JP5268478B2 - Dental curable material kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable curable material comprising, as a photopolymerization initiator, an &alpha;-diketone compound and an aliphatic amine compound, which rapidly cures and exhibits high strength even when applied to a surface treated with a pretreating material exhibiting self-etching primer performances. <P>SOLUTION: The curable material kit for a dental treatment comprises (A) a pretreatment material comprising (I) a polymerizable monomer bearing an acidic group and (II) water and (B) a curable material comprising (I) a polymerizable monomer bearing no acidic group, (II) a metal ion-containing glass filler, (III) a photopolymerization initiator comprising a combination of at least (i) an &alpha;-diketone compound and (ii) an aliphatic amine compound, particularly a photopolymerization initiator comprising, in addition to the components (i) and (ii), (iii) an aromatic amine compound and (iv) an s-triazine compound bearing a trihalomethyl group as a substituent group and/or an aryl iodonium salt and (IV) an inorganic filler. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a dental curable material kit comprising a pretreatment material and a curable material, more specifically, a pretreatment material having a self-etching primer ability, and curing of an orthodontic member adhesive, a tooth filling restoration material, and the like. The present invention relates to a dental curable material kit comprising a functional material.

  In recent years, an adhesive for orthodontic members (hereinafter, this adhesive is also simply referred to as “orthodontic adhesive”) is used because of its simplicity. These photo-curing orthodontic adhesives are used to light up at any timing after determining the mounting position of an orthodontic member (hereinafter referred to simply as “correcting member”) on the tooth surface. It can be cured and bonded, and has excellent operability. In general, as a bonding method, the following pretreatments are sequentially performed before the orthodontic adhesive is applied to the dentin. That is, 1) application of a pretreatment material for etching hard teeth, and 2) application of a pretreatment material called a primer, which acts as a penetration enhancer into the tooth.

  Of these, as the pretreatment material for the former etching treatment, an acid aqueous solution that decalcifies the tooth surface is generally used, and aqueous solutions of phosphoric acid, citric acid, maleic acid and the like have been used. On the other hand, as the primer, it is said that the adhesive needs to permeate and harden the rough enamel surface by decalcification of the acid aqueous solution, so that an amphiphilic monomer such as hydroxyethyl methacrylate (HEMA), Or the polymerizable monomer composition which has this and an organic solvent etc. as a main component is used.

  However, since the two-stage pretreatment of the etching treatment and the primer treatment is complicated, a pretreatment material having both a deashing function of an acid aqueous solution and a primer penetration promoting function has already been proposed for the purpose of reducing the operation. Has been. That is, at least a part of the polymerizable monomer component contains an acid group such as a phosphoric acid group and a carboxylic acid group, which has an effect of improving affinity for tooth and decalcification of tooth, In addition, a pretreatment material having a self-etching primer ability, in which water necessary for tooth decalcification is blended, has been developed for bonding orthodontic members. (For example, see Patent Document 1).

  Further, such a pretreatment material having a self-etching primer ability is widely applied to a photo-curable composite resin used for restoration of a tooth damaged by caries or the like (for example, Patent Document 2). And Patent Document 3).

  By the way, the basic composition of the orthodontic adhesive and the photo-curable composite resin to be bonded to the tooth subjected to the pretreatment material having the self-etching primer ability is composed of a polymerizable monomer and a photopolymerization initiator, In order to impart mechanical strength, the composition contains a large amount of inorganic filler. In order to maintain the mechanical strength at a high level, the polymerizable monomer has an acidic group that is used in the pretreatment material having the self-etching primer ability, and the use thereof is refrained. (These polymerizable monomers having an acidic group are generally those having a low mechanical strength of the cured product, and there is a possibility that the decomposition of the resin skeleton by the acidic group may proceed) .

  Further, as the photopolymerization initiator, it can be activated in the visible light wavelength region of a dental light irradiator, and since the resin in the composition can be quickly cured, α-diketone compounds are widely used, This is often used in combination with an amine compound having an action of promoting radical generation. In particular, when an aliphatic amine compound and an aromatic amine compound are used in combination as an amine compound, and an s-triazine compound having a trihalomethyl group as a substituent is further added to this, the curing speed is greatly increased. It is possible to improve and shorten the light irradiation time, which is useful (see Patent Document 4). Therefore, if a photopolymerization initiator having such a composition is used, for example, a large number of teeth must be treated, and in a bonding operation of an orthodontic member, it can be operated quickly and the burden on the patient can be greatly reduced. Can be achieved.

JP 2002-226314 A JP-A-6-9327 JP-A-6-24928 JP 2005-89729 A

  However, when such an orthodontic adhesive or a curable material of a photocurable composite resin, an aliphatic amine compound is used as an amine compound together with the α-diketone compound as a photopolymerizable initiator, the curable material is When the pretreatment material having the self-etching primer ability (that is, the pretreatment material containing an acidic group-containing polymerizable monomer and water) is applied to the treatment surface of the tooth, it does not exhibit sufficient polymerization activity. Was discovered. This is because, when the aliphatic amine compound blended as a component of the photopolymerization initiator is applied to the treated surface of the pretreatment material and brought into contact with the acidic group-containing polymerizable monomer, it is exceptional among the amine compounds. This is presumably due to the fact that salt is easily formed and deactivated.

  In particular, when a photopolymerization initiator using the aliphatic amine compound and the aromatic amine compound in combination is further used in combination with an s-triazine compound having a trihalomethyl group as the substituent described above. However, the rapid curing rate inherent in the catalyst system of the composition is hardly manifested, and the significance when the polymerizable initiator is applied to the adhesive for orthodontic members, etc. is only to the extent that it cannot be satisfied at all. It was not obtained.

  Against this background, the present invention is applied to the treatment surface of a pretreatment material having a self-etching primer ability in a photopolymerization type curable material in which the photopolymerization initiator uses an α-diketone compound and an aliphatic amine compound. Even so, the object is to develop a material that cures quickly and with high strength.

  In view of the above problems, the present inventors have continued intensive studies. As a result, it has been found that the above problems can be solved by adding a metal ion-containing glass filler to the curable material using the photopolymerization initiator, and the present invention has been completed.

That is, the present invention includes (A) (I) an acidic group-containing polymerizable monomer, and (II) pretreatment material comprising water (B) (I) an acidic group-free polymerizable monomer And a polymerizable monomer component not containing an acidic group-containing polymerizable monomer, (II) a metal ion-containing glass filler, (III) i) an α-diketone compound, and ii) an aliphatic amine compound. A dental curable material kit comprising a photopolymerization initiator, and (IV) a curable material containing an inorganic filler.

  In the dental curable material kit of the present invention, first, (A) the pretreatment material exhibits the function of demineralizing the tooth and the function of promoting penetration into the tooth. Accordingly, the cured product of the (B) curable material applied thereon has improved adhesion to the tooth.

  And although this (B) curable material is applied to the processing surface of the said pre-processing material which has the said self-etching primer ability, it is the aliphatic amine compound mix | blended as a component of a photopolymerization initiator. Deactivation is suppressed, and the polymerization activity of the α-diketone compound is improved satisfactorily. In particular, when an α-diketone compound and an aliphatic amine compound are used in combination with an s-triazine compound having a trihalomethyl group as a substituent or an aryl iodonium salt, the curing rate is extremely rapid. The adhesive strength is extremely high.

  Therefore, when the curable material is an adhesive for an orthodontic member, the treatment time is greatly shortened, the burden on the patient is reduced, and the orthodontic orthodontic member bonded to each individual tooth is Even if a high binding force is applied to the straightening wire, it is bonded to a high strength that is extremely difficult to come off. In addition, even when the curable material is a tooth restoration material such as a photo-curable composite resin, a rapid operation and a highly reliable restoration can be realized, which is extremely significant.

The greatest feature of the present invention is that the kit comprises (I) a polymerizable monomer component containing an acidic group-free polymerizable monomer and not containing an acidic group-containing polymerizable monomer , (III) (B) a curable material comprising (i) an α-diketone compound and (ii) a photopolymerization initiator in which an aliphatic amine compound is combined, and (IV) an inorganic filler. It is in the point which contained the glass filler. With this configuration, the curable material can be applied to a treatment surface for a tooth of a pretreatment material comprising (A) (I) an acidic group-containing polymerizable monomer and (II) water. The deactivation of the aromatic amine compound is suppressed, and a high polymerization activity by the α-diketone compound and the aliphatic amine compound is expressed. The reason for this is not necessarily clear, but when a curable material is applied to the treated surface of the pretreatment material, metal ions are caused by the action of the acidic group-containing polymerizable monomer and water present on the treated surface. This is not because metal ions are eluted from the contained glass filler, which forms a salt with an acidic group of the acidic group-containing polymerizable monomer to weaken its acidity, thereby suppressing the deactivation of the aliphatic amine compound. It is guessed.

  In general, the (A) pretreatment material applied to the tooth is usually blown with air to remove the coarse water contained therein, but still a slight amount remains. In addition, since moisture such as saliva present in the oral cavity is added to this, when the curable material having the composition of the present invention is applied to the treated surface of the pretreatment material, the above-mentioned fat is extracted from the metal ion-containing glass filler. Usually, a sufficient amount of moisture is present to elute the metal ions necessary to suppress the deactivation of the group amine compound.

  (B) In the curable material constituting the dental curable material kit, the characteristic component (II) metal ion-containing glass filler is a glass particle containing metal ions, and is in contact with an acid aqueous solution. Further, a part of the glass skeleton collapses and the metal ions are eluted. Moreover, after elution of metal ions, the particles become a porous particle having a network-like structure, and has an action of improving the strength of the curable material. Even if the metal ion contained in the glass filler is a monovalent metal ion such as sodium or potassium, the effect of the present invention is sufficiently recognized. However, the metal ion is preferably a polyvalent metal ion for the following reason. That is, the polyvalent metal ion has the effect of further significantly increasing the adhesive strength of the cured body to the tooth, in addition to efficiently exhibiting the effect of lowering the acidity due to salt formation. More specifically, if the eluted metal ion is polyvalent, a plurality of acidic groups and the polyvalent metal ion will form a salt in the polymer of the acidic group-containing polymerizable monomer. For this reason, ionic cross-linking occurs three-dimensionally, which greatly improves the adhesive force at the application interface between the pretreatment material and the curable material.

  Examples of such polyvalent metal ions include metal ions such as calcium, strontium, barium, aluminum, zinc, and lanthanoids. Among these, the efficiency of forming a salt with an acidic group-containing polymerizable monomer is said to be good. From the viewpoint, it is more preferable to contain trivalent ions such as aluminum as at least a part. The content of such polyvalent metal ions is desirably 70 mol% or more, particularly desirably 80 mol% or more, based on the total metal ions.

The metal ion-containing glass filler is not particularly limited as long as it satisfies the above conditions. However, when the metal ion is contained as a salt with a counter anion that can be eluted simultaneously with the metal ion, the elution-dissociated glass filler is contained. Many counter anions (excluding fluorine ions described later) may adversely affect the adhesive strength on the coating interface between the pretreatment material and the curable material. It is preferable to use one that does not elute. Of course, in this sense, the metal ion elution source contained in the curable material is not the water-soluble metal salt or the like but uses the above-mentioned metal ion-containing glass filler.

  As the metal ion-containing glass filler, in the present invention, glass having a chain-like, layer-like, or network-like skeleton containing metal ions in the gap between the skeletons is preferably used. When a preferable example is given, oxide glass, fluoride glass, etc. can be mentioned as glass which has frame | skeleton of a chain | strand shape, a layer form, and a network-like structure for containing a metal ion. Examples of the oxide glass include those made of aluminosilicate glass, borosilicate glass, soda lime glass, and the like, and examples of the fluoride glass include zirconium fluoride glass. Among the metal ion-containing glass fillers, those made of aluminosilicate glass are more preferably used in terms of improving the strength of the cured body, and further release fluoride ions that strengthen the tooth structure after bonding, so-called fluorine gradual release. Those made of fluoroaluminosilicate glass having releasability are most preferably used.

  The elution characteristics of metal ions in the metal ion-containing glass filler can be controlled by the mixing ratio of each element. For example, if the content of polyvalent metal ions such as aluminum and calcium is increased, these elution amounts generally increase, and the elution amount of these metal ions can be changed by changing the content of sodium and phosphorus. Therefore, the elution characteristics of metal ions can be controlled relatively easily.

  As the fluoroaluminosilicate glass that can be suitably used as the metal ion-containing glass filler component, a known one used for dental cement, for example, glass ionomer cement can be used. The composition of commonly known fluoroaluminosilicate glasses is, in terms of ionic mass percent, silicon, 10-33; aluminum, 4-30; alkaline earth metal, 5-36; alkali metal, 0-10; 2 to 16; fluorine, 2 to 40 and residual oxygen are preferably used. More preferred compositional ranges include silicon, 15-25; aluminum, 7-20; alkaline earth metal, 8-28; alkali metal, 0-10; phosphorus, 0.5-8; fluorine, 4-40 and Remaining oxygen. What substituted some or all of calcium with magnesium, strontium, and barium is also preferable. The alkali metal is most commonly sodium, but it is also preferable to replace part or all of it with lithium, potassium or the like. If necessary, a part of the aluminum can be replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like.

  In the present invention, the shape of the metal ion-containing glass filler is not particularly limited, and may be pulverized particles or spherical particles obtained by ordinary pulverization, and if necessary, particles such as plate and fiber are mixed. You can also.

  In addition, the metal ion-containing glass filler preferably has an average particle diameter of 0.01 μm to 30 μm, more preferably 0.05 μm to 20 μm, and further 0.1 μm, from the viewpoint of facilitating the production of the curable material. The thing of the range of-10 micrometers is the most preferable. Furthermore, when 0.1 g of filler is immersed in 10 ml of a 10% by weight maleic acid aqueous solution at a temperature of 23 ° C., the amount of metal ions eluted after 3 minutes is 0.5 to 100 meq / g-filler. preferable. More preferably, it is 1.0-30 meq / g-filler. The amount of metal ions at this time can be measured by ICP (inductively coupled plasma) emission spectroscopic analysis. The amount of metal ions eluted after 3 minutes under the above conditions is also referred to as “3 minutes of ion elution”. In addition, it is preferable that such a metal ion containing glass filler is 5.0-500 meq / g-filler in the quantity of the metal ion which eluted after performing immersion of the said conditions for 24 hours. More preferably, it is 10-100 meq / g-filler. The amount of metal ions at this time can also be measured by ICP emission spectroscopic analysis. The amount of metal ions eluted after 24 hours under the above conditions is hereinafter also referred to as “24 hours eluted ion amount”.

  As a method for controlling the elution characteristics, a generally known method can be used. As a typical method, a metal ion on the filler surface is removed in advance by treating the metal ion-eluting filler with an acid. And a method for controlling the elution characteristics. As the acid used in this method, generally known acids such as inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as maleic acid and citric acid are used. The acid concentration, treatment time, etc. may be appropriately determined according to the amount of ions to be removed.

  In the curable material (B) of the present invention, the amount of the (II) metal ion-containing glass filler is not particularly limited, but the aliphatic amine compound in the curable material is (A) From the viewpoint of preventing inactivation by contact with the (I) acidic group-containing polymerizable monomer in the pretreatment material, (B) (I) the acidic group-free polymerizable monomer in the curable material It is preferred that the amount per 100 parts by mass is 0.5 to 50 parts by mass, particularly 1 to 30 parts by mass, and optimally 3 to 25 parts by mass. If the blending amount of the metal ion-containing glass filler is less than 0.5 parts by mass, the necessary amount of metal ions will not be eluted when in contact with the acid, and the acidity will not be sufficiently lowered, and the aliphatic amine will be deactivated. Can not be sufficiently suppressed, and the adhesive strength is reduced. On the other hand, when the content of the metal ion-containing glass filler is more than 50 parts by mass, the cured body tends to be too hard. For example, if the curable material is an orthodontic adhesive, It becomes difficult to remove the residual cured product on the tooth surface.

  As is apparent from the above description, in the present invention, (II) a photopolymerization initiator used for (B) a curable material containing a metal ion-containing glass filler is (i) an α-diketone compound. And ii) a combination of at least aliphatic amine compounds.

  Here, i) α-diketone compound is used without limitation as a sensitizer in photopolymerization, and specifically, camphorquinones such as camphorquinone and diacetylcamphorquinone; acetylbenzoyl, 2, 3 -Pentadione, 2,3-octadione, 9,10-phenanthrenequinone, acenaphthenequinone and the like. These α-diketone compounds may be appropriately selected and used depending on the wavelength and intensity of light used for the polymerization, the time of light irradiation, or the type and amount of other components to be combined, either alone or in combination of two or more. It can also be used. Among these, considering the use for dentistry, it is preferable to have a maximum absorption wavelength in the visible light region. Generally, camphorquinones are preferably used, and camphorquinone is particularly preferable.

  (B) In the (III) photopolymerization initiator used for the curable material, the compounding amount of the above-mentioned i) α-diketone compound is not particularly limited, and other components to be combined and the polymerizability to be photopolymerized Although it may be appropriately selected depending on the kind of the monomer, it is usually 0.01 to 10 parts by mass, particularly 0 to 10 parts by mass with respect to 100 parts by mass of the (I) acidic group-free polymerizable monomer. It is good to make it exist in a photoinitiator in the quantity which can ensure the quantity of the range of 03-5 mass parts, 0.07-1 mass part optimally. In general, the greater the amount of α-diketone compound, the shorter the curing time with active light, while the smaller the amount, the better the ambient light stability.

  On the other hand, as the ii) aliphatic amine compound, known compounds used as radical generation accelerators can be used without limitation. Any of primary amines, secondary amines and tertiary amines can be used, but primary and secondary amines are highly volatile and have problems such as generation of odors. Especially for dental use, a tertiary amine having no such problem is preferably used.

  Further, in order to further improve the storage stability, among the tertiary amines, three saturated aliphatic groups have a tertiary amino group bonded to a nitrogen atom, and the saturated aliphatic group At least two of them are preferably compounds having an electron-withdrawing group as a substituent. A tertiary amine tends to exhibit a higher polymerization activity than a primary amine or a secondary amine, but has a specific tertiary amino group (aliphatic tertiary amino group) as described above. By using (aliphatic tertiary amine), higher polymerization activity can be obtained, and further excellent storage stability can be obtained.

  The electron withdrawing group in the aliphatic tertiary amino group is a group having an inducing effect of attracting an electron from the carbon atom of the saturated aliphatic group to which the group is bonded. In consideration of chemical stability, hydroxyl groups; aryl groups such as phenyl groups and naphthyl groups; unsaturated aliphatic groups such as ethenyl groups (vinyl groups), 1-propenyl groups and ethynyl groups; fluorine atoms An alkoxyl group; a carbonyl group; a carbonyloxy group; a cyano group; Among these, an aryl group, an unsaturated aliphatic group, or a hydroxyl group is preferable in terms of excellent stability of the compound, easy synthesis, and excellent solubility in a polymerizable monomer. A hydroxyl group is particularly preferred.

  The saturated aliphatic group to which such an electron-withdrawing group is bonded is not particularly limited, and may be linear, branched, or cyclic, but is straight-chain in terms of synthesis and availability. Or a saturated aliphatic group having 1 to 6 carbon atoms, particularly a linear or branched carbon atom having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group or butyl group, more preferably carbon It is preferable that it is a C1-C3 alkyl group. Further, the position and number of substitution (bonding) of the electron-withdrawing group are not particularly limited, but the bond to the carbon atom closer to the nitrogen atom of the amino group tends to improve the storage stability. For example, it is preferable that an electron-withdrawing group is bonded to the carbon atom bonded to the nitrogen atom (position 1 of the saturated aliphatic group) or the adjacent carbon atom (position 2).

  Specific examples of the saturated aliphatic group having such an electron-withdrawing group as a substituent include 2-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 2,3-dihydroxypropyl. Having a hydroxyl group (electron withdrawing group) such as a group; having an unsaturated aliphatic group (electron withdrawing group) such as an allyl group (ethenylmethyl group), 2-propynyl group (ethynylmethyl group), 2-butenyl group, etc. Those having an aryl group (electron-withdrawing group) such as a benzyl group;

  That is, in the present invention, the aliphatic tertiary amine suitably used as the aliphatic amine compound has a tertiary amino group in which three saturated aliphatic groups are bonded to a nitrogen atom. Such tertiary amino groups are roughly classified into the following three types (α) to (γ).

  (Α) None of the three saturated aliphatic groups bonded to the nitrogen atom has the electron-withdrawing group as a substituent. Third having a tertiary amino group of this type (α) Examples of the tertiary amine include triethylamine and tributylamine.

(Β) Of the three saturated aliphatic groups bonded to the nitrogen atom, one has the electron-withdrawing group as a substituent (two have the electron-withdrawing group as a substituent) Not)
Examples of the tertiary amine having such a type (β) tertiary amino group include dimethylaminoethanol, diethylaminoethanol, dimethylaminopropanol, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl. And methacrylate.

(Γ) Among three saturated aliphatic groups bonded to a nitrogen atom, two or more have the electron-withdrawing group as a substituent. A tertiary amino group of this type (γ) Examples of the tertiary amine having an electron-withdrawing group-substituted saturated aliphatic group number such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, and N-ethyldibenzylamine are 2. And those having 3 electron-withdrawing group-substituted saturated aliphatic groups such as triethanolamine, tri (isopropanol) amine, tri (2-hydroxybutyl) amine, triallylamine, and tribenzylamine.

  As already mentioned, tertiary amines having a tertiary amino group of type (γ) are most preferably used in the present invention. As a result, as shown in the examples described later, the number of the tertiary amino group or the electron-withdrawing group-substituted saturated aliphatic group of type (α) whose number of electron-withdrawing group-substituted saturated aliphatic groups is 0 is one. The storage stability can be further improved as compared with the case where a tertiary amine having a type (β) tertiary amino group is used.

  (B) In the photopolymerization initiator (III) used for the curable material, the blending amount of the above ii) aliphatic amine compound is not particularly limited and is appropriately selected depending on the α-diketone compound to be combined and other components. Usually, it is 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, optimally 0, per 100 parts by weight of (I) an acidic group-free polymerizable monomer. .1 to 0.8 parts by mass.

  In the present invention, the (III) photopolymerization initiator has excellent polymerization activity as long as the above i) α-diketone compound and ii) aliphatic amine compound are combined, but it is stable to ambient light. From the viewpoint of greatly improving the reaction activity against irradiation light while maintaining the above, it is further used as a compound containing iii) an aromatic amine compound and iv) an s-triazine compound having a trihalomethyl group as a substituent. Is preferred. That is, the photopolymerization initiator obtained by having the above composition has high stability with respect to light as weak as ambient light (less than 1 mW / cm 2 at 360 to 500 nm), and further, halogen lamp, xenon lamp, etc. By irradiating with strong light by the irradiator, polymerization can be completed in a very short time, and good cured product properties can be obtained. In addition, in the above composition, the same advantageous effects as those described above can be satisfactorily exhibited even when an aryliodonium salt is used instead of iv) an s-triazine compound having a trihalomethyl group as a substituent.

  In order to develop such an effect, the amine compound needs to be used in combination with the aliphatic amine compound together with the aromatic amine compound. By using both of these compounds in combination, only one of them can be used. Compared to the case of the present invention, much better polymerization activity is exhibited, and the composition can be cured in a shorter time without sacrificing the stability to ambient light.

  Here, the iii) aromatic amine compound may be an amine compound in which at least one of the organic groups bonded to the nitrogen atom of the amino group is an aromatic group, and any known compound is not particularly limited. It can be used, but it has higher polymerization activity, less volatility, less odor, and is easy to obtain. In terms of availability, an aromatic group in which one aromatic group and two aliphatic groups are bonded to the nitrogen atom. An amine compound (aromatic tertiary amine) having a tertiary amino group is preferred. Representative aromatic tertiary amines include those represented by the following general formula.

In the formula, R ¹ and R ² are each independently an alkyl group, and R ³ is hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, or an alkyloxycarbonyl group.

  As said alkyl group, a C1-C6 thing is preferable, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group etc. can be mentioned. Further, the alkyl group may be a substituted alkyl group having a substituent as a matter of course, and examples of such a substituted alkyl group include halogen-substituted alkyl groups such as a fluoromethyl group and a 2-fluoroethyl group; Examples thereof include a hydroxyl group-substituted alkyl group such as a 2-hydroxyethyl group.

  Further, any of the above aryl group, alkenyl group, alkoxy group and alkyloxycarbonyl group may have a substituent. Examples of the aryl group include those having 6 to 12 carbon atoms such as a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group, and a 4-biphenylyl group. 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. Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and an amyloxycarbonyl group. And those having 1 to 10 carbon atoms in the alkyloxy group such as isoamyloxycarbonyl group.

In the aromatic tertiary amine of the above general formula, the groups R ¹ and R ² are preferably alkyl groups having 1 to 6 carbon atoms, and in particular, unsubstituted alkyl groups having 1 to 3 carbon atoms (for example, Methyl group, ethyl group, n-propyl group), 2-hydroxyethyl group, and the like are more preferable. The group R ³ is particularly preferably an alkyloxycarbonyl group. When such an aromatic amine having an alkyloxycarbonyl group-substituted aromatic group is combined with the above ii) aliphatic amine compound, better storage stability can be obtained.

Specific examples of the tertiary amine having an aromatic group in which the group R ³ is an alkyloxycarbonyl group include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, Examples include amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate, and the like.

  Examples of other aromatic amines represented by the above general formula include N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine. N, N-di (β-hydroxyethyl) -p-toluidine and the like.

  (B) In the (III) photopolymerization initiator used for the curable material, the blending amount of the above iii) aromatic amine compound is not particularly limited and is appropriately selected depending on the aliphatic amine compound to be combined and other components Usually, it is 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, optimally 0, per 100 parts by weight of (I) an acidic group-free polymerizable monomer. .1 to 0.8 parts by mass.

  It is preferable to mix with the above iii) aromatic amine compound in the (III) photopolymerization initiator of the present invention, iv) s-triazine compound having a trihalomethyl group as a substituent (hereinafter also referred to simply as “triazine compound”) For example, a known s-triazine compound satisfying such a specific structure can be used without any limitation. A particularly preferred triazine compound is represented by the following general formula.

(Wherein R ⁴ and R ⁵ are an organic group, an alkyl group, or an alkoxy group having an unsaturated bond that can be conjugated with a triazine ring, and X is a halogen atom.)
In the above general formula, the halogen atom represented by X may be any of chlorine, bromine and iodine, but chlorine is generally used. Therefore, the substituent (CX ₃ ) bonded to the triazine ring is trichloromethyl. Groups are common.

R ⁴ and R ⁵ may be any of an organic group having an unsaturated bond that can be conjugated with the triazine ring, an alkyl group, and an alkoxy group, but in order to improve storage stability, at least one of R ⁴ and R ⁵ must be An organic group having an unsaturated bond that can be conjugated with a triazine ring is preferable. On the other hand, when at least one of R ⁴ and R ⁵ is a halogen-substituted alkyl group, it is easier to obtain better polymerization activity, and when both are halogen-substituted alkyl groups, the polymerization activity is particularly good.

  The organic group bonded by an unsaturated bond that can be conjugated to the triazine ring may be any known organic group, but is preferably an organic group having 2 to 30 carbon atoms, particularly 2 to 14 carbon atoms. Specific examples of such an organic group include carbon number such as phenyl group, methoxyphenyl group, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group, naphthyl group, 4-methoxy-1-naphthyl group, etc. 6-14 aryl groups; C2-C14 alkenyl groups such as vinyl, 2-phenylethenyl, 2- (substituted phenyl) ethenyl and the like are exemplified. In addition, as a substituent which the said substituted phenyl group has, C1-C6 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group An alkylthio group having 1 to 6 carbon atoms such as a methylthio group, an ethylthio group and a propylthio group; a phenyl group; a halogen atom and the like.

In R ⁴ and R ⁵ , the alkyl group and the alkoxy group may have a substituent, and as such an alkyl group, those having 1 to 10 carbon atoms are preferable, for example, methyl group, ethyl Group, unsubstituted alkyl group such as n-propyl group, i-propyl group, n-butyl group, n-hexyl group; halogen such as trichloromethyl group, tribromomethyl group, α, α, β-trichloroethyl group Examples thereof include a substituted alkyl group. Furthermore, as an alkoxy group, a C1-C10 thing is preferable, for example, unsubstituted alkoxy groups, such as a methoxy group, an ethoxy group, a butoxy group; 2- {N, N-bis (2-hydroxyethyl) amino} Amino such as ethoxy group, 2- {N-hydroxyethyl-N-ethylamino} ethoxy group, 2- {N-hydroxyethyl-N-methylamino} ethoxy group, 2- {N, N-diallylamino} ethoxy group Examples thereof include an alkoxy group substituted with a group.

  Specific examples of the trihalomethyl group-substituted s-triazine compound represented by the above general formula include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tri Bromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4 , 6-Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (o-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis ( Lichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-tri Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-me Ruamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, etc. Illustrated.

  Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable in terms of polymerization activity, and 2-phenyl- in terms of storage stability. 4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis (Trichloromethyl) -s-triazine. These triazine compounds may be used alone or in combination of two or more.

  On the other hand, the same effects as those of the triazine compound are exhibited, and as the iv) aryl iodonium salt that can be used in place of the triazine compound, the known compound is used without any limitation. Specific examples of the aryl iodonium salt that can be preferably used in the present invention include diphenyl iodonium, bis (p-chlorophenyl) iodonium, ditolyl iodonium, 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-phenoxyphenyl Cations such as phenyliodonium, chloride, bromide, benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, Tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) gallate, hexafluorophosphate, hexafluoroarsenate, and a salt comprising anions such as hexafluoroantimonate.

  Among these aryliodonium salts, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) gallate are used in terms of solubility in radical polymerizable monomers. , Hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate salts are preferred, and tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) gallate and hexafluoroantimonate salts are particularly preferred from the viewpoint of storage stability. Is preferred. These aryl iodonium salts may be used alone or in combination of two or more.

  (B) In the photopolymerization initiator (III) used for the curable material, iv) The blending amount of the s-triazine compound and / or aryl iodonium salt is not particularly limited, and each amine compound to be combined and others In general, the amount is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight per 100 parts by weight of the (I) non-acidic group-containing polymerizable monomer. The optimum range is 0.1 to 0.8 parts by mass.

  In addition, the (III) photopolymerization initiator used in the present invention is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 used for the purpose of generating radicals. Of known photopolymerization initiators such as acylphosphine oxide derivatives such as 1,4-trimethylpentylphosphine oxide, known sensitizers other than α-diketone compounds such as coumarin dyes, and promotion of radical generation other than amine compounds You may use an agent etc. suitably. If necessary, known chemistry such as known peroxides, peroxyketals, hydroperoxides, diaryl peroxides, peroxyesters, diacyl peroxides, organic peroxides classified into peroxydicarbonates, etc. A polymerization initiator may be appropriately used.

  In the curable material (B) of the present invention, the blending amount of the (III) photopolymerization initiator is not particularly limited. From the viewpoint of improving the strength of the curable material, (B) the curable material. In the above, the total amount of the above components i) to iv) and other photopolymerization initiator components is 0.02 to 20 parts by mass, particularly 0.04, per 100 parts by mass of (I) the acidic group-free polymerizable monomer. It is preferable to be in the range of ˜15 parts by mass, optimally 0.5 to 3 parts by mass. When the blending amount of this photopolymerization initiator is less than 0.02 parts by mass, the polymerization activity tends to decrease and the cured product strength tends to decrease and the adhesive strength tends to decrease. Conversely, if it exceeds 20 parts by mass, the compound cannot be polymerized. When the abundance of is increased, the cured body strength tends to decrease and the adhesive strength tends to decrease.

In the present invention, for use in (B) a curable material (I) polymerizable monomer state, and are not no acidic group, it does not include an acidic group-containing polymerizable monomer.
That is, the acidic group-containing polymerizable monomer generally has a low mechanical strength of the cured body, and there is a possibility that the resin skeleton may be decomposed by the acidic group. As the main component of the polymerizable monomer, those having no acidic group are used . Further, when an acidic group-containing polymerizable monomer is used, during the storage of the curable material, the acidic group causes ii) the aliphatic amine compound to be deactivated by the acidic group, Alternatively, (II) the metal ion is eluted from the metal ion-containing glass filler to form a salt, and the effect of the present invention is not exhibited.

The acidic group-free polymerizable monomer is a (meth) acrylate polymerizable monomer having no acidic group (sulfonic acid group, carboxyl group, phosphoric acid residue, etc.). It is preferably used from the viewpoint of mechanical properties, water resistance, color resistance, storage stability, etc., and in particular, a polyfunctional (meth) acrylate polymerizable monomer having a plurality of polymerizable functional groups is preferable. . As the polyfunctional (meth) acrylate polymerizable monomer, known ones can be used without particular limitation. Examples of those generally used preferably include those shown in the following (1) to (3).
(1) Bifunctional polymerizable monomer (1-1) Aromatic compound type 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis ( 4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxy) Tetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-Methacryloyloxytriethoxyphenyl) propane 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyiso) Propoxyphenyl) propane; acrylates corresponding to the above-mentioned various methacrylates; and diaducts obtained from addition of an OH group-containing vinyl monomer and a diisocyanate compound having an aromatic group.

(Examples of the OH group-containing vinyl monomer include methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate, or acrylates corresponding to these methacrylates. Examples of the diisocyanate include diisocyanate methylbenzene and 4,4′-diphenylmethane diisocyanate.)
(1-2) Aliphatic compound-based 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; and OH group-containing vinyl monomers and fats Diaducts obtained from addition with a group diisocyanate compound.
(Examples of the OH group-containing vinyl monomer include the same as those exemplified above, and examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, And methylene bis (4-cyclohexyl isocyanate).
(2) Trifunctional polymerizable monomers: methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate; and acrylates corresponding to these methacrylates.

(3) Tetrafunctional polymerizable monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate; and a diadduct obtained from an adduct of a diisocyanate compound and glycidol dimethacrylate;
(As the above diisocyanate compounds, diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4- A diisocyanate etc. can be mentioned.

  The polyfunctional (meth) acrylate monomer described above may be used in combination of a plurality of types as required.

  Furthermore, you may use polymerizable monomers other than a monofunctional (meth) acrylate type monomer and said polyfunctional (meth) acrylate type monomer as needed. Monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and glycidyl. A (meth) acrylate etc. can be mentioned.

  In the curable material (B) of the present invention, the amount of the (I) acidic group-free polymerizable monomer is not particularly limited, but from the viewpoint of curing the curable material with high strength. In the curable material, it is generally 10 to 85% by mass, particularly 15 to 80% by mass. If the blending amount of the acidic group-free polymerizable monomer is less than 10% by mass, the property of the curable material paste itself tends to be too hard and the operability tends to deteriorate. Many unpolymerized components remain on the cured product and the adhesive strength tends to decrease.

  In the present invention, (B) the inorganic filler (IV) used for the curable material is a known inorganic filler other than the (II) metal ion-containing glass filler and used for a dental curable material. Things can be used without restriction. Specific examples include spherical particles or amorphous particles such as amorphous silica, silica-zirconia, silica-titania, silica-titania-barium oxide, silica-titania-zirconia, quartz, and alumina. When the photopolymerizable composition of the present invention is used for a dental crown material or a dental filling restorative material, silica-based particles are preferable. As silica-based particles, spherical inorganic particles of composite oxides, which contain silica and zirconia, silica and titania, or silica and barium oxide as main constituents, have X-ray contrast and more wear resistance. Since a cured product of a composite composition having excellent surface smoothness can be obtained, it is particularly preferably used.

  The particle size of the inorganic filler is not particularly limited, but the average particle size is preferably 30 μm or less, more preferably 0.001 to 20 μm, and most preferably 0.01 to 15 μm.

  These inorganic fillers improve the mechanical strength and water resistance by improving hydrophobicity with a surface treatment agent typified by a silane coupling agent to improve compatibility with non-acidic group-containing polymerizable monomers. Can do. The hydrophobization method may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, etc. hexamethyldisilazane is preferably used.

  In the curable material (B) of the present invention, the blending amount of the inorganic filler (IV) is not particularly limited, but from the viewpoint of improving the strength of the curable material, (I ) It is preferably 25 to 850 parts by weight, more preferably 110 to 600 parts by weight, and most preferably 130 to 350 parts by weight per 100 parts by weight of the acidic group-free polymerizable monomer. If the blending amount of the inorganic filler is less than 25 parts by mass, the strength of the cured body tends to be remarkably lowered and the adhesive strength tends to be lowered. The operability tends to be poor.

  Furthermore, in the curable material (B) of the present invention, various additives such as an ultraviolet absorber, a dye, a fluorescent agent, an antistatic agent, a pigment, and a fragrance are selected as necessary within a range not deteriorating the performance. Can also be used.

  Next, (A) pretreatment material constituting the dental curable material kit of the present invention will be described. This pretreatment agent has (I) an acidic group-containing polymerizable monomer and (II) water, so that it has a decalcifying action and a penetrating action on the tooth. Here, the acidic group-containing polymerizable monomer is not particularly limited as long as it is a compound having at least one acidic group and at least one polymerizable unsaturated group in one molecule, and a known compound can be used. . Examples of the acidic group present in the molecule of the acidic group-containing polymerizable monomer include the following.

  Examples of the polymerizable unsaturated group present in the molecule of the acidic group-containing polymerizable monomer include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. Can be mentioned.

  Examples of compounds that can be suitably used as the acidic group-containing polymerizable monomer used in the present invention include vinylphosphonic acids in which a phosphonic acid group is directly bonded to a vinyl group, acrylic acid, Examples thereof include methacrylic acid and vinyl sulfonic acid.

In the above compounds, R ¹ represents a hydrogen atom or a methyl group. These compounds may be used alone or as a mixture of two or more kinds, among which group -O-P (= O) ( OH) 2, group _{(-O-) 2 P (= O} ) OH , etc. Most preferably, it is used in the above combination of polymerizable monomers containing a phosphoric acid group. In such a system, not only the decalcification action of the tooth (mainly due to having a phosphate group with strong acidity) is high, but also the intrinsic binding power to the tooth is high, especially high. Adhesive strength is obtained.

  The acidic group-containing polymerizable monomer is preferably a compound having an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group as a polymerizable unsaturated group from the viewpoint of curing speed.

  In the (A) pretreatment material of the present invention, the blending amount of the (I) acidic group-containing polymerizable monomer may be appropriately determined in relation to the other components described later. When the amount of the polymerizable monomer is small, the adhesion strength to the enamel tends to decrease due to a decrease in the decalcification property. On the other hand, when the amount is large, the adhesion strength to the dentin tends to decrease due to a decrease in the permeability. There is. In a state where such an effective amount of the acidic group-containing polymerizable monomer is blended, the (A) pretreatment material constituting the kit of the present invention has a pretreatment material composition pH measured at 23 ° C. of 0. The range is generally from 0.01 to 3.2, more preferably from 0.1 to 2.8, and most preferably from 1.0 to 2.2.

  In addition, (A) In the pretreatment material, the polymerizable monomer component may consist only of the acidic group-containing polymerizable monomer, but it has better adhesive strength and durability against the tooth. It is preferable to further include a polymerizable monomer that does not contain an acidic group from the viewpoint of obtaining properties and adjusting the strength of the adhesive interface and the permeability of the pretreatment material to the tooth. As such a non-acidic group-containing polymerizable monomer, the same monomers as those described as the component (I) of the (B) curable material can be used. When a highly hydrophobic polymerizable monomer is used as the acidic group-free polymerizable monomer, an amphiphilic monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is used. It is preferable in terms of adhesive strength to use a monomer and prevent separation of water, which is an essential component of the pretreatment material of the present invention, to have a uniform composition.

  (A) In the pretreatment material, the blending amount of the non-acidic group-containing polymerizable monomer is the total polymerizable monomer component consisting of the total of (I) the acidic group-containing polymerizable monomer. However, from the viewpoint of the strength of the adhesive strength to both enamel and dentin, it is preferably 5 to 60% by mass, particularly preferably 15 to 45% by mass.

  In the pretreatment material (A) of the present invention, the (II) water contained together with the (I) acidic group-containing polymerizable monomer is used for demineralization of the tooth and the permeability of the acidic group-containing polymerizable monomer. In order to improve, it is necessary for further promoting the reaction between the metal ion-containing glass filler and the acidic group of the acidic group-containing polymerizable monomer. As this water, distilled water or deionized water which does not substantially contain impurities harmful to storage stability and medical components is preferably used.

  In the pretreatment material (A) of the present invention, the blending amount of the above (II) water is not particularly limited, but it improves tooth permeability decalcification and penetrability of acidic group-containing polymerizable monomers. From the viewpoint, the range of 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and most preferably 100 parts by mass of the total polymerizable monomer component including the (I) acidic group-containing polymerizable monomer. It is suitable that it is 10-30 mass parts. When the blending amount of water is small, the demineralization property of the tooth tends to be lowered and the adhesive force tends to be lowered.

  In this invention, you may mix | blend a small amount of metal ion containing glass fillers with the said (A) pretreatment material in the range which can maintain the acidity which can exhibit the decalcification property of the tooth. In particular, when the metal ions contained in the metal ion-containing glass filler are polyvalent metal ions, in the polymer of acidic group-containing polymerizable monomers in the pretreatment material, a plurality of acidic groups and the polyvalent Since metal ions come to form a salt, ion crosslinking occurs three-dimensionally, and the mechanical strength is improved. As such a metal ion containing glass filler, the same thing as what was demonstrated as said (II) component of the said (B) curable material can be used. The blending amount is preferably limited to an amount capable of maintaining the acidity in the effective pH range (pH 0.01 to 3.2) for functioning as a pretreatment material.

By the way, when the pretreatment material is mixed with the polyvalent metal ion-containing glass filler as described above, the three-dimensional ion cross-linking is performed during the storage period of the pretreatment material when all these compositions are mixed in one liquid. Develops excessively and becomes easy to gel. To improve this, adjust the amount of polyvalent metal ions and water eluted from the polyvalent metal ion-containing glass filler to a specific range, and then add a specific amount of volatile water-soluble organic solvent. Is effective. Specifically, it is preferable to use the following composition that the applicant previously applied for a patent (International Application No. PCT / JP2007 / 061148).
That is, (A) a polymerizable monomer component containing 5% by mass or more of an acidic group-containing polymerizable monomer;
(B) a polyvalent metal ion-eluting filler;
(C) a volatile organic solvent;
(D) water;
Containing
The polyvalent metal ion-eluting filler (B) is an amount such that the amount of polyvalent metal ions eluted from the filler is 1.0 to 7.0 meq per 1 g of the polymerizable monomer component (A). The volatile organic solvent (C) is blended in the range of 30 to 170 parts by mass per 100 parts by mass of the polymerizable monomer component (A) and the following formula (1):
α ≧ 20 · X (1)
[Wherein α is a blending amount per 100 parts by mass of the polymerizable monomer component (A) of the volatile organic solvent (C), and X is the polyvalent metal ion-eluting filler (B) The amount of polyvalent metal ions eluted from 1 and the amount (meq) per 1 g of the polymerizable monomer component (A)]
In such an amount that satisfies the conditions represented by
The water (D) is a pretreatment material having a composition blended in an amount of 3 to 30 parts by mass per 100 parts by mass of the polymerizable monomer component (A).

  In this pretreatment material, the amount of polyvalent metal ions eluted from the polyvalent metal ion-containing glass filler and dilution hardening with water and a volatile organic solvent are difficult to cause gelation during storage, At the time of application to the tooth surface, it can be concentrated by dispersing the water and volatile organic solvent by air blow, and the three-dimensional ion crosslinking by the acidic group and the polyvalent metal ion can be developed well. This is preferable because it gives the cured body high strength.

  In the present invention, a small amount of an inorganic filler can be added to the pretreatment material (A) described above for the purpose of improving the strength of the pretreatment material layer after curing. The same inorganic filler as that described as the component (IV) of the curable material (B) can also be used. As the compounding quantity, it is the range of 2-20 mass parts with respect to 100 mass parts of all the polymerizable monomer components containing an acidic group containing polymerizable monomer, More preferably, it is 5-15 mass parts. . If the amount is less than 2 parts by mass, the effect of improving the strength is not sufficiently obtained, and if the amount exceeds 20 parts by mass, the viscosity increases, and the permeability to the tooth is inhibited, and the effect of improving the adhesive strength of the tooth may not be sufficiently obtained. is there.

  Furthermore, in this invention, you may mix | blend a photoinitiator with the (A) pretreatment material from a viewpoint of improving the sclerosis | hardenability and improving adhesive strength. The same photopolymerization initiator as that described as the component (III) of the curable material (B) can be used. However, ii) the aliphatic amine compound is deactivated when it coexists with the (I) acidic group-containing polymerizable monomer, and therefore cannot be used in this pretreatment material. As a compounding quantity of this photoinitiator, (I) The range of 0.01-15 mass parts with respect to 100 mass parts of all the polymerizable monomer components containing an acidic group containing polymerizable monomer, More preferably 0.03 to 10 parts by mass, and optimally 0.5 to 5 parts by mass.

  In addition, it is possible to add an organic thickener such as a polymer compound such as polyvinylpyrrolidone, carboxymethylcellulose, and polyvinyl alcohol to the pretreatment material (A) as long as the performance is not deteriorated. Various additives such as ultraviolet absorbers, dyes, fluorescent agents, antistatic agents, pigments, and fragrances can be selected and used as necessary.

  In the dental curable material kit of the present invention, (A) the pretreatment material and (B) the curable material are used by mixing the above-described components in one package. It is preferable from the viewpoint of simplicity. In this case, for (A) the pretreatment material, (II) use of a polyvalent metal ion-containing glass filler as the metal ion-containing glass filler tends to cause gelation during storage as described above. The amount of polyvalent metal ions eluted from the valent metal ion-containing glass filler is adjusted to a specific amount, and at the same time, a specific amount of water and a volatile organic solvent are mixed and diluted to make this gelation unlikely to occur. preferable. Of course, in such a (A) pretreatment material, an embodiment using a polyvalent metal ion-containing glass filler, or in the (A) pretreatment material or (B) curable material, a plurality of photopolymerization initiators are used. In the case of an embodiment using components that are not stable enough when mixed and stored in one agent, the components are packaged and stored in several parts so that the reaction during storage does not occur. Further, it is also possible to adopt a mode in which these members are mixed and used during use. In order to manufacture each of these packages, mixing of the respective compounding components may be performed in accordance with a standard method. In general, all components to be compounded are measured under an inert light such as red light to form a uniform solution. Mix well.

  In the dental curable material kit of the present invention, as the curable material (B), a curable material that is an object to be bonded to a tooth in the dental treatment field can be applied without limitation. Because of its excellent adhesiveness, it is most preferable to use it for an adhesive for correction. It can also be applied to photocurable composite resins. In addition, it is useful for a dental cement composition containing a photopolymerization initiator and a dental nail polish composition. The method of using the kit is to apply the (A) pretreatment material to the tooth surface, and if air and water are contained by air blowing, remove the rough air and then remove the pretreatment The (B) curable material may be applied or filled on the treated surface of the material, and light may be irradiated to polymerize and cure.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. The abbreviations, abbreviations, adhesion strength measurement methods, storage stability evaluations, and metal ion content measurement methods shown in the examples are as follows.
(1) Abbreviations and abbreviations [acidic group-containing polymerizable monomer; (A) (I)]
PM-a: 2: 1 mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate PM-b: 2-methacryloyloxyethyl dihydrogen phosphate and bis (2 -Methacryloyloxyethyl) 1: 1 mixture of hydrogen phosphate MAC-10: 11-methacryloyloxy-1,1-undecanedicarboxylic acid [acidic group-free polymerizable monomer; (B) (I)]
D26E: 2,2'-bis (4- (methacryloxyethoxy) phenyl) propane BisGMA: 2,2'-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane 3G: triethylene glycol di Methacrylate HEMA: 2-hydroxyethyl methacrylate [metal ion-containing glass filler; (B) (II)]
MF1: Metal ion-containing glass filler obtained by the following production method Fluoroaluminosilicate glass (Tokuso ionomer, manufactured by Tokuyama Dental Co., Ltd.) using a wet continuous ball mill (New My Mill, manufactured by Mitsui Mining Co., Ltd.) After pulverizing to 0.5 μm, the filler surface was treated for 40 minutes with 20 g of 5.0 N hydrochloric acid with respect to 1 g of powder to obtain a metal ion-containing glass filler MF1 having an average particle size of 0.5 μm.

The amount of the metal ions eluted after 3 minutes and 24 hours when the obtained metal ion-containing glass filler MF1 0.1 g was immersed in 10 ml of a 10 wt% maleic acid aqueous solution at a temperature of 23 ° C. was subjected to ICP emission spectroscopic analysis. As a result of analysis using this metal ion-containing glass filler MF1, the amount of ions eluted for 3 minutes was 3.8 meq / g-filler, and the amount of ions eluted for 24 hours was 10 meq / g-filler.
MF2: Metal ion-containing glass filler obtained by the following production method In the production method of MF1, except that the filler surface treatment time with 20 g of 5.0 N hydrochloric acid is set to 20 minutes for 1 g of powder obtained by pulverizing fluoroaluminosilicate glass. In the same manner, a metal ion-containing glass filler MF2 having an average particle size of 0.5 μm was obtained.
As a result of ICP emission spectroscopic analysis, the amount of ions eluted for 3 minutes of this metal ion-containing glass filler MF2 was 9.5 meq / g-filler, and the amount of ions eluted for 24 hours was 25 meq / g-filler.
MF3: Metal ion-containing glass filler obtained by the following production method In the production method of MF1, the same applies except that 1 g of powder obtained by pulverizing fluoroaluminosilicate glass is not subjected to filler surface treatment time with 20 g of 5.0 N hydrochloric acid. As a result, a metal ion-containing glass filler MF3 having an average particle diameter of 0.5 μm was obtained. As a result of ICP emission spectroscopic analysis, the amount of ions eluted for 3 minutes of this metal ion-containing glass filler MF3 was 20 meq / g-filler, and the amount of ions eluted for 24 hours was 50 meq / g-filler.
[Photopolymerization initiator]
(III) i)
CQ: camphorquinone (III) ii)
MDEOA: N-methyldiethanolamine EDEOA: N-ethyldiethanolamine (III) iii)
DMBE: ethyl p-N, N-dimethylaminobenzoate (III) iv)
TAZ: 2,4,6-tris (trichloromethyl) -S-triazine IMDPI: 4-methylphenyl-4′-isopropylphenyliodonium tetrakis (pentafluorophenyl) borate / other photopolymerization initiator TPO: 2,4 6-Trimethylbenzoyldiphenylphosphine oxide [inorganic filler; (IV)]
F1: amorphous silica, particle size 0.02 μm, methyltrichlorosilane treatment F2: amorphous silica, particle size 0.01 μm, dimethyldichlorosilane treatment F3: pulverized quartz, particle size 6 μm, γ-methacryloyloxypropyltrimethoxy Mixture of silane hydrophobized product and F1 having a mass ratio of 80:20 F4: Amorphous silica-zirconia, particle size 4 μm, γ-methacryloyloxypropyltrimethoxysilane hydrophobized product, and F2 having a mass ratio of 8 0:20 mixture F5: spherical silica-zirconia, particle size 0.4 μm, γ-methacryloyloxypropyltrimethoxysilane hydrophobized product, spherical silica-titania, particle size 0.08 μm, γ-methacryloyloxypropyltrimethoxy Mixture having a mass ratio of hydrophobized silane of 70:30
[Volatile water-soluble organic solvent]
IPA: isopropyl alcohol [polymerization inhibitor]
HQME: Hydroquinone monomethyl ether BHT: 2,6-di-t-butyl-p-cresol (2) Shear adhesive strength measurement method A bovine front tooth was removed within 24 hours after slaughter, and a test piece having a cut neck was tested at room temperature. The resin was embedded using a cured resin (manufactured by Nano Factor Co., Ltd.). The labial surface of the test piece was polished with a tooth surface abrasive (manufactured by Neo Pharmaceutical Co., Ltd.), washed with tap water, and then dried by blowing compressed air. A pretreatment material was applied to the polished surface, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. The surface of the pretreatment material applied with a curable material applied to the adhesive base (area, 10.5 mm2) of a metal orthodontic bracket (for medium incisors, made of dents ply tri-gold) The adhesive was removed with the tip of a tweezer. Thereafter, the mesial and distal ends of the bracket were irradiated with a visible light irradiator (Toxo Power Light) every 10 seconds.

After immersing the adhesive test piece in water at 37 ° C. for 24 hours, it was sheared at a crosshead speed of 1 mm / min using a compression shear tester (Autograph, manufactured by Shimadzu Corporation), and the shear bond strength between the tooth and the orthodontic bracket Was measured. The shear strength of four pieces per one test was measured by the above method, and the average value was defined as the adhesive strength.
(3) Tensile bond strength measurement method The bovine front teeth were removed within 24 hours after slaughter, and the enamel and dentin planes were cut out under water injection so as to be parallel to the lip with # 600 emery paper. Next, after compressed air was blown onto these surfaces for about 10 seconds and dried, a double-sided tape with a hole having a diameter of 3 mm was fixed to this plane, and then a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm was fixed. A simulated cavity was formed by fixing to the same center on the circular hole. A pretreatment material was applied into the simulated cavity and left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Further, a curable material was filled thereon and irradiated with light with a visible light irradiator (Toxo Power Light) for 10 seconds to prepare an adhesion test piece.

After the above-mentioned adhesion test piece is immersed in water at 37 ° C. for 24 hours, it is pulled at a crosshead speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation), and the tensile bond strength between the tooth and the curable material is determined. It was measured. Four tensile bond strengths per test were measured by the above method, and the average value was defined as the bond strength.
[(B) Preparation of curable material]
Production Examples 1-25, Comparative Production Examples 1-2
(I) 6.0 g of BisGMA (60 parts by mass) and 4.0 g of 3G (40 parts by mass) were used as the acidic group-free polymerizable monomer. (III) The photopolymerization initiator uses i) 0.02 g of CQ (0.2 parts by mass) as an α-diketone compound, and ii) 0.04 g of MDEOA (0.4 parts by mass) as an aliphatic amine compound. It was. These components and 0.01 g of BHT (0.1 part by mass), which is a polymerization inhibitor, were added as other components, and the mixture was stirred until it became uniform in a dark place. 3.5 g of the composition obtained above, (IV) 6.3 g of F3 (182.3 parts by mass) as an inorganic filler, and (II) 0.2 g of MF2 (5.7 as a metal ion-containing glass filler) (Part by mass) was mixed in an agate mortar and defoamed under vacuum to obtain a photocurable (B) curable material PA1 having a filling rate of 65.0% of the inorganic filler. The composition is shown in Table 1.

  Similarly, in the composition shown in Table 1, Table 2, Table 3, Table 4, and Table 5, as Production Examples 2 to 25, curable materials PA2 to PA25 are used as Comparative Production Examples 1 and 2, and curable materials CPA1 to CPA1 are used. 2 was obtained. All prepared curable materials were stored in a light-shielding container.

[(A) Preparation of pretreatment material]
Production Examples 26 to 29, Comparative Production Examples 3 to 4
(I) Using 6.5 g (65 parts by mass) of PM as the acidic group-containing polymerizable monomer, and further using 3.5 g of HEMA (35 parts by mass) which is an acidic group-free polymerizable monomer. The polymerizable monomer component was used. As (II), 1.5 g of distilled water (15 parts by mass) was used. As other components, volatile water-soluble organic solvent 5.0 g IPA (50 parts by mass) and polymerization inhibitor BHT 0.002 g (0.02 parts by mass) are added, and these are added. The mixture was stirred and mixed until a uniform solution was obtained to obtain (A) pretreatment material Pr1. The composition is shown in Table 6. In addition, it was 1.52 when pH at 23 degreeC of this pretreatment material Pr1 was measured with the pH meter (IM-20E digital ion concentration meter, the Toa Denpa Kogyo make).

  Similarly, with the compositions shown in Table 6 and Table 8, pretreatment materials Pr2 to Pr4 were prepared as Production Examples 27 to 29, and pretreatment materials CPr1 and 2 were prepared as Comparative Production Examples 3 to 4. The prepared pretreatment materials Pr3 to 4 of Production Examples 28 to 29 were each stored in a light shielding container.

Production Examples 30 to 36
(I) 6.2 g of PM (62 parts by mass) is used as the acidic group-containing polymerizable monomer, and 0.5 g of BisGMA (5 parts by mass), which is a non-acidic group-containing polymerizable monomer, 0.3 g of 3G (3 parts by mass) and 3.0 g of HEMA (30 parts by mass) were used as polymerizable monomer components. As (II), 2.2 g of distilled water (22 parts by mass) was used. As these components and other components, 0.75 g of MF2 (7.5 parts by mass) which is a metal ion-containing glass filler, 1.2 g of F1 (12 parts by mass) which is an inorganic filler, volatile water-soluble Add 10.0 g of IPA (100 parts by mass) which is an organic solvent and 0.002 g (0.02 parts by mass) of BHT which is a polymerization inhibitor, and stir and mix them for 3 hours or more to obtain (A) A pretreatment material Pr5 was obtained. The composition is shown in Table 5. In addition, it was 1.95 when pH at 23 degreeC of this pretreatment material Pr5 was measured with the pH meter.

  Similarly, pretreatment materials Pr6 to Pr11 were obtained as Production Examples 31 to 36 with the compositions shown in Tables 6 and 7. The prepared pretreatment materials Pr6 to 11 were all stored in a light shielding container.

Examples 1-55
Using the curable material PA1 obtained in Production Example 1 and the pretreatment material Pr1 obtained in Production Example 26, shear bond strength measurement and tensile bond strength measurement were performed. As a result, the shear bond strength was 10.4 MPa, the tensile bond strength to the enamel was 12.2 MPa, and the tensile bond strength to the dentin was 11.8 MPa.

  Similarly, in Examples 2 to 55, shear adhesive strength measurement and tensile adhesive strength measurement were performed using combinations of curable materials and pretreatment materials shown in Table 9, Table 10, and Table 11. The evaluation results are shown in Table 9, Table 10, and Table 11. As a result, good values were obtained in both the shear bond strength measurement and the tensile bond strength measurement.

Comparative Examples 1-10
In Comparative Example 1, shear adhesive strength measurement and tensile adhesive strength measurement were performed using the curable material CPA1 obtained in Comparative Production Example 1 and the pretreatment material Pr1 obtained in Production Example 26. As a result, the shear bond strength was 5.6 MPa, the tensile bond strength with respect to the enamel was 5.6 MPa, and the tensile bond strength with respect to the dentin was 5.3 MPa.

  Similarly, in Comparative Examples 2 to 10, shear bond strength measurement and tensile bond strength measurement were performed using combinations of curable materials and pretreatment materials shown in Table 12. The evaluation results are shown in Table 12. As a result, sufficient adhesive strength was not obtained in either shear bond strength measurement or tensile bond strength measurement.

Claims (5)

(A) (I) an acidic group-containing polymerizable monomer, and (II) a pretreatment material comprising water (B) (I) an acidic group-free polymerizable monomer , and an acidic group-containing polymerization A polymerizable monomer component that does not contain a photopolymerizable monomer, (II) a metal ion-containing glass filler, (III) i) an α-diketone compound, and ii) a photopolymerization initiator comprising at least an aliphatic amine compound, And (IV) a dental curable material kit comprising a curable material comprising an inorganic filler. (B) In the curable material, (III) i) an α-diketone compound and ii) a photopolymerization initiator comprising at least an aliphatic amine compound, iii) an aromatic amine compound, and iv) a substituent The dental curable material kit according to claim 1, comprising an s-triazine compound having a trihalomethyl group and / or an aryl iodonium salt. (B) in the curable material, (III) the photopolymerization initiator ii) the aliphatic amine compound has a tertiary amino group in which three saturated aliphatic groups are bonded to the nitrogen atom, and The dental curable material kit according to claim 1 or 2, wherein at least two of the saturated aliphatic groups are compounds having an electron-withdrawing group as a substituent. The dental curable material kit according to any one of claims 1 to 3, wherein the (II) metal ion-containing glass filler in the (B) curable material is a polyvalent metal ion-containing glass filler. (B) The curable material is an orthodontic member adhesive, The dental curable material kit according to any one of claims 1 to 4.