JP2022132064A - One-component dental adhesive composition - Google Patents

Abstract

To provide one-component dental adhesive compositions that can exhibit high adhesion to a wide range of visible-light-curing dental materials without pre-curing.SOLUTION: There is provided a one-component dental adhesive composition containing 0.5 to 5 pts.mass of an α-aminoacetophenone-type photoinitiator such as 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone to 100 pts.mass of a polymerizable monomer component containing acidic group-containing polymerizable monomer, and becoming curable by further containing 0.1 to 4 pts.mass of camphorquinone or by visible light irradiation by supplying camphorquinone from the outside (for example, a visible light-curable dental material containing camphorquinone, which is to be an adherend).SELECTED DRAWING: None

Description

The present invention relates to a one-component dental adhesive composition.

Composite resin, which is widely used in dental treatment, consists of a curable composition containing a polymerizable monomer, a polymerization initiator, and an optional filling material. It is a dental material that restores teeth by filling and then hardening. The composite resin type resin cement is a curable composition having the same composition as the composite resin. It is a dental material that is used for tooth restoration by applying it to a dental prosthesis restorative material such as metal, ceramics, or polymer material and pressing it against the restorative material. Depending on the polymerization initiator used, such dental materials (hereinafter sometimes abbreviated as "CR, etc.") are chemically polymerized using a chemical polymerization initiator, or photopolymerized using a photopolymerization initiator. It is classified into a polymerization type and a dual-cure type that uses both polymerization initiators, but the photo-polymerization type and dual-cure type that can be cured by light irradiation (hereinafter also referred to as "photo-curing type CR, etc.") are widely used. is doing. Since these CR etc. themselves have almost no adhesiveness to the tooth substance, when performing treatment (restoration of teeth), in order to firmly bond the hardening material such as CR to the tooth substance, it is necessary to use CR etc. Prior to filling or crimping, a dental adhesive (also called bonding material) must be applied to the tooth surface.

Such dental adhesives are composed of a curable composition containing a polymerizable monomer component containing a polymerizable monomer having a functional group such as an acidic group for improving adhesiveness, and a polymerization initiator. are generally known, and are classified according to the type of polymerization initiator like CR, etc., and are appropriately used based on the characteristics of each type (see Patent Documents 1 and 2). In the case of using a chemical polymerization initiator, there is no need to irradiate light using a light irradiator, but it is necessary to divide it into two liquids and store them and mix them when using. When only the agent is used, light irradiation is required, but there is an advantage that it can be stored as one liquid and mixing operation is not required.

When these conventional dental adhesives are used, they are applied to the surface of the tooth to be treated (restored) and then polymerized and cured to form an adhesive layer before filling with CR or the like. is common. However, in order to perform such curing before filling CR etc. (hereinafter also referred to as "pre-curing"), not only is operation and time required for polymerization, but also the generation of polymerization heat may cause patient discomfort. In addition, there is a risk that the surface of the adhesive layer will be contaminated with saliva, blood, etc. during operation, and the desired adhesive strength will not be obtained. For this reason, dental adhesives have also been developed that do not require pre-curing.

For example, Patent Document 3 describes a one-liquid dental adhesive that not only has the above-described feature of not requiring pre-curing, but also does not require a mixing operation during application. 100 parts by mass of a one-liquid dental adhesive composition for adhering the filling material of (a1) to dentin, containing 1 to 40 parts by mass of (a1) an acidic group-containing polymerizable monomer (A) a polymerizable monomer, 0.05 parts by mass to 2 parts by mass of (B) a divalent copper compound, and 0.1 parts by mass to 10 parts by mass of (c1) an organic peroxide, (C) a peroxide containing at least one of 0.01 to 5 parts by mass of (c2) an inorganic peroxide, and 0.1 to 10 parts by mass of (d1) a bisacylphosphine oxide , containing (D) a photopolymerization initiator, 1 part by mass to 50 parts by mass of (E) water, and 10 parts by mass to 300 parts by mass of (F) an organic solvent, and containing a reducing agent A dental adhesive composition that does not" is disclosed.

JP 2009-137960 A JP 2018-027913 A Japanese Patent Application Laid-Open No. 2020-138911 JP-A-2005-89729 Patent No. 6250245 WO 2020/050123 Pamphlet

Bunichiro Yamada, "Chemistry of Organic Dental Materials: Basic Knowledge and Applications," 1st Edition, Yamamoto Precious Metal Co., Ltd., July 5, 2016, p. 72

The adhesive composition for dental use disclosed in Patent Document 3 adopts a one-liquid structure, and has high adhesion by applying CR or the like without curing after application and curing the CR or the like at the same time. It exhibits an excellent effect that a strong adhesive layer can be formed. However, in order to obtain such effects, it is necessary to use a photocurable dental filling material (such as a photocurable CR) containing an aromatic amine as the dental filling material (such as CR). That is, the dental adhesive composition is intended to be cured by irradiating the (D) photopolymerization initiator contained therein with light that is irradiated when curing CR or the like. Since the intensity of the light reaching the adhesive is reduced by transmission, photocuring alone is not sufficient, and in order to form an adhesive layer with sufficient curing strength, it is contained in the dental adhesive composition (B ) the divalent copper compound and (C) the peroxide and the aromatic amine supplied by the dental filling must form a highly active chemical initiator to function.

Since ultraviolet rays are harmful to the human body, ordinary photocurable CRs are visible light curable types that can be cured by irradiation with light (470 nm) from a general dental light irradiator, and many of them contain a reducing agent. including amine compounds as However, an aliphatic amine is sometimes used as an amine compound (see Patent Document 4), and when the dental adhesive composition is applied to a photocurable CR or the like using only an aliphatic amine, However, since the highly active chemical polymerization initiator is not formed, the desired effect cannot be obtained. In addition, even when used for photocurable CR containing aromatic amine as a reducing agent, the type and amount of aromatic amine contained varies, and there are cases where sufficient effects cannot be obtained. There is also concern that

Therefore, when the present invention is used for visible light curable CR etc., regardless of whether the visible light curable CR etc. contain an amine compound, even if it contains an amine compound, the type irrespective of the blending amount, it is possible to fill the visible light-curable CR etc. without pre-curing and cure it at the same time as the visible light-curable CR etc., and form a high strength adhesive layer by curing at that time. An object of the present invention is to provide a one-liquid type dental adhesive composition capable of

The present invention is intended to solve the above problems, and the first form of the present invention is a polymerizable monomer component containing an acidic group-containing polymerizable monomer: 100 mass and α-aminoacetophenone type photopolymerization Initiator: 0.5 to 5 parts by mass, further containing camphorquinone: 0.1 to 4 parts by mass, or camphorquinone being supplied from the outside so that it can be cured by visible light irradiation. A one-liquid dental adhesive composition characterized by:

The one-liquid dental adhesive composition of the above form (hereinafter also referred to as "the one-liquid dental adhesive composition of the present invention" or "the adhesive composition of the present invention") contains camphorquinone:0. It is preferable to contain 1 to 4 parts by mass.

Further, it is a one-liquid dental adhesive composition for a photocurable dental material comprising a photocurable composition that contains a polymerizable monomer and a photopolymerization initiator and is cured by irradiation with visible light. is preferred. The one-liquid type dental adhesive composition of the present invention is a photocurable composition which contains a photopolymerization initiator containing a polymerizable monomer and camphor-quinone, and which is cured by irradiation with visible light. A one-component dental adhesive composition for a photocurable dental material, which is substantially free of camphorquinone, and is supplied with camphorquinone from the photocurable dental material Also included are one-part dental adhesive compositions that are curable by visible light irradiation.

In the one-component dental adhesive composition of the present invention, the α-aminoacetophenone type photopolymerization initiator is represented by the following general formula (1)

(In the formula, Ph represents a phenyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent organic group or a hydrogen atom.)
and the α-aminoacetophenone type photopolymerization initiator undergoes a triplet energy transfer photosensitization reaction and has a triplet excitation energy of 62 kcal/mol or less. It is preferable to consist of

Furthermore, it is preferable to further contain tertiary amine (excluding α-aminoacetophenone type photopolymerization initiator): 1 to 5 parts by mass, and a solvent component consisting of water and / or an organic solvent: 20 to 450 parts by mass. Further containing is also preferable.

A second aspect of the present invention is a photocurable dental material comprising a photocurable composition that contains a polymerizable monomer and a photopolymerization initiator and is cured by visible light irradiation, and a dental adhesive composition. and wherein the photocurable dental material is a 1 mm thick sample made of a cured product of the photocurable dental material, and has a color difference with a black background and a white background. Y stimulus value on black background: Yb (black background) and Y stimulus value on white background: Yw (contrast ratio defined as the ratio of white background: Yb/Yw = 0.45 The following photocurable dental material, wherein the dental adhesive composition is the one-component dental adhesive composition according to any one of claims 1 to 8. The dental restoration kit (hereinafter also referred to as "the kit of the present invention").

A third aspect of the present invention is a visible light radical polymerization initiator (hereinafter referred to as "visible light radical polymerization initiator of the present invention It is also called "agent".).

According to the visible light type radical polymerization initiator of the present invention, it is possible to sufficiently cure the radically polymerizable monomer even by irradiation with low intensity visible light (for example, light in the wavelength range of 400 to 500 nm). The one-liquid type dental adhesive composition of the present invention contains the visible light type radical polymerization initiator of the present invention, or a visible light curable CR that is cured by irradiation of visible light, which is an object to be adhered during use. Since the visible light radical polymerization initiator of the present invention can be formed by using camphorquinone supplied from the It can be adhered with adhesive strength. Therefore, it is possible to reduce the burden on the patient and to prevent the adhesion strength from being lowered due to adhesion of saliva, blood, etc. to the adhesive layer.

In addition, since the above effect is not affected by components such as amine compounds contained in visible light-curable CR, etc., visible light-curable CR, etc. to which the one-component dental adhesive composition of the present invention can be applied. The range is extremely wide.

1. Overview of the visible light radical polymerization initiator of the present invention and the one-component dental adhesive composition of the present invention Visible light curing to which the one-component dental adhesive composition described in Patent Document 3 is applied The type CR, etc. must contain an aromatic amine, which narrows the range of applicable visible light-curable CR, etc. The reason why the aromatic amine is essential is that it constitutes a specific chemical polymerization initiator together with the components contained in the dental adhesive composition. We believe that there is no limit to visible light-curable CR, etc., as long as it can be sufficiently cured only by the action of the photopolymerization initiator, and it provides sufficient curing strength even with (low intensity) transmitted light. We investigated the photoinitiator. As a result, α-aminoacetophenone-type photopolymerization initiators are not activated by visible light alone, but when they coexist with camphorquinone, they exhibit high polymerization activity even with low-intensity visible light irradiation. I have found that it can work.

(1) a visible light type radical polymerization initiator containing an α-aminoacetophenone type photopolymerization initiator having the above properties and camphorquinone (the visible light type radical polymerization initiator of the present invention); If it is used as a photopolymerization initiator for an adhesive composition, high-strength adhesion can be obtained by curing at the same time as curing the visible light-curable CR, etc., without pre-curing any visible light-curable CR, etc. (2) With regard to camphorquinone, if the photocurable dental material to be adhered contains camphorquinone, this camphorquinone can also be used. As a result, the present invention has been completed.

The α-aminoacetophenone type photopolymerization initiator is used in UV offset inks and liquid resists because its absorption wavelength range is in the ultraviolet region of 300 to 430 nm. Since it does not cause a photoreaction with the light (470 nm) of the instrument (requires ultraviolet light irradiation that is harmful to the human body), it is not usually used as a photocurable material that is directly applied to the human body in dental treatment. In addition, camphor-quinone is widely used as a component of photopolymerization initiators such as photocurable CR (see Non-Patent Document 1), and is included in the photocurable dental material of (2) above. Even when camphorquinone is used, the range of applicable visible light-curing CR and the like is quite wide.

Although the present invention is not bound by any logic, it is presumed that the reason why the above effects are obtained is as follows. That is, the reason why the visible light type radical polymerization initiator of the present invention, in which an α-aminoacetophenone type photopolymerization initiator coexists with camphorquinone, can exhibit high polymerization activity even with low-intensity visible light irradiation is because It is presumed that one molecule of camphorquinone interacts with multiple molecules of α-aminoacetophenone type photopolymerization initiator to generate initiation radicals. For example, in the case of (2) above, after applying the adhesive composition of the present invention in a form containing no camphorquinone to the inner surface of the cavity formed in the tooth (without curing it), the photocurable CR etc., and curing is performed by irradiating with visible light, the camphor-quinone contained in the photocurable CR and the like, including some that has migrated into the adhesive composition of the present invention, is irradiated with visible light. is absorbed and becomes an excited state. Then, the α-aminoacetophenone type photopolymerization initiator contained in the adhesive composition is decomposed by interaction with camphor-quinone in an excited state present in the vicinity of or inside the adhesive composition to generate initiation radicals. hardening proceeds. On the other hand, since camphor-quinone returns to the ground state and repeats the above cycle, it is presumed that high polymerization activity was obtained even with low-intensity visible light irradiation.

As described above, even when the adhesive composition of the present invention does not particularly contain camphorquinone, α-aminoacetophenone is formed by a small amount of camphorquinone supplied from a photocurable CR or the like or camphorquinone in an excited state. It is believed that the photopolymerization initiator of the type is activated and functions effectively as a radical polymerization initiator (because it can generate radicals necessary for polymerization and curing), resulting in high adhesive strength. In the combination of camphorquinone and a tertiary amine, in principle, one molecule of camphorquinone generates one molecule of initiating radical. Adequate curing cannot be obtained with this combination.

In the visible light type radical polymerization initiator of the present invention, 0.04 to 1.6 parts by mass, particularly 0.08 to 0.08 part by mass of camphorquinone is added to 1 part by mass of the α-aminoacetophenone type photopolymerization initiator. It is preferable to contain 8 parts by mass. In addition, it is preferable to contain 0.4 to 2 parts by mass, particularly 0.8 to 1.6 parts by mass of a tertiary amine (other than the α-aminoacetophenone type photopolymerization initiator) described later based on the above criteria.

Hereinafter, a photocurable CR, etc., to which the one-component dental adhesive composition of the present invention is applied (hereinafter also referred to as a "target photocurable CR, etc.") and a one-component dental adhesive composition of the present invention are described. The sexual composition will be described in detail. In this specification, unless otherwise specified, the notation "x to y" using numerical values x and y means "x or more and y or less". In such notation, when only the numerical value y is given a unit, the unit is also applied to the numerical value x. Moreover, in this specification, the term "(meth)acrylic" means both "acrylic" and "methacrylic". Similarly, the term "(meth)acrylate" means both "acrylate" and "methacrylate", and the term "(meth)acryloyl" means both "acryloyl" and "methacryloyl".

2. Target Photocurable CR, etc. and Kit of the Present Invention As described above, the target photocurable CR, etc. (target photocurable CR, etc.) using the one-liquid type dental adhesive composition of the present invention is It differs slightly depending on whether or not the one-component dental adhesive composition of the invention contains camphorquinone, and if it does contain camphorquinone, there is no particular limitation. It becomes a photocurable CR or the like.

The target photocurable CR or the like is not particularly limited to those composed of a photocurable composition containing a polymerizable monomer and a photopolymerization initiator, and those used in conventional photocurable CR and the like. Can be used without restrictions. As the polymerizable monomer, for example, those that are preferably used as the "(a2) acidic group-free polymerizable monomer" in the adhesive composition of the present invention, which will be described later, can be suitably used. Also, the photopolymerization initiator used in photocurable CR, especially visible light curable CR, etc., can be used without limitation, but a combination of camphor-quinone and tertiary amine can also be used. preferred. As the tertiary amine, those suitably used as "(C) tertiary amine" in the adhesive composition of the present invention, which will be described later, can be suitably used. The content of camphorquinone (CQ) and tertiary amine is usually CQ: 0.2 to 2 parts by mass and tertiary amine: 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. , CQ: 0.2 to 0.5 parts by mass and 0.02 to 10 parts by mass of a tertiary amine.

The target photocurable dental filling material may be treated with an inorganic filler such as silica, zirconia, silica-zirconia (a surface treatment agent such as a silane coupling agent) in order to enhance polishing properties and mechanical strength. ) is contained in an amount of 50 to 1,500 parts by weight, particularly 70 to 1,000 parts by weight based on 100 parts by weight of the polymerizable monomer.

Furthermore, additives such as chemical polymerization initiators, polymerization inhibitors, ultraviolet absorbers, and pigments may be included as appropriate.

Ordinary photocurable CR and the like have translucency to a certain extent or more so that they are cured to the inside by irradiation with light (visible light that serves as activation light). Therefore, the light during the light irradiation reaches the one-liquid dental adhesive composition of the present invention that has been applied in advance, and cures it to form a film, thereby eliminating the need for pre-curing. The one-liquid dental adhesive composition of the present invention is from the viewpoint that the desired adhesive strength can be reliably obtained without pre-curing even for a photocurable CR or the like in a relatively deep cavity during treatment. , Y stimulus value on a black background: Yb (black background) and Y stimulus value on a white background: Yw ( Contrast ratio defined as the ratio of the white background: Yb/Yw is used as a dental restorative kit (kit of the present invention) in combination with a photocurable dental material (target photocurable CR, etc.) of 0.45 or less When used as such a kit, even if the thickness of the photocurable dental material (target photocurable CR, etc.) is, for example, 2.0 mm, pre-curing is unnecessary and sufficient. From the viewpoint of such effects, it is preferable to make a dental restorative kit in combination with a photocurable dental material (target photocurable CR, etc.) having a Yb/Yw ratio of 0.40 or less. Although the lower limit of Yb/Yw is not particularly limited, it is usually 0.25 or more, preferably 0.3 or more.

The contrast ratio Yb/Yw is an index of the transparency of the cured product. The lower the contrast ratio, the higher the transparency, and the lower the contrast ratio, the higher the transparency. In addition, the contrast ratio (transparency) of CR before curing does not match the contrast ratio of the cured product, and may be slightly lower or higher depending on the composition. Since the cured body (after curing) is also irradiated with light, if the contrast ratio of the cured body is within the above range, a sufficient adhesive strength can be reliably obtained without pre-curing.

The photocurable dental material (target photocurable CR, etc.) used in the kit of the present invention is not particularly limited as long as it satisfies the above conditions. 3) Because the amount of coloring agents such as pigments is small and the color tone harmony with teeth is high, structural colors that develop colors by the interference effect of light, such as those described in Patent Documents 5 and 6, are used. Light-curing CR, etc. (hereinafter referred to as Also referred to as “structural color system CR”) is preferably used.

Here, the structural color system CR is composed of (1) a polymerizable monomer, (2) a spherical particle group having a predetermined average primary particle diameter in the range of 100 to 1000 nm, and individual constituents of the spherical particle group. The particles are composed of substantially the same substance, and 90% (number) or more of the individual particles are present in the range of 5% before and after the average primary particle size, one or more "same particle size spherical Inorganic particles comprising a "particle group" (G-PID), and (3) a spherical particle containing a photopolymerization initiator and constituting the G-PID at 25 ° C. The refractive index for the sodium D line is the same as the polymerization A curable composition having a higher refractive index than the cured product of the curable composition, wherein the cured product of the curable composition develops a structural color with a constant color tone regardless of changes in the incident angle of light. means a CR, etc., composed of an organic composition.

3. Concerning each component of the one-liquid type dental adhesive composition of the present invention 3-1. (A) Polymerizable Monomer (Monomer) Component (A) Polymerizable monomer (monomer) component is a compound having at least one radically polymerizable unsaturated group in one molecule. The adhesive composition of the present invention is cured by radical polymerization of the (A) monomer. (A) The monomer contains at least (a1) an acidic group-containing polymerizable monomer (acid monomer).

3-1-1. (a1) acidic group-containing polymerizable monomer (acid monomer)
(a1) The acidic group-containing polymerizable monomer (acid monomer) means a polymerizable monomer containing at least one acidic group in addition to at least one radically polymerizable unsaturated group in one molecule. (a1) Acid monomers are mainly composed of dentin (dentin, enamel), base metals (iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, etc., or alloys containing these as main components), and It improves adhesion to metal oxides (zirconia ceramics, alumina, titania, etc.) containing metal such as zirconium and oxygen as main components. In addition, the acid monomer (a1) has the effect of demineralizing the dentine and the effect of improving the permeability to the dentine, thereby improving the adhesiveness of the filling restorative material to the dentine.

The (a1) acid monomer used in the present invention is not particularly different from the acid monomers used in conventional dental adhesives, and the radically polymerizable unsaturated group includes an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylic group. It has an amide group, a styryl group, etc., and the acidic group includes a phosphono group {-P(=O)(OH) ₂ }, a carboxyl group {-C(=O)OH}, a dihydrogen phosphate monoester group { —OP(=O)(OH) ₂ }, hydrogen phosphate diester group {(-O-) ₂ P(=O)OH}, sulfo group (-SO ₃ H), and acid anhydride skeleton {- C(=O)-OC(=O)-} etc. are used without particular limitation. Among these, the polymerizable unsaturated group is preferably an acryloyl group and/or a methacryloyl group from the viewpoint of adhesion to CR or the like. In addition, at least one selected from a carboxyl group, a dihydrogen phosphate monoester group, and a hydrogen phosphate diester group from the viewpoint of high stability to water and gentle dissolution of the smear layer on the tooth surface and tooth demineralization. Polymerizable monomers having a seed group are preferred, and polymerizable monomers having at least one group selected from a dihydrogen phosphate monoester group or a hydrogen phosphate diester group are most preferred.

Examples of (a1) acid monomers that can be preferably used include the following. That is, those having a carboxyl group include acrylic acid, methacrylic acid, 4-(meth)acryloxyethyltrimellitic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di(meth) ) acryloyloxypyromellitic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid and the like. Further, examples of those having a sulfo group include 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, and vinylsulfonic acid. Furthermore, as those having a dihydrogen phosphate monoester group or a hydrogen phosphate diester group, 2-(meth) acryloyloxyethyl dihydrogen phosphate, bis[2-(meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 6-(meth) acryloyloxyhexylphenyl hydrogen phosphate, 10-(meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-dihydrogenphosphate, 1,3-di(meth)acryloylpropane-2-phenylhydrogenphosphate, bis[5-{2-(meth)acryloyloxyethoxycarbonyl }heptyl]hydrogen phosphate and the like.

These acidic group-containing polymerizable monomers may be used alone or in combination of two or more.

The amount of the (a1) acid monomer in the target adhesive composition is the total weight of the (A) monomer component, that is, the total weight of the (a1) acid monomer and (a2) a non-acid monomer described later is 100 parts by weight. The amount of the (a1) acid monomer is preferably 3 parts by mass to 30 parts by mass, more preferably 5 parts by mass to 20 parts by mass.

3-1-2. (a2) Acidic group-free polymerizable monomer (non-acid monomer)
(a2) The polymerizable monomer containing no acidic group (non-acid monomer) is a known compound that does not contain an acidic group and contains one or more radically polymerizable unsaturated groups in one molecule. It can be used without any particular limitation. The radically polymerizable unsaturated group is preferably an acryloyl group and/or a methacryloyl group, like the acid monomer.

(a2) Examples of suitable non-acid monomers include the following. That is, the monofunctional polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, benzyl methacrylate, polyethylene Glycol mono(meth)acrylate, allyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, glyceryl mono(meth)acrylate and the like can be mentioned. Further, as the polyfunctional polymerizable monomer, 2,2'-bis{4-[2-hydroxy-3-(meth)acryloyloxypropoxy]phenyl}propane, triethylene glycol methacrylate, 2,2-bis [(4-(meth)acryloyloxypolyethoxyphenyl)propane], 1,6-bis(methacrylethyloxycarbonylamino)-2,2,4-trimethylhexane, 1,6-bis(methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane, trimethylolpropane trimethacrylate, and the like.

(a2) Non-acid monomers may be used alone or in combination of two or more.

(a2) The blending ratio of the non-acid monomer is the remainder after subtracting the content of the (a1) acid monomer from the mass of the (A) monomer component, that is, (a2) in 100 parts by mass of the (A) monomer component. The content of the non-acid monomer is preferably 70 to 97 parts by mass, more preferably 80 to 95 parts by mass.

3-2. (B) α-aminoacetophenone-type photopolymerization initiator The adhesive composition of the present invention interacts with camphor-quinone in CR etc. in order to eliminate the need for light irradiation in the stage before filling CR etc. (B) an α-aminoacetophenone-type photopolymerization initiator is blended as a component for curing.

(B) The α-aminoacetophenone-type photopolymerization initiator is a compound represented by the following general formula (1), and means a compound that generates radicals by a cleavage reaction caused by light irradiation.

In general formula (1) above, Ph represents a phenyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent organic group or a hydrogen atom. A monovalent organic group is preferably a methyl group, an ethyl group, or a benzyl group.

The α-aminoacetophenone type photopolymerization initiator is preferably a compound that satisfies the above conditions and undergoes a triplet energy transfer photosensitization reaction. A compound having a concentration of 62 kcal/mol or less is more preferable. Compounds that can be preferably used include 2-benzyl-2-(dimethylamino)-4′-morpholinobtyrophenone (manufactured by BASF Japan, trade name IRGACURE369: triplet excitation energy 60 kcal/mol), 2-(4-methyl- Benzyl)-2-(dimethylamino)-4'-morpholinobutyrophenone (manufactured by BASF Japan, trade name IRGACURE379: triplet excitation energy 60 kcal/mol), and 2-methyl-4'-(methylthio)-2-morpholinopro Piophenone (manufactured by BASF Japan, trade name IRGACURE907: triplet excitation energy 61 kcal/mol) and the like can be mentioned.

In addition, the amount of (B) α-aminoacetophenone type photopolymerization initiator in the target adhesive composition is the total mass of (A) monomers, that is, the sum of (a1) acid monomers and (a2) non-acid monomers. The amount of the (B) α-aminoacetophenone type photopolymerization initiator is 0.5 to 5 parts by mass, preferably 1 to 4 parts by mass, based on 100 parts by mass.

3-3. (C) Other Photopolymerization Initiator Components The one-component dental adhesive composition of the present invention contains (B) an α-aminoacetophenone type photopolymerization initiator other than (C) other photopolymerization initiator components. A polymerization initiator component may be included. Here, the photopolymerization initiator component means a compound that becomes excited by light irradiation and generates radicals by a hydrogen abstraction reaction or a cleavage reaction, and a compound that promotes the generation of such radicals. As the photopolymerization initiator, known photopolymerization initiators can be used without limitation. For example, α-diketones such as camphor-quinone, acylphosphine oxides, thioxanthones and the like can be used.

Among these, from the viewpoint of broadening the range of target photocurable CR, etc., (c1) camphorquinone is contained in the visible light radical polymerization of the present invention in the one-liquid dental adhesive composition of the present invention. It is preferred to keep the initiator included. The content of camphorquinone is generally 0.1 to 4 parts by weight, preferably 0.2 to 2 parts by weight, per 100 parts by weight of the total weight of the (A) monomers.

Moreover, it is preferable that (c2) a tertiary amine is included as another photopolymerization initiator component for the purpose of improving adhesiveness. (c2) The tertiary amine increases the polymerization activity as a hydrogen donor, and also improves adhesion by reducing polymerization inhibition by oxygen.

Such (c2) tertiary amines are not particularly limited as long as they are tertiary amines other than α-aminoacetophenone type photopolymerization initiators, and aromatic tertiary amines having an aromatic ring in the molecule, Any known compound of aliphatic tertiary amines that does not have an aromatic ring in the molecule can be used without limitation.

Examples of those that can be preferably used as aromatic tertiary amines include the following. That is, methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, p -Propyl diethylaminobenzoate and the like can be mentioned.

Moreover, if the thing which can be used suitably as an aliphatic tertiary amine is illustrated, the following can be mentioned. Examples include triethanolamine, N-methyldiethanolamine, triethylamine, tributylamine, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate and the like.

Each of the (c1) aromatic tertiary amine and (c2) aliphatic tertiary amine may be used alone, or two or more thereof may be used in combination.

Particularly in the present invention, aliphatic tertiary amines are preferred from the viewpoint of adhesion, and N,N-dimethylaminoethyl methacrylate containing a radically polymerizable unsaturated group is most preferred.

Further, the amount of the tertiary amine (c2) in the target adhesive composition is preferably 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the total mass of the monomers (A), and 2 parts by mass to 4 parts by mass is more preferred.

3-4. (D) Solvent Component The adhesive composition of the present invention preferably contains a solvent component (D) comprising water and/or an organic solvent from the viewpoint of operability and storage stability.

(D) Water, which is a solvent component, preferably does not substantially contain harmful impurities from the viewpoint of storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water, distilled water, and the like. .

Organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, butanol and isobutyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, 1,4-dioxane and tetrahydrofuran; ethyl acetate, ethyl formate and the like. aromatic solvents such as toluene, xylene and benzene; hydrocarbon solvents such as pentane, hexane, heptane and octane; chlorinated solvents such as methylene chloride, chloroform and 1,2-dichloroethane; can be used. Among these, ketones and alcohols are preferable, and acetone, methyl ethyl ketone, ethanol, isopropyl alcohol, and tertiary butyl alcohol are particularly preferable from the viewpoint of solubility and storage stability.

In addition, the amount of the solvent component (D) in the target adhesive composition is preferably 20 parts by mass to 450 parts by mass when the total mass of the monomers (A) is 100 parts by mass, and 40 parts by mass to 200 parts by mass. Parts by mass are more preferable.

3-5. Other Components The one-component dental adhesive composition of the present invention may contain components such as various additives other than the components described above, if necessary. Examples of additives include fillers and polymerization inhibitors.

A filler is added to improve the mechanical strength and operability of the adhesive layer obtained by curing the dental adhesive composition. The filler is not particularly limited, and known inorganic fillers, organic fillers, and inorganic-organic composite fillers can be used.

Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, and the like.

Moreover, if it is a part of the components of the chemical polymerization initiator consisting of a combination of a plurality of compounds, it can be included as long as it does not function as a chemical polymerization initiator (to the extent that it can be stored as one liquid). For example, (B) a divalent copper compound and (C) a peroxide contained in the dental adhesive composition described in Patent Document 3 can be included. When one containing an aromatic amine is used, a highly active chemical polymerization initiator is formed similarly to the dental adhesive composition described in Patent Document 3, and curability can be further enhanced.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

1. Raw Materials First, substances used as raw materials in Examples, Comparative Examples, and Reference Examples and their abbreviations are shown below.

1-1. (A) polymerizable monomer (monomer)
(a1) acidic group-containing polymerizable monomer (acid monomer)
• MDP: 10-methacryloxydecyl dihydrogen phosphate • SPM: a mixture of mono(2-methacryloxyethyl) acid phosphate and bis(2-methacryloxyethyl) acid phosphate.

(a2) Acidic group-free polymerizable monomer (non-acid monomer)
BisGMA: 2.2′-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate UDMA: 2,2,4 -trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate D-2,6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl).

1-2. (B) α-aminoacetophenone type photopolymerization initiator IC369: 2-benzyl-2-(dimethylamino)-4′-morpholinobtyrophenone (manufactured by BASF Japan, IRGACURE369)
· IC379: 2-(4-methyl-benzyl)-2-(dimethylamino)-4'-morpholinobtyrophenone (manufactured by BASF Japan, IRGACURE379)
- IC907: 2-methyl-4'-(methylthio)-2-morpholinopropiophenone (manufactured by BASF Japan, IRGACURE907).

1-3. (c1) photopolymerization initiator other than α-aminoacetophenone type CQ: camphor-quinone BTPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

1-4. (c2) tertiary amine • DMEM: 2-(dimethylamino)ethyl methacrylate • TEA: triethanolamine • DMBE: 4-(dimethylamino)ethyl benzoate.

1-5. (D) Solvents Acetone Ethanol IPA: Isopropanol Water.

2. Examples and Comparative Examples Example 1
(1) Preparation of one-liquid type adhesive composition Acid monomer MDP: 20 parts by mass, non-acid monomer Bis-GMA: 33 parts by mass and 3G: 22 parts by mass, HEMA: 25 parts by mass, (B) An adhesive composition was obtained by mixing 2.5 parts by mass of IRGACURE 369 as an α-aminoacetophenone type photopolymerization initiator, 40 parts by mass of ethanol and 20 parts by mass of water as a solvent.

(2) Target photocurable CR, etc. As a dental composite resin (CR) to be a target photocurable CR, Esterite Universal Flow Shade CE {manufactured by Tokuyama Dental, contrast ratio: Yb/Yw = 0.39, below , EUF(CE). } was used to evaluate the adhesive strength to the dentin, which will be described later.
The above contrast ratio was measured by placing CR in a mold having a through hole of 7 mmφ × 1 mm, pressing polyester films on both sides, and applying a visible light irradiator (e.g., Eliper, manufactured by 3M, irradiation intensity 1200 mW / cm ² ) for a cured body sample with a thickness of 1 mm obtained by curing by irradiating both sides with light for 10 seconds each, measured with a color difference meter (manufactured by Tokyo Denshoku, "TC-1800MKII") on black and white backgrounds, respectively. It means the value of Yb/Yw determined based on Yb and Yw obtained from the calculation.

(3) Evaluation of adhesive strength (adhesive strength) to dentin Bovine anterior teeth extracted within 24 hours after slaughter were polished with water-resistant abrasive paper P600 under water, and ivory was applied so that it was parallel and flat to the lip surface. A double-faced tape having a hole of 3 mm in diameter was attached to the polished surface obtained by scraping out the textured surface. Subsequently, the adhesive composition was applied to the adhesive surface exposed through the holes of the double-sided tape among the polished surfaces, and dried by blowing air for 5 seconds.

Paraffin wax having a thickness of 0.5 mm and a hole having a diameter of 8 mm was attached to the adhesive surface coated with the dental adhesive composition so that the hole in the paraffin wax and the hole in the double-sided tape were concentric. A simulated cavity with a depth of 0.5 mm was created. After filling the above-mentioned EUF (CE) into this simulated cavity and lightly pressing it with a polyester film, photocuring was performed by light irradiation for 10 seconds using a visible light irradiator (Eliper, manufactured by 3M, irradiation intensity 1200 mW/cm ² ). gone. After that, a pre-polished SUS304 round bar (diameter 8 mm, height 18 mm) was adhered with resin cement (Bistite II, manufactured by Tokuyama Dental). Finally, a sample for adhesive strength measurement was obtained by immersing it in water at 37°C for 24 hours. The composite resin (Esterite Universal Flow) used is a photopolymerizable composition containing CQ.

The tensile adhesive strength (adhesive strength) of the prepared sample was measured using an autograph manufactured by Shimadzu Corporation (crosshead speed: 2 mm/min). The measured values of the four samples were averaged to give a measured value of 12.0 MPa. Incidentally, if the tensile strength is 10 MPa or more, it is judged to be good.

Examples 2-29
A one-component dental adhesive composition of the present invention was obtained and evaluated in the same manner as in Example 1, except that the composition was changed as shown in Tables 1 and 2. Evaluation results are shown in Tables 1 and 2. In addition, "↑" in these tables means "same as above".

Comparative Examples 1-4
A one-component dental adhesive composition of the present invention was obtained and evaluated in the same manner as in Example 1, except that the composition was changed as shown in Table 3. Table 3 shows the evaluation results. In addition, "↑" in Table 3 means "same as above".

As shown in Tables 1 and 2, the adhesion test results were good in all cases in Examples 1 to 26.

On the other hand, as shown in Table 3, Comparative Example 1 did not contain (B) the α-aminoacetophenone-type photopolymerization initiator, so the adhesive strength was low. Comparative Example 2 did not contain an acid monomer exhibiting adhesiveness to tooth substance, so the adhesive strength was low. Also, in Comparative Examples 3 and 4 using photopolymerization initiators other than (B) α-aminoacetophenone type, good adhesion test results were not obtained.

Example 30
(1) Preparation of Curability Evaluation Sample Acid monomer MDP: 20 parts by mass, non-acid monomer Bis-GMA: 33 parts by mass and 3G: 22 parts by mass, HEMA: 25 parts by mass, (B) α- 0.4 parts by mass of IRGACURE 369, which is an aminoacetophenone-type photopolymerization initiator, (C) DMBE, which is a tertiary amine other than the α-aminoacetophenone-type photopolymerization initiator: 0.5 parts by weight, and CQ: 0.5 parts by weight. A sample for curability evaluation was obtained by mixing 3 parts by mass.

(2) Curability evaluation of cured product A polytetrafluoroethylene mold having a hole of 6 mmφ × 1.0 mm was filled with a sample for curability evaluation and pressed with a polypropylene film. The irradiator was brought into close contact with a polypropylene film and irradiated with light for a specified period of time to prepare a cured product. Vickers hardness was obtained from the diagonal length of the indentations formed in the test piece under a load of 50 gf and a load holding time of 30 seconds using a Vickers indenter with a microhardness tester (MHT-1 model manufactured by Matsuzawa Seiki Co., Ltd.). rice field. Table 4 shows the results. The Vickers hardness obtained was 5.6 when the light irradiation time was 5 seconds and 6.7 when the light irradiation time was 20 seconds. In this evaluation, in order to compare cured bodies with different monomer compositions, the ratio (%) of the Vickers hardness at 5 seconds to the Vickers hardness at 20 seconds is defined as the degree of immediate curing. did. It is judged that the higher the instant curing degree, the better the photopolymerization initiator that can be cured even with short (weak) light irradiation.

Comparative Examples 5-8
A sample for evaluating curability was obtained and evaluated in the same manner as in Example 30, except that the composition was changed as shown in Table 4. Table 4 shows the evaluation results.

As shown in Table 4, in Example 30, (a1) an acid monomer and (B) an α-aminoacetophenone type photopolymerization initiator and CQ added assuming supply from dental materials are included, so immediate curing It was judged to be an excellent photopolymerization initiator with a high degree of polymerization.
On the other hand, as shown in Table 4, in Comparative Example 5, since the composition did not contain (B) the α-aminoacetophenone type photopolymerization initiator, the degree of immediate curing was low.
Curing did not proceed in Comparative Example 6 because CQ was not included. As a result, the Vickers hardness could not be measured.
In Comparative Example 7, since the (a1) acid monomer was not included, the degree of immediate curing was low.
In Comparative Example 8, the degree of immediate curing was low because (a1) an acid monomer and (B) an α-aminoacetophenone type photopolymerization initiator were not included.
Compared to Comparative Example 8, Comparative Example 7 showed a lower Vickers hardness, so when (a1) monomer (A) containing no acid monomer was used, (B) α-aminoacetophenone type photopolymerization It was suggested that the initiator would inhibit the polymerization.

Examples 31-32
In Example 1, the dental composite resin to be filled in the simulated cavity was Esterite Universal Flow Medium Shade A1 (manufactured by Tokuyama Dental Co., Ltd., contrast ratio 0.51) in Example 31. Adhesion strength to tooth substance was evaluated in the same manner as in Example 1 except that Light Universal Flow Medium Shade A4 (manufactured by Tokuyama Dental Co., Ltd., contrast ratio 0.53) was used. As a result, the adhesive strength in Example 31 was 11.5 MPa, and the adhesive strength in Example 32 was 11.3 MPa.

Examples 33-35
By changing the thickness of the 0.5 mm-thick paraffin wax with a hole of 8 mm in diameter to 2.0 mm, the depth of the simulated cavity is set to 2.0 mm, and the dental composite resin to be filled in the simulated cavity is displayed. Evaluation of adhesive strength to tooth substance was carried out in the same manner as in Example 1, except that the one shown in 5 was used. Table 5 shows the results.

The abbreviations in the dental composite resin: CR column in Table 5 mean the following CR.

- EUF (CE): Same as used in Example 1, Esterite Universal Flow Medium Shade CE (manufactured by Tokuyama Dental, contrast ratio 0.39)
・ OCF: Omni Chroma Flow (Structural color system CR manufactured by Tokuyama Dental, contrast ratio 0.31)
- OC: Omni Chroma (Tokuyama Dental Co., Ltd. structural color system CR, contrast ratio 0.39).

Claims (10)

Polymerizable monomer component containing acidic group-containing polymerizable monomer: 100 mass and α-aminoacetophenone type photopolymerization initiator: 0.5 to 5 mass parts, camphorquinone: 0.1 to 4 A one-liquid type dental adhesive composition characterized in that it further contains parts by mass or is made curable by irradiation with visible light by externally supplying camphorquinone. Camphorquinone: The one-liquid dental adhesive composition according to claim 1, containing 0.1 to 4 parts by mass. A one-liquid dental adhesive composition for a photocurable dental material comprising a photocurable composition that contains a polymerizable monomer and a photopolymerization initiator and is cured by irradiation with visible light. 2. The one-component dental adhesive composition according to 2 above. A one-liquid type dental adhesive composition for a photocurable dental material, comprising a photocurable composition that contains a photopolymerization initiator containing a polymerizable monomer and camphor-quinone and that is cured by irradiation with visible light. being a thing,
2. The one-liquid dental adhesive composition according to claim 1, which does not substantially contain camphorquinone and is curable by irradiation with visible light by supplying camphorquinone from the photocurable dental material. . The α-aminoacetophenone type photopolymerization initiator has the following general formula (1)

(In the formula, Ph represents a phenyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent organic group or a hydrogen atom.)
The one-component dental adhesive composition according to any one of claims 1 to 4, comprising a compound represented by 6. The α-aminoacetophenone type photopolymerization initiator comprises a compound that undergoes a triplet energy transfer photosensitization reaction and has a triplet excitation energy of 62 kcal/mol or less. 1. The one-component dental adhesive composition according to Item 1. The one-component dental adhesive composition according to any one of claims 1 to 6, further comprising 1 to 5 parts by mass of a tertiary amine (excluding an α-aminoacetophenone type photopolymerization initiator). . The one-component dental adhesive composition according to any one of claims 1 to 7, further comprising 20 to 450 parts by mass of a solvent component consisting of water and/or an organic solvent. A dental restoration comprising a combination of a photocurable dental material comprising a photocurable composition which contains a polymerizable monomer and a photopolymerization initiator and which is cured by irradiation with visible light, and a dental adhesive composition is a kit,
The photocurable dental material is obtained by tristimulus value measurement with a color difference meter using a black and white background for a sample with a thickness of 1 mm made of a cured product of the photocurable dental material, Y on a black background Stimulation value: Yb (black background) and Y stimulation value on a white background: Yw (contrast ratio defined as the ratio of the white background: Yb/Yw is a light-curing dental material of 0.45 or less,
The dental adhesive composition is the one-component dental adhesive composition according to any one of claims 1 to 8,
The dental restorative kit, characterized in that: A visible light type radical polymerization initiator comprising an α-aminoacetophenone type photopolymerization initiator and camphorquinone.