of this photopolymerizable composite resin were evaluated. The results are shown in Table 2.
- Examples 9 to 17 and Comparative Examples 7 to 13 A photopolymerizable composite resin was produced in the same manner as in Example 8 except that the photopolymerization initiator was changed to the combination described in Table 2. The Vickers hardness, flexural strength and environmental light stability of these photopolymerizable composite resins were evaluated under the conditions described above. The results are shown in Table 2.
- Comparative Examples 7 and 8 are examples in which the aryliodonium salt (c) in which the acid dissociation constant in water (25 ° C.) of the acid generated by the cleavage reaction is -3.0 or more is not blended. In this case, the Vickers hardness was lower than those of Examples 8 to 17.
- Comparative Example 9 is an example in which the photosensitizer CQ and the tertiary amine compound DMBE are increased in Comparative Example 7. In this case, although the Vickers hardness and the bending strength were improved as compared with Comparative Example 7, the environmental light stability was lowered.
- Comparative Example 10 is an example in which the tertiary amine compound (b) is not blended, and Comparative Example 11 is an example in which the photosensitizer (a) is not blended.
- the Vickers hardness and the bending strength were lower than those in the case where the aryliodonium salt (c) was not added.
- Comparative Examples 12 and 13 use aryliodonium salts in which the acid dissociation constant in water (25 ° C.) of the acid generated by the cleavage reaction is less than ⁇ 3.0. In this case, although the Vickers hardness and the bending strength were higher than those of Comparative Example 7, the Vickers hardness and the bending strength were lower than those of Examples 8 to 17.
- Example 18 A paste-like composition was prepared according to the following formulation. Polymerizable monomer (100 parts by mass); Bis-GMA: 60 parts by mass 3G: 40 parts by mass Filler (150 parts by mass); E-1: 105 parts by mass E-2: 45 parts by mass Polymerization inhibitor (HQME): 0.15 parts by mass
- This paste-like composition is further mixed with a photopolymerization initiator having the composition shown in Table 3 to give light A cured composite resin was obtained. The Vickers hardness, flexural strength and environmental light stability of this photopolymerizable composite resin were evaluated. The results are shown in Table 3.
- Examples 19 to 27 and Comparative Examples 14 to 20 A photopolymerizable composite resin was prepared in the same manner as in Example 18, except that the photopolymerization initiator was changed to the combination described in Table 3. The Vickers hardness, flexural strength and environmental light stability of these photopolymerizable composite resins were evaluated under the conditions described above. The results are shown in Table 3.
- the cured products using the photopolymerization initiator of the present invention exhibited high Vickers hardness and flexural strength.
- Comparative Examples 14 and 15 are examples in which the aryliodonium salt (c) in which the acid dissociation constant in water (25 ° C.) of the acid generated by the cleavage reaction is -3.0 or more is not blended. In this case, the Vickers hardness was lower than those of Examples 18-27.
- Comparative Example 16 is an example in which the photosensitizer CQ and the tertiary amine compound DMBE are increased in Comparative Example 14. In this case, although the Vickers hardness and the bending strength were improved as compared with Comparative Example 14, on the other hand, the environmental light stability decreased.
- Comparative Example 17 is an example in which the tertiary amine compound (b) is not blended, and Comparative Example 18 is an example in which the photosensitizer (a) is not blended.
- the Vickers hardness and the bending strength were lower than those in the case where the aryliodonium salt (c) was not added.
- Comparative Examples 19 and 20 use aryliodonium salts in which the acid dissociation constant in water (25 ° C.) of the acid generated by the cleavage reaction is less than ⁇ 3.0. In this case, although the Vickers hardness and the bending strength were higher than those of Comparative Example 14, the Vickers hardness and the bending strength were lower than those of Examples 18 to 27.
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Abstract
Description
このような光重合開始剤としては、光を吸収することによりエネルギーを発生し、発生したエネルギーにより重合活性種を生成する光増感剤が使用されるが、光増感剤と組み合わせて、重合促進機能を有する還元剤(電子供与体)なども使用される。
また、光増感剤としては、種々の色素も知られている。
さらに、還元剤としては、アミン化合物が代表的であり、特に第3級アミンは、上記のα-ジケトンと組み合わせて広く使用されている。
一般に、このような活性光は、360~500nm程度の波長域(α-ジケトン化合物の主たる吸収域である)における光強度が100~1500mW/cm2程度の出力の光源を用い、約10mm以下の距離から照射される。
例えば、歯科医院において、コンポジットレジンを、修復すべき歯牙の窩洞に充填して歯牙の形に成形した後に、専用の光照射器を用いて活性光を照射して重合硬化させて歯の修復が行われている。また、歯科技工所内において、コンポジットレジンを石膏模型上で修復すべき歯牙の形に築盛し、これを光照射により重合硬化させ、次いで歯科医院において得られた硬化体を、歯科用接着剤を用いて歯質に接着させることによっても歯の修復が行われる。
一般的な環境光は、視認性等を考慮して500~10000ルクス程度に調整されている。光源にもよるが、α-ジケトン化合物の主たる吸収域(360~500nm)における環境光の光強度は1mW/cm2以下であり、前記活性光の数%にも満たない。然るに、α-ジケトン化合物と第3級アミン化合物の組み合わせからなる重合開始剤は、可視域の光に対して良好な重合活性を有するものであり、その重合活性の良さゆえ、上記のような環境光に対しても鋭敏に感応して硬化が開始する。従って、充填や築盛等の操作に不可欠な環境光の下で作業を行うと、この重合活性の高さが逆に不利に働き、徐々に硬化が進行してしまい、上記のような問題を生じるものである。
即ち、光重合開始剤の添加量を減らすなどの方法では、レーザーダイオード等の光照射器を用いた場合に硬化時間の短縮や硬化体の強度の向上を図ることができず、患者に負担をかけずに、重合硬化を迅速に且つ十分に進行させることが困難である。
本発明の他の目的は、歯科用コンポジットレジンとして好適に使用される光硬化性組成物を提供することにある。
前記アリールヨードニウム塩(c)として、25℃の水中での解離定数が-3.0以上の酸を発生させるものが選択されていることを特徴とする光重合開始剤が提供される。
(1)前記アリールヨードニウム塩(c)が、ジフェニルヨードニウム-2-カルボキシレートモノハイドレートであること。
(2)前記光増感剤(a)が、α-ジケトンであること。
(3)前記第3級アミン化合物(b)が、芳香族第3級アミン(b1)を含むこと。
(4)前記第3級アミン化合物(b)が、芳香族第3級アミン(b1)と脂肪族第3級アミン(b2)とを含むこと。
(5)前記光増感剤(a)100質量部当り、前記第3級アミン化合物(b)を10~1000質量部、および前記アリールヨードニウム塩(c)を10~2000質量部の量で含有していること。
(6)前記第3級アミン化合物(b)とアリールヨードニウム塩(c)との合計量を基準として、10~80質量%の量でアリールヨードニウム塩(c)を含有していること。
(1)前記重合性単量体として、ラジカル重合性単量体が使用されていること、
(2)前記光重合開始剤は、該光重合開始剤中の光増感剤(a)の量が、前記重合性単量体100質量部当り0.01~10質量部となる量で配合されていること、
(3)さらに充填材を含み、歯科用コンポジットレジンとして使用されること、
が好適である。
即ち、本発明の光重合開始剤が配合された光硬化性組成物は、ハロゲンランプやキセノンランプ、あるいはレーザーダイオードを備えた照射器に対する感度(活性光に対する感度)が向上しており、その硬化速度が極めて速い。
即ち、光重合開始剤(特に光増感剤)の配合量を少なくすることにより、環境光に対する安定性を高めることができるのであるが、従来公知の重合開始剤では、その配合量を少なくすると、当然、活性光に対する感度が低下し、重合硬化に長時間を要することとなる。しかるに、本発明の光重合開始剤は、活性光に対する感度が極めて高いため、その配合量を少なくした場合においても、活性光照射による重合硬化性の低下が有効に回避されており、短時間の光照射により、活性光照射による重合硬化を完了させることができる。
例えば、本発明の光重合開始剤が配合された光硬化性組成物では、後述する実施例に示されているように、照射面での光強度が0.3mW/cm2となるように環境光が照射されたとき、重合開始までに85秒以上、特に90秒以上を要するように、活性光に対する重合硬化性を低下させることなく、各成分の配合量を調節することができる。
本発明の光重合開始剤は、必須成分として、(a)光増感剤、(b)第3級アミン化合物及び(c)アリールヨードニウム塩を含み、さらに、この光重合開始特性が損なわれない範囲で、適宜の添加剤を含んでいてもよい。
本発明において使用される光増感剤(a)は、光吸収によりエネルギーを発生し、このエネルギー移動(或いは電子移動)により、ラジカルのような重合に有効な活性種を生成させる化合物であり、最大吸収波長を350~700nmに有する。
上記で挙げた光増感剤の内、好適に使用されるものの具体例としては、以下のものを挙げることができる。
カンファーキノン
9,10-フェナントレンキノン、
ベンジル
ジアセチル
アセチルベンゾイル
2,3-ペンタジオン
2,3-オクタジオン
4,4’-ジメトキシベンジル
アセナフテンキノン
4,4-ビス(ジメチルアミノ)ベンゾフェノン
9-フルオレノン
3,4-ベンゾ-9-フルオレノン
2-ジメチルアミノ-9-フルオレノン
2-メトキシ-9-フルオレノン
2-クロロ-9-フルオレノン
2,7-ジクロロ-9-フルオレノン
2-ニトロ-9-フルオレノン
2-アセトキシ-9-フルオレノン
ベンズアントロン
アントラキノン
2、4-ジヒドロキシベンゾフェノン
3-チエノイルクマリン
3-(4-メトキシベンゾイル)クマリン
3-(4-シアノベンゾイル)クマリン
3-チエノイル-7-メトキシクマリン
3-ベンゾイル-7-メトキシクマリン
5,7-ジメトキシ-3-(4-メトキシベンゾイル)クマリン
3-アセチル-7-ジメチルアミノクマリン
7-ジエチルアミノ-3-(4-シアノベンゾイル)クマリン
7-ジエチルアミノ-3-(4-ジメチルアミノベンゾイル)クマリン
3-シンナモイル-7-ジエチルアミノクマリン
3-カルボキシ-7-ジエチルアミノクマリン
3-(4-カルボキシベンゾイル)-7-ジエチルアミノクマリン
3,3’-カルボニルビス(7-ジエチルアミノ)クマリン
2,3,6,7-テトラヒドロ-1,1,7,7-テトラメチル
-10-(ベンゾチアゾイル)-11-オキソ-1H,5H,11H
-[1ベンゾピラノ[6,7,8-ij]キノリジン
3,3’-カルボニルビス(5,7-)ジメトキシ3,3’-ビス
クマリン
3-(2’-ベンズオキサゾイル)-7-ジエチルアミノクマリン
3-(5’-フェニルチアゾイル-2’)-7-ジエチルアミノ
クマリン
3,3’-カルボニルビス(4-シアノ-7-ジエチルアミノ)
クマリン
1,3,3,1’,3,3’-ヘキサメチル-2,2’-インド
シアニンパークロレート
1,3’-ジエチル-2,2’-キノ-セレナシアニンアイオダイド
1,1’-ジエチル-2,4’-キノシアニンアイオダイド
3,3’-ジエチル-2,2’-チアゾリノカルボシアニン
アイオダイド
3,3’、9-トリエチル-5,5’-ジフェニル-2,2’-
オキサカルボシアニンアイオダイド
3,3’-ジエチル-2,2’-チアカルボシアニンアイオダイド
1,1’-ジエチル-2,4’-キノカルボシアニンアイオダイド
3,3’-ジエチル-2,2’-オキサジカルボシアニンアイオダイド
3,3’-ジエチル-2,2’-(4,5,4’、5’-ジベンゾ)
チアジカルボシアニンアイオダイド
3,3’-ジエチル-2,2‘-オキサトリカルボシアニンアイオ
ダイド
3-エチル-5-[2-(3-メチル-2-チアゾリジニリデン)
エチリデン]-2-チオ-2,4-オキサゾリジンジオン
3-カルボキシメチル-5-[2-(3-エチル-2-ベンゾ
チアゾリニリデン)エチリデン]ローダニン
3-エチル-5-[2-(3-エチル-4-メチル-2-チアゾ
リニリデン)エチリデン]ローダニン
メチレンブルー
チオニンクロライド
リボフラビン
1-アミノ-4-ニトロフェナジン
1-アミノアクリジン
9-(2’-ヒドロキシスチリル)アクリジン
アクリルオレンジ
アクリジンイエロー
ローダミン
フルオレセイン
ローズベンガル
ジヒドロ-3-[2-ヒドロキシ-3-(5-イソプロピル-3,8
-ジメチル-1-アジレニル)-4-オキソ-2-シクロブテン-1
-イリデン]-7-イソプロピル-1,4-ジメチルアズレニウム
ヒドロオキサイド
トリフェニルピリリウムパークロレート
2,6-ビス(4-メチルフェニル)-4-(4-フェニルチオクロロ
パールクレート)
また、上記で例示した光増感剤の内、カンファーキノン、9,10-フェナントレンキノン、ベンジル、ジアセチル、アセチルベンゾイル、2,3-ペンタジオン、2,3-オクタジオン、4,4’-ジメトキシベンジル、アセナフテンキノン等のα-ジケトン化合物が最も好適に使用される。
本発明において使用される第3級アミン化合物(b)は、所謂還元剤(或いは電子供与体)であり、重合促進機能を有する。
このような第3級アミン化合物(b)としては、分子中に芳香族環を有する芳香族第3級アミン(b1)や、分子中に芳香族環を有していない脂肪族第3級アミン(b2)の何れも使用することができる。
また、これらのアルキル基は、当然のことながら置換基を有していてもよい、このような置換基としては、例えばフッ素原子等のハロゲン原子や水酸基を挙げることができる。例えば、R1~R3は、フロロメチル基、2-フロロエチル基等のハロゲノアルキル基や、2-ヒドロキシエチル基等のヒドロキシアルキル基などであってよい。
アルケニル基としては、ビニル基、アリル基、2-フェニルエテニル基等の炭素数2~12のものを挙げることができる。
アルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基等の炭素数1~10のもの等が挙げられる。
アルキルオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、アミルオキシカルボニル基、イソアミルオキシカルボニル基等のアルキルオキシ基部分の炭素数が1~10のものが例示される。
また、R3としてはアルキルオキシカルボニル基であることが好ましい。
p-ジメチルアミノ安息香酸メチル
p-ジメチルアミノ安息香酸エチル
p-ジメチルアミノ安息香酸プロピル
p-ジメチルアミノ安息香酸アミル
p-ジメチルアミノ安息香酸イソアミル
p-ジエチルアミノ安息香酸エチル
p-ジエチルアミノ安息香酸プロピル
N,N-ジメチルアニリン、
N,N-ジベンジルアニリン、
N,N-ジメチル-p-トルイジン、
N,N-ジエチル-p-トルイジン、
N,N-ジ(β-ヒドロキシエチル)-p-トルイジン
トリエタノールアミン、
N-メチルジエタノールアミン、
トリエチルアミン、
トリブチルアミン、
N,N-ジメチルアミノエチルメタクリレート、
N,N-ジエチルアミノエチルメタクリレート
特に、本発明では、芳香族第3級アミン(b1)を好適に使用することができるが、高い重合活性を示し、照射光による短時間での重合硬化性を維持し、尚且つ高い硬化体物性を発現させ、さらには、硬化体を太陽光等の紫外光に暴露したときの着色を低減するという点で、芳香族第3級アミン(b1)と脂肪族アミン(b2)とを併用することが好ましい。例えば、芳香族第3級アミン(b1)と脂肪族アミン(b2)とを、
b1:b2=1:99~99:1
好ましくは、40:60~80:20
より好ましくは、50:50~70:30
の質量比で使用することが望ましい。
本発明において使用されるアリールヨードニウム塩(c)は、所謂酸発生剤として公知の化合物であり、光照射による開裂反応によって、分子中に存在するアニオンに由来する酸を生成するという性質を有している。このようなアリールヨードニウム塩(c)として、本発明では、生成する酸の水中(25℃)での酸解離定数が-3.0以上となるものが選択されている。
即ち、このアリールヨードニウム塩(c)が、前述した光増感剤(a)及び第3級アミン化合物(b)と共存している光硬化性組成物に、活性光を照射して重合反応が開始すると、下記式(3)で示されるように、アリールラジカル及びアリールヨードニウム塩の対アニオンに由来する酸を発生する。
ところで、重合開始剤中にアミン化合物、特に第3級アミン化合物が存在する場合では、酸性度の高い酸は、第3級アミン化合物と中和反応を起こして塩を生成してしまうため、第3級アミン化合物の特性(還元性もしくは電子供与性)を損ない、この結果、重合活性が大きく損なわれてしまう。
しかるに、本発明で使用するアリールヨードニウム塩は、上記のような開裂反応により生じる酸の酸性度が低く、このため、この酸と第3級アミン化合物との中和反応が有効に抑制され、酸と共に生成するアリールラジカルが重合開始に有効に作用し、極めて優れた重合活性を示すこととなる。
因みに、種々の酸の水中(25℃)での酸解離定数を参考までに示すと以下のとおりである。
HCl:-3.7
HBr:-4.1
HNO3:-1.8
クロロ酢酸:2.9
安息香酸:4.2
フェノール:9.9
アリールヨードニウム(カチオン)の例;
ジフェニルヨードニウム
ビス(p-クロロフェニル)ヨードニウム
ジトリルヨードニウム
ビス(p-メトキシフェニル)ヨードニウム
ビス(p-tert-ブチルフェニル)ヨードニウム
p-イソプロピルフェニル-p-メチルフェニルヨードニウム
ビス(m-ニトロフェニル)ヨードニウム
p-tert-ブチルフェニルフェニルヨードニウム
p-メトキシフェニルフェニルヨードニウム
p-オクチルオキシフェニルフェニルヨードニウム
p-フェノキシフェニルフェニルヨードニウム
カウンターアニオンの例;
ニトレートアニオン
アセテートアニオン
クロロアセテートアニオン
カルボキシレートアニオン
フェノラートアニオン
また、このようなアリールヨードニウム塩(c)は、前述した第3級アミン化合物(b)を中和して該化合物(b)の性能低下をもたらさないため、この化合物(b)に対して比較的多く配合して活性光照射に際しての硬化速度を速めることができる。例えば、このアリールヨードニウム塩(c)は、第3級アミン化合物(b)とアリールヨードニウム塩(c)との合計量当り、10~80質量%、特に15~70質量%、さらには30~60質量%となるような量で使用することができる。
上述した本発明の光重合開始剤を含む光硬化性組成物は、その用途に応じて、重合性単量体及び本発明の光重合開始剤以外に、活性光に対する重合性や環境光に悪影響を及ぼさない範囲で、用途に応じて適宜の配合剤を添加することができる。例えば、この光硬化性組成物は、歯科材料、フォトレジスト材料、印刷製版材料、ホログラム材料等の種々の用途に使用することができ、このような用途に応じて、公知の配合剤を適宜配合することができる。特に、本発明の光重合開始剤が配合された光硬化性組成物は、活性光に対する重合硬化性に優れており、しかも、環境光に対する安定性を高めることができるため、歯の修復用のコンポジットレジンとして極めて有用である。
以下、この光硬化性組成物中に配合される各種成分について説明する。
本発明において、重合性単量体としては、ラジカル重合性単量体や、これ以外の重合性単量体、例えば、ビニルエーテル化合物、エポキシ化合物、オキセタン化合物、アジリジン化合物、アゼチジン化合物、エピスルフィド化合物、環状アセタール、ビシクロオルトエステル、スピロオルトエステル、スピロオルトカーボネート、テトラヒドロフラン等のカチオン重合性単量体も使用することができるが、本発明の光重合性単量体の性能を十分に発揮するためには、ラジカル重合性単量体が好適に使用される。
(I-i)芳香族化合物系二官能重合性単量体
2,2-ビス(メタクリロイルオキシフェニル)プロパン
2,2-ビス[4-(3-メタクリロイルオキシ)-2-ヒドロキシ
プロポキシフェニル]プロパン(以下、Bis-GMAと略記する)
2,2-ビス(4-メタクリロイルオキシフェニル)プロパン
2,2-ビス(4-メタクリロイルオキシポリエトキシフェニル)プ
ロパン(以下、D-2.6Eと略記する)
2,2-ビス(4-メタクリロイルオキシジエトキシフェニル)プロ
パン
2,2-ビス(4-メタクリロイルオキシテトラエトキシフェニル)
プロパン
2,2-ビス(4-メタクリロイルオキシペンタエトキシフェニル)
プロパン
2,2-ビス(4-メタクリロイルオキシジプロポキシフェニル)プ
ロパン
2(4-メタクリロイルオキシジエトキシフェニル)-2(4-メタ
クリロイルオキシトリエトキシフェニル)プロパン、
2(4-メタクリロイルオキシジプロポキシフェニル)-2-(4-
メタクリロイルオキシトリエトキシフェニル)プロパン
2,2-ビス(4-メタクリロイルオキシプロポキシフェニル)プロ
パン
2,2-ビス(4-メタクリロイルオキシイソプロポキシフェニル)
プロパン
上記の各種メタクリレートに対応するアクリレート
芳香族基を有するジイソシアネート化合物にOH基を有するビニルモ
ノマーを付加して得られるジアダクト
エチレングリコールジメタクリレート
ジエチレングリコールジメタクリレート
トリエチレングリコールジメタクリレート(以下、3Gと略記する)
テトラエチレングリコールジメタクリレート
ネオペンチルグリコールジメタクリレート
1,3-ブタンジオールジメタクリレート
1,4-ブタンジオールジメタクリレート
1,6-ヘキサンジオールジメタクリレート
上記の各種メタクリレートに対応するアクリレート
1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロポキ
シ)エチル
ジイソシアネート化合物にOH基を有するビニルモノマーを付加して
得られるジアダクト
メチロールプロパントリメタクリレート
トリメチロールエタントリメタクリレート
ペンタエリスリトールトリメタクリレート
トリメチロールメタントリメタクリレート
上記の各種メタクリレートに対応するアクリレート
ペンタエリスリトールテトラメタクリレート
ペンタエリスリトールテトラアクリレート
ジイソシアネート化合物にグリシドールジメタクリレートを付加して
得られるジアダクト
尚、ジイソシアネート化合物としては、ジイソシアネートメチルベンゼン、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)、4,4-ジフェニルメタンジイソシアネート、トリレン-2,4-ジイソシアネートが例示される。
フマル酸エステル類、例えばフマル酸モノメチル、フマル酸ジエチル、
フマル酸ジフェニル;
スチレンあるいはα-メチルスチレン誘導体、例えばスチレン、ジビニ
ルベンゼン、α-メチルスチレン、α-メチルスチレンダイマー;
アリール化合物、例えばジアリールテレフタレート、ジアリールフタレ
ート、ジアリールジグリコールカーボネート;
上記の光重合開始剤及び重合性単量体以外に適宜配合される配合剤として代表的なものは充填材であり、充填材の配合により、得られる硬化体の機械的強度等を向上させることができる。
このような充填材としては、以下の無機充填材が代表的である。
金属の単体、例えば周期律第I、II、III、IV族金属、遷移金属;
上記金属の酸化物や複合酸化物;
金属塩、例えば上記金属のフッ化物、炭酸塩、硫酸塩、珪酸塩、水酸化
物、塩化物、亜硫酸塩、燐酸塩又はこれらの複合物;
金属酸化物、例えば非晶質シリカ、石英、アルミナ、チタニア、ジルコ
ニア、酸化バリウム、酸化イットリウム、酸化ランタン、酸化イッテルビ
ウム;
シリカ系複合酸化物、例えばシリカ-ジルコニア、シリカ-チタニア、
シリカ-チタニア-酸化バリウム、シリカ-チタニア-ジルコニア;
ガラス、例えばホウ珪酸ガラス、アルミノシリケートガラス、フルオロ
アルミノシリケートガラス;
金属フッ化物、例えばフッ化バリウム、フッ化ストロンチウム、フッ化
イットリウム、フッ化ランタン、フッ化イッテルビウム;
無機炭酸塩、例えば炭酸カルシウム、炭酸マグネシウム、炭酸ストロン
チウム、炭酸バリウム;
金属硫酸塩、例えば硫酸マグネシウム、硫酸バリウム;
メチルトリメトキシシラン
メチルトリエトキシシラン
メチルトリクロロシラン
ジメチルジクロロシラン
トリメチルクロロシラン
ビニルトリクロロシラン
ビニルトリエトキシシラン
ビニルトリス(β-メトキシエトキシ)シラン
γ-メタクリロイルオキシプロピルトリメトキシシラン
γ-クロロプロピルトリメトキシシラン
γ-グリシドキシプロピルトリメトキシシラン
ヘキサメチルジシラザン
また、歯科用コンポジットレジンとして使用される場合には、上記充填材の中でもとりわけ球状形状を有するものが好ましく、これにより、得られる硬化体の表面滑沢性が増し、優れた歯科修復材となり得る。
かかるコンポジットレジンでは、歯牙の色調に合わせるために、上述した各成分に加えて、顔料、蛍光顔料、染料、紫外線に対する変色防止のために紫外線吸収剤を添加してもよいし、その他、歯科用コンポジットレジンの成分として公知の添加剤を、本発明の効果に影響のない範囲で配合することができる。
このような光重合型のコンポジットレジンは、遮光下、配合する各成分を所定量秤とり、均一になるまで混練することにより調製することができる。
CQ;
カンファーキノン
[第3級アミン化合物(b)]
DMBE;
p-ジメチルアミノ安息香酸エチル
DMPT;
N,N-ジメチル-p-トルイジン
MDEOA;
N-メチルジエタノールアミン
[アリールヨードニウム塩(c)]
(括弧内は25℃における水中での酸解離定数を示す)
DPICH;
ジフェニルヨードニウム‐2-カルボキシレートモノハイドレート
(4.2)
DPIN;
ジフェニルヨードニウムニトレート(-1.8)
DPIC;
ジフェニルヨードニウムクロリド(-3.7)
DPIB;
ジフェニルヨードニウムブロリド(-4.1)
[重合性単量体]
Bis-GMA;
2,2-ビス[4-(3-メタクリロイルオキシ-2-ヒドロキシ
プロピルオキシ)フェニル]プロパン
3G;
トリエチレングリコールジメタクリレート
UDMA:
1,6-ビス(メタクリルエチルオキシカルボニルアミノ)トリメ
チルヘキサン
D-2.6E;
下記式で示される化合物
E-1;
球状シリカ-ジルコニア(γ-メタクリロイルオキシプロピルトリ
メトキシシラン表面処理物、平均粒径;0.5μm)
E-2;
球状シリカ-チタニア(γ-メタクリロイルオキシプロピルトリメ
トキシシラン表面処理物、平均粒径;0.08μm)
[その他の成分]
HQME;
ハイドロキノンモノメチルエーテル
重合性単量体に対し各々所定量の光重合開始剤と充填材、及びその他の配合成分を加え、赤色光下にて均一に攪拌、脱泡して調製した。
以下の歯科用光照射器を用いて、次に示す方法で硬化体の硬度を測定した。即ち、6mmφ×1.0mmの孔を有するポリテトラフルオロエチレン製のモールドに光硬化性組成物を充填してポリプロピレンフィルムで圧接し、歯科用光照射器としてトクソーパワーライトを用い、当該照射器をポリプロピレンフィルムに密着して20秒間照射し、硬化体を調製した。得られた硬化体を微小硬度計(松沢精機製MHT-1型)にてヴィッカース圧子を用いて、荷重100gf、荷重保持時間30秒で試験片にできたくぼみの対角線長さにより求めた{トクソーパワーライト:光出力密度700mW/cm2、照射面における光強度640~650mW/cm2、光源はハロゲンランプ、トクヤマデンタル社}。
ステンレス製型枠に光硬化性組成物を充填し、ポリプロピレンで圧接した状態で、一方の面から20秒×3回、全体に光が当たるように場所を変えてトクソーパワーライトにてポリプロピレンに密着させて光照射を行なった。ついで、反対の面からも同様にポリプロピレンに密着させて20秒×3回光照射を行い硬化体を得た。#800の耐水研磨紙にて、硬化体を2×2×25mmの角柱状に整え、この試料片を試験機(島津製作所製、オートグラフAG5000D)に装着し、支点間距離20mm、クロスヘッドスピード1mm/分で3点曲げ破壊強度を測定した。
ペースト状の光硬化性組成物試料の表面が10000ルクスになるように光源と試料との距離を設定した。光源にはデンタルライト(光源:ハロゲン光、タカラベルモント社製)を用い、照度計にて測定される照度が上記照度になるよう、試料と光源の距離を設定した。この照射面での光強度は0.3mW/cm2であった。作製した光硬化性組成物試料をポリプロピレンフィルムに0.03g量り採り、上記デンタルライトの光を所定時間時間照射した後、試料を押しつぶし、試料内部が固まり始めた時間を計測した。なお、照射時間は5秒間隔とした。この時間が長いほど環境光安定性に優れ、よって良好な操作余裕時間を得ることができる。
なお照度計は東京硝子器械社、デジタルルックスメーターFLX-1330を用いた。この照度計は400~700nmに感度を有する。
下記処方により、暗所にて各成分を混合し、光硬化性組成物の均一溶液を調製した。
重合性単量体(100質量部);
D-2.6E:70質量部
3G:25質量部
UDMA:5質量部
光重合開始剤(0.9質量部);
CQ:0.3質量部
DMBE:0.5質量部
DPICH:0.4質量部
上述の条件で、この溶液から作成した硬化体のヴィッカース硬度を評価した。結果を表1に示す。
光重合開始剤を表1に記載した組み合わせに変更した以外は、実施例1と同様にして溶液を作成した。上述の条件でこれらの溶液から作成した硬化体のヴィッカース硬度を評価した。結果を表1に示す。
比較例3は、第3級アミン化合物(b)を配合しなかった例、比較例4は、光増感剤(a)を配合しなかった例である。これらの場合には、アリールヨードニウム塩(c)を配合しない例よりもさらにヴィッカース硬度が低かった。
比較例5及び6は、開裂反応により生じる酸の水中(25℃)での酸解離定数が-3.0未満であるアリールヨードニウム塩を用いている。この場合、比較例1よりもヴィッカース硬度が高いものの、実施例と比べるとヴィッカース硬度が低かった。
下記処方により、ペースト状の組成物を調製した。
重合性単量体(100質量部);
D-2.6E:70質量部
3G:25質量部
UDMA:5質量部
充填材(400質量部);
E-1:160質量部
E-2:240質量部
重合禁止剤(HQME):0.15質量部
このペースト状の組成物に、さらに表2に示す組成の光重合開始剤を配合した光重合型コンポジットレジンを得た。この光重合型コンポジットレジンのヴィッカース硬度、曲げ強度及び環境光安定性を評価した。結果を表2に示す。
光重合開始剤を表2に記載した組み合わせに変更した以外は、実施例8と同様にして光重合型コンポジットレジンを作成した。上述の条件でこれらの光重合型コンポジットレジンのヴィッカース硬度、曲げ強度及び環境光安定性を評価した。結果を表2に示す。
比較例9は、比較例7において、光増感剤であるCQ、第3級アミン化合物であるDMBEを増量した例である。この場合、比較例7よりもヴィッカース硬度及び曲げ強度が向上したものの、一方で、環境光安定性が低下した。このように、光増感剤及び第3級アミン化合物の増量では、硬化性と環境光安定性を両立する光重合型コンポジットレジンを得ることは困難である。
比較例10は、第3級アミン化合物(b)を配合しなかった例、比較例11は、光増感剤(a)を配合しなかった例である。これらの場合には、アリールヨードニウム塩(c)を配合しない例よりもさらにヴィッカース硬度及び曲げ強度が低かった。
比較例12及び13は、開裂反応により生じる酸の水中(25℃)での酸解離定数が-3.0未満であるアリールヨードニウム塩を用いている。この場合、比較例7よりもヴィッカース硬度及び曲げ強度が高いものの、実施例8~17と比べるとヴィッカース硬度及び曲げ強度が低かった。
下記処方により、ペースト状の組成物を調製した。
重合性単量体(100質量部);
Bis-GMA:60質量部
3G:40質量部
充填材(150質量部);
E-1:105質量部
E-2:45質量部
重合禁止剤(HQME):0.15質量部
このペースト状の組成物に、さらに表3に示す組成の光重合開始剤を配合して光硬化型コンポジットレジンを得た。この光重合型コンポジットレジンのヴィッカース硬度、曲げ強度及び環境光安定性を評価した。結果を表3に示す。
光重合開始剤を表3に記載した組み合わせに変更した以外は、実施例18と同様にして光重合型コンポジットレジンを調製した。上述の条件でこれらの光重合型コンポジットレジンのヴィッカース硬度、曲げ強度及び環境光安定性を評価した。結果を表3に示す。
比較例16は、比較例14において、光増感剤であるCQ及び第3級アミン化合物であるDMBEを増量した例である。この場合、比較例14よりもヴィッカース硬度及び曲げ強度が向上したものの、一方で環境光安定性が低下した。
このように、光増感剤及び第3級アミン化合物の増量では、硬化性と環境光安定性を両立する光重合型コンポジットレジンを得ることは困難である。
比較例17は、第3級アミン化合物(b)を配合しなかった例、比較例18は、光増感剤(a)を配合しなかった例である。これらの場合には、アリールヨードニウム塩(c)を配合しない例よりもさらにヴィッカース硬度及び曲げ強度が低かった。
比較例19及び20は、開裂反応により生じる酸の水中(25℃)での酸解離定数が-3.0未満であるアリールヨードニウム塩を用いている。この場合、比較例14よりもヴィッカース硬度及び曲げ強度が高いものの、実施例18~27と比べるとヴィッカース硬度及び曲げ強度が低かった。
Claims (11)
- (a)光増感剤、(b)第3級アミン化合物および(c)アリールヨードニウム塩を含む光重合開始剤において、
前記アリールヨードニウム塩(c)として、25℃の水中での解離定数が-3.0以上の酸を発生させるものが選択されていることを特徴とする光重合開始剤。 - 前記アリールヨードニウム塩(c)が、ジフェニルヨードニウム-2-カルボキシレートモノハイドレートである請求項1に記載の光重合開始剤。
- 前記光増感剤(a)が、α-ジケトンである請求項1に記載の光重合開始剤。
- 前記第3級アミン化合物(b)が、芳香族第3級アミン(b1)を含む請求項1に記載の光重合開始剤。
- 前記第3級アミン化合物(b)が、芳香族第3級アミン(b1)と脂肪族第3級アミン(b2)とを含む請求項4に記載の光重合開始剤。
- 前記光増感剤(a)100質量部当り、前記第3級アミン化合物(b)を10~1000質量部、および前記アリールヨードニウム塩(c)を10~2000質量部の量で含有している請求項1に記載の光重合開始剤。
- 前記第3級アミン化合物(b)とアリールヨードニウム塩(c)との合計量を基準として、10~80質量%の量でアリールヨードニウム塩(c)を含有している請求項6に記載の光重合開始剤。
- 請求項1に記載の光重合開始剤と、重合性単量体とを含む光硬化性組成物。
- 前記重合性単量体として、ラジカル重合性単量体が使用されている請求項8に記載の光硬化性組成物。
- 前記光重合開始剤は、該光重合開始剤中の光増感剤(a)の量が、前記重合性単量体100質量部当り0.01~10質量部となる量で配合されている請求項8に記載の光硬化性組成物。
- さらに充填材を含み、歯科用コンポジットレジンとして使用される請求項8に記載の光硬化性組成物。
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WO2021251023A1 (ja) * | 2020-06-12 | 2021-12-16 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
JP2021195526A (ja) * | 2020-06-12 | 2021-12-27 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
Families Citing this family (3)
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JP6779506B2 (ja) * | 2018-09-21 | 2020-11-04 | 株式会社トクヤマデンタル | 光硬化性組成物 |
CN111234054B (zh) * | 2020-01-15 | 2022-03-22 | 山东非金属材料研究所 | 一种双效引发剂及光聚合和热聚合的方法 |
CN113402665A (zh) * | 2020-03-16 | 2021-09-17 | 株式会社松风 | 包含高溶解性光致酸产生剂的牙科用光固化性组合物 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4386154A (en) * | 1981-03-26 | 1983-05-31 | Minnesota Mining And Manufacturing Company | Visible light sensitive, thermally developable imaging systems |
JPS5998103A (ja) * | 1982-09-18 | 1984-06-06 | チバ−ガイギ−・アクチエンゲゼルシヤフト | 光重合性組成物および該組成物の製造方法 |
JPH11130945A (ja) * | 1997-08-21 | 1999-05-18 | Espe Dental Ag | 光誘導されたカチオン硬化を起こす組成物及びそれらの使用 |
JP2001318464A (ja) * | 2000-05-10 | 2001-11-16 | Fuji Photo Film Co Ltd | ポジ型感放射線性組成物 |
JP2002527566A (ja) * | 1998-10-09 | 2002-08-27 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 光硬化可能な着色接着剤を使用する光ファイバコネクタ |
CN101477309A (zh) * | 2009-01-21 | 2009-07-08 | 北京波米科技有限公司 | 正性光敏性聚酰胺酸酯树脂组合物及其制备方法与应用 |
JP2009542724A (ja) * | 2006-07-06 | 2009-12-03 | ビスコ インコーポレイテッド | 減少した黄変性を有する発光ダイオード硬化性アクリレート |
WO2015087020A1 (fr) * | 2013-12-13 | 2015-06-18 | Laboratoires Urgo | Composition liquide photopolymerisable |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3808006A (en) * | 1971-12-06 | 1974-04-30 | Minnesota Mining & Mfg | Photosensitive material containing a diaryliodium compound, a sensitizer and a color former |
US3729313A (en) | 1971-12-06 | 1973-04-24 | Minnesota Mining & Mfg | Novel photosensitive systems comprising diaryliodonium compounds and their use |
US3741769A (en) * | 1972-10-24 | 1973-06-26 | Minnesota Mining & Mfg | Novel photosensitive polymerizable systems and their use |
US4518676A (en) | 1982-09-18 | 1985-05-21 | Ciba Geigy Corporation | Photopolymerizable compositions containing diaryliodosyl salts |
CA1323949C (en) | 1987-04-02 | 1993-11-02 | Michael C. Palazzotto | Ternary photoinitiator system for addition polymerization |
US6187836B1 (en) * | 1998-06-05 | 2001-02-13 | 3M Innovative Properties Company | Compositions featuring cationically active and free radically active functional groups, and methods for polymerizing such compositions |
US7084182B2 (en) | 2003-03-13 | 2006-08-01 | Tokuyama Corporation | Photopolymerization initiator |
JP4596786B2 (ja) * | 2004-02-02 | 2010-12-15 | 株式会社トクヤマ | 光硬化型歯科用複合修復材料 |
KR20080086525A (ko) * | 2005-12-29 | 2008-09-25 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 치과용 조성물 및 다환식 방향족 성분을 포함하는 개시제시스템 |
JP4841973B2 (ja) * | 2006-03-03 | 2011-12-21 | 株式会社トクヤマ | 光ラジカル重合開始剤、及びこれを配合した光ラジカル重合性組成物 |
JP5435892B2 (ja) * | 2008-05-21 | 2014-03-05 | 株式会社トクヤマデンタル | 光重合性組成物 |
US9205029B2 (en) * | 2008-10-15 | 2015-12-08 | 3M Innovative Properties Company | Dental compositions with fluorescent pigment |
EP2390273B1 (en) * | 2008-12-11 | 2015-11-04 | Tokuyama Dental Corporation | Dual-cure curable material kit |
RU2408644C1 (ru) * | 2009-06-10 | 2011-01-10 | Учреждение Российской Академии наук Институт металлоорганической химии им. Г.А. Разуваева РАН (ИМХ РАН) | Фотоотверждаемая клеевая композиция и способ ее отверждения |
CN104940027A (zh) * | 2015-06-25 | 2015-09-30 | 南京理工大学 | 低收缩牙科修复树脂及其制备方法 |
WO2018164074A1 (ja) * | 2017-03-06 | 2018-09-13 | 株式会社トクヤマデンタル | 光硬化性組成物及び歯科用修復充填材料 |
-
2017
- 2017-03-08 CA CA3014414A patent/CA3014414A1/en active Pending
- 2017-03-08 BR BR112018067870-8A patent/BR112018067870B1/pt active IP Right Grant
- 2017-03-08 KR KR1020187025233A patent/KR102269808B1/ko active IP Right Grant
- 2017-03-08 RU RU2018132016A patent/RU2709201C1/ru active
- 2017-03-08 WO PCT/JP2017/009248 patent/WO2017154983A1/ja active Application Filing
- 2017-03-08 AU AU2017230543A patent/AU2017230543B2/en active Active
- 2017-03-08 JP JP2018504558A patent/JP6821199B2/ja active Active
- 2017-03-08 EP EP17763323.7A patent/EP3427716B1/en active Active
- 2017-03-08 CN CN201780011740.7A patent/CN108697586B/zh active Active
- 2017-03-08 US US16/078,000 patent/US11098138B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4386154A (en) * | 1981-03-26 | 1983-05-31 | Minnesota Mining And Manufacturing Company | Visible light sensitive, thermally developable imaging systems |
JPS5998103A (ja) * | 1982-09-18 | 1984-06-06 | チバ−ガイギ−・アクチエンゲゼルシヤフト | 光重合性組成物および該組成物の製造方法 |
JPH11130945A (ja) * | 1997-08-21 | 1999-05-18 | Espe Dental Ag | 光誘導されたカチオン硬化を起こす組成物及びそれらの使用 |
JP2002527566A (ja) * | 1998-10-09 | 2002-08-27 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 光硬化可能な着色接着剤を使用する光ファイバコネクタ |
JP2001318464A (ja) * | 2000-05-10 | 2001-11-16 | Fuji Photo Film Co Ltd | ポジ型感放射線性組成物 |
JP2009542724A (ja) * | 2006-07-06 | 2009-12-03 | ビスコ インコーポレイテッド | 減少した黄変性を有する発光ダイオード硬化性アクリレート |
CN101477309A (zh) * | 2009-01-21 | 2009-07-08 | 北京波米科技有限公司 | 正性光敏性聚酰胺酸酯树脂组合物及其制备方法与应用 |
WO2015087020A1 (fr) * | 2013-12-13 | 2015-06-18 | Laboratoires Urgo | Composition liquide photopolymerisable |
Non-Patent Citations (1)
Title |
---|
See also references of EP3427716A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021251023A1 (ja) * | 2020-06-12 | 2021-12-16 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
JP2021195526A (ja) * | 2020-06-12 | 2021-12-27 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
JP7195549B2 (ja) | 2020-06-12 | 2022-12-26 | 株式会社トクヤマデンタル | 臼歯治療用歯科用充填修復材料 |
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JP6821199B2 (ja) | 2021-01-27 |
CA3014414A1 (en) | 2017-09-14 |
AU2017230543A1 (en) | 2018-08-09 |
KR102269808B1 (ko) | 2021-06-28 |
EP3427716A1 (en) | 2019-01-16 |
KR20180122614A (ko) | 2018-11-13 |
RU2709201C1 (ru) | 2019-12-17 |
CN108697586A (zh) | 2018-10-23 |
AU2017230543B2 (en) | 2022-02-17 |
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