JP2016006040A - Dental adhesive composition and mobile tooth-fixing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental adhesive composition which has excellent bending toughness and good strength, and is suitable as a mobile tooth-fixing material.SOLUTION: The invention provides a dental adhesive composition which contains a polymerization monomer (A), and the repeated bending test durability of the composition in which the polymerization monomer (A) is polymerized is 3 times or more. The composition contains a filler (B) expressing flexibility. The reaction force of the filler (B) when compressed 10% is 30 MPa or less. Further, the ratio of the solid content which remains without dissolving (residual solid content weight after drying a solvent after immersion/pre-immersion weight) of the filler is 30% by weight or more when being immersed into acetone under conditions of room temperature and 24 hours.

Description

  The present invention relates to a dental adhesive composition. More specifically, the present invention relates to a dental adhesive composition having excellent bending toughness and good strength and suitable as a rocking tooth fixing material.

  As the elderly and periodontal disease increase, gingival retraction occurs, making it difficult to support the teeth sufficiently, and the teeth become loose and easily fall off. These wobbled teeth are called swaying teeth. In the treatment of this oscillating tooth, a method is adopted in which the oscillating tooth is fixed to a healthy tooth to suppress tooth wobble, and during that time the cause of gingival recession is removed. As a material used when fixing a rocking tooth to a healthy tooth, a rocking tooth fixing material can be mentioned. It is required not to drop off. In order to meet the demand as this material, it is necessary for the rocking tooth fixing material that the cured body is excellent in strength. Moreover, since fixation with a healthy tooth | gear needs adhesion | attachment with a tooth | gum and several months period is required depending on the fixation period, it is also required to have favorable adhesiveness.

  Currently, Super Bond (manufactured by Sun Medical Co., Ltd.) is listed as one of the rocking tooth fixing materials. This superbond includes (A) a compound having at least one acidic group and a polymerizable group in the molecule, (B) a compound having one polymerizable group in the molecule and having no acidic group, (C) poly ( It is a dental adhesive composition comprising (meth) acrylate) particles (hereinafter referred to as (meth) acrylate as a generic term for acrylate and methacrylate) and (D) a polymerization initiator. This composition is widely used as a rocking tooth fixing material because it is excellent in adhesiveness to a tooth and exhibits excellent toughness against external stress. However, since this composition needs to be divided into three components, that is, a monomer component consisting of component (A) and component (B), a powder component of component (C), and a catalyst component of component (D), Is complicated.

  For this reason, the rocking tooth fixing material is excellent in strength when made into a hardened body, has a good adhesiveness to the tooth, and has a composition 1 for easy operation at the time of use. There is a need to be in the form of ingredients.

  By the way, Patent Document 1 (Japanese Patent No. 4162738) discloses a photopolymerization type orthodontic resin composition. This is a resin composition suitable for the production of splints or bite plates used for the treatment of jaw movement dysfunction (temporomandibular disorders), bruxism, occlusal abnormalities and the like in dentistry.

  The cured product of this resin composition is blended with a crosslinked polyurethane powder in order to achieve an appropriate elasticity, but only with the use of the undercut of the dentition, with regard to adhesion to the tooth. Is not taken into consideration at all, and therefore it cannot be used as a reference in the field of a rocking tooth fixing material or the like that requires adhesion to the tooth.

  Further, Patent Document 2 (Japanese Patent Laid-Open No. 2013-1000025) discloses a powder liquid adhesive resin cement used in a brushing method, and has a description that it is used in a dental rocking tooth fixing method. This is a brush stacking method, that is, a powder material and a liquid material are prepared separately, the liquid material is contained in the small brush, and then the ball tip is brought into contact with the powder material to produce a ball-shaped resin mud on the brush tip. The resin mud is a dental adhesive material that is used as an adhesive by placing it on the adherend surface or a place where the resin mud is desired to be built up.

Although this dental adhesive material has achieved adhesion to the tooth and is perfect as a swinging tooth fixing material, the operation of the writing method with separate powder material and liquid material is complicated and easy to use Cannot achieve proper operation.
Accordingly, it has been desired to make the composition into a one-component form in order to be excellent in strength, have good adhesion to the tooth, and simplify the operation during use.

Japanese Patent No. 4162738 JP 2013-1000025 A

  The present invention is excellent in strength and has good adhesiveness to the tooth for the purpose of being able to be easily operated as well as preventing the destruction and falling off of the cured body in the fixed tooth fixation treatment. And it makes it a subject to provide a composition with the form of 1 component, in order to simplify operation at the time of use.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor, in particular, in a rocking tooth fixing material, etc. We have found that the measured flexibility parameters are important. Among them, when a flexible filler or a polyfunctional (meth) acrylate compound having a urethane bond is used as a polymerizable monomer, it is possible to obtain toughness and flexibility, and further, crosslinking as a flexible filler. The present invention has been achieved by obtaining toughness and flexibility by blending a porous polyurethane powder and the like.

  That is, the present invention is a dental adhesive composition containing a polymerizable monomer (A), and the composition obtained by polymerizing the polymerizable monomer (A) has a repeated bending test resistance of 3 times or more. It is the dental adhesive composition characterized.

  The present invention is a dental adhesive composition that is excellent in flexibility, has good adhesiveness to the tooth, and is simple to operate during use.

Next, the dental adhesive composition of the present invention will be specifically described.
In the present specification, regarding the description of necessary or suitable numerical ranges, for example, “preferably XX to YY” (XX, YY are numerical values, etc.) is described as “preferably XX or more and / or YY. It is the following.

  The present invention is a dental adhesive composition containing a polymerizable monomer (A), wherein the composition obtained by polymerizing the polymerizable monomer (A) has a repeated bending test resistance of 3 times or more. A dental adhesive composition.

  The bending test is a three-point bending test in which one surface of the specimen is supported by two fulcrums and stress is applied from the opposite surface to the center position between the two fulcrums. The resistance to repeated bending test is to add and return the stress until the specimen is bent to a certain length, and to count how many times the specimen can withstand without breaking.

  More specific details of the test are as follows. In other words, a specimen prepared with a width of 2 mm and a thickness of 2 mm was set so that the distance between the two unconstrained fulcrums was 20 mm, and a crosshead speed of 20 mm / This is a method in which bending stress is applied under the condition that the stroke length is 3 mm.

The polymer obtained by polymerizing the composition of the present invention preferably has a resistance to repeated bending test of the above-mentioned method of 3 (more preferably 5, more preferably 10) times or more.
Such resistance to repeated bending tests can be achieved from a uniform composition of monomers capable of forming a tenacious polymer, but various performances such as adhesion to teeth, abrasion resistance, water resistance, and discoloration resistance. In order to achieve this while maintaining the characteristics, it is desirable to construct a composite material, which makes it possible to achieve the above problem more easily.

  The specific design of the composite material includes physical properties such as adhesion to teeth, abrasion resistance, water resistance, and discoloration resistance in cured products obtained by polymerizing monomers. The material mechanical strength is realized by the filler (B) scattered in the polymerized cured body matrix.

Filler (B)
The shape of the filler is not particularly limited as long as it is a filler. Typically, the filler is a substantially spherical particle, but the particle is not limited to this shape. For example, an elliptical shape, star shape, plate shape, layer shape, polyhedron shape, fiber shape, mesh shape, spiral shape, porous shape, ring shape, chained chain shape, rod shape, pipe including those having an extreme flatness Various shapes such as a shape, a crescent shape and a zigzag shape can be exemplified.

In the case of the design as described above, since the filler is preferably flexible, the material is preferably organic. As the flexibility, the reaction force when the filler is compressed to 10% less than the original length is preferably 25 (more preferably 15, more preferably 5) MPa or less. Alternatively, the reaction force when the filler is compressed to 30% less than the original length is preferably 50 (more preferably 30, more preferably 10) MPa or less. These can be easily measured by performing a micro compression test on one filler particle. Examples of such a measuring instrument include a microcompression tester MCT-510 manufactured by Shimadzu Corporation. In this testing machine, the calculation can be performed by applying the following formula shown in JIS R 1639-5 (2007) used in the test method for compressive fracture strength.
Cs = 2.48 × (P / π · d ² )
(Where Cs is strength (MPa), reaction force here, P is test force (N), and d is particle diameter (mm).)

  Furthermore, in order for the polymer matrix and the filler to realize the functional role sharing, it is preferable that after polymerization, the composite material is formed by phase separation, for example, in the shape of sea islands. Therefore, it is preferable that the filler component does not dissolve in the solvent and the domain does not disappear. Further, when the filler is dissolved in the polymerizable monomer or is significantly swollen (to the extent that the boundary between the filler and the matrix becomes unclear at the resolution level of the optical microscope), the dental adhesive composition gels and has operability. Undesirably worsening. For this purpose, it is preferable that the filler does not dissolve or swell under the conditions in which the filler is actually exposed.

  The solubility of the filler can be evaluated by the following method. The ratio of the solid content that remains immersed without being dissolved in the component that the filler is actually exposed at a certain temperature and time (the weight of the remaining solid after drying after drying / the weight before immersion) ). Since a methacrylic ester derivative is often used as a monomer for dental adhesives, it is appropriate to immerse in acetone as a solvent having similar solubility, for example, at room temperature for 24 hours. Can be tested. The ratio of the solid content remaining undissolved under the test conditions is preferably 30 (more preferably 60, still more preferably 90) wt% or more.

  Conversely, if the affinity between the monomer before polymerization and / or the polymer after polymerization (hereinafter referred to as a matrix as the union of both) and the filler is too low, integrity as a composite material cannot be maintained. In this case, the adhesive strength is lowered, which is not preferable. It is desirable that the matrix and the filler have a high affinity. For example, the filler may slightly swell in the matrix or the like (to the extent that the boundary between the filler and the matrix is kept clear at the optical microscope resolution level), or the filler and the matrix. Can be exemplified by a chemical bond or a physical bond such as covalent bond, ionic bond, and intermolecular force. More specifically, the filler surface has a highly compatible molecular chain with the matrix, etc., has an ethylenic double bond capable of radical polymerization with the matrix, or other highly reactive matrix. And a group having a highly active group such as an isocyanate group, a carboxylic acid group, a phosphoric acid group, an amino group, and a hydroxyl group, which can form a bond by reacting with a site.

  As a suitable example, a molecule has a hard segment (hereinafter abbreviated as Hs) and a soft segment (hereinafter abbreviated as Ss). There are many examples in which high elongation, flexibility, and bending resistance are manifested in those that are tightly bound and move freely in Ss. When both the filler and the matrix have such a similar molecular structure, if the Hs on both the filler side and the matrix side are tightly bound together, the above characteristics such as high elongation are effectively expressed. In addition, the binding property between the filler and the matrix becomes extremely strong. Furthermore, in this case, there is an advantage that there is no need to introduce an ethylenic double bond for bonding to both the filler and the matrix by a chemical reaction or a highly active reactive group to cause a binding reaction as appropriate at the time of adhesion. . In other words, the filler and the matrix are preferably Hs / Ss type molecules capable of firmly binding each Hs, specifically, polyurethane (Hs: polyurethane (crystalline phase), Ss: polyester or Polyether), polyamide (Hs: polyamide (crystalline phase), Ss: polyether), polyester (Hs: polyester (crystalline phase), Ss: polyether), polystyrene (Hs: polystyrene (freezing phase), Ss: Examples thereof include polybutadiene or polyisoprene) and polyolefins (Hs: polypropylene (frozen phase), Ss: ethylene propylene rubber).

  The organic material constituting the filler is polyurethane, polybutyl acrylate, polyacrylate ester, polyamide, silicone, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / acrylic acid copolymer, polyethylene glycol, Flexible polymers such as polypropylene glycol, polystyrene, nitrile rubber, polybutadiene, polyisoprene, and ethylene / α-olefin copolymers are used. The above-mentioned crosslinked polymer or copolymer can be used in the same manner. Acrylic acid includes (meth) acrylic acid, and acrylic acid ester includes (meth) acrylic acid ester.

  As described above, since the filler component is flexible, it is preferable that the domain does not disappear when dissolved in a solvent or a monomer, and the matrix and the filler preferably have high affinity. Cross-linked polyacrylic acid esters and ethylene / acrylic acid copolymers are preferred.

  Crosslinked urethane powder can be illustrated as a suitable filler component mix | blended with the dental adhesive composition of this invention. This crosslinked urethane powder has the effect of lowering the elastic modulus of the cured product by utilizing the flexibility of urethane, and further, as a polymerizable monomer (A), a polyfunctional (meth) acrylate compound having a urethane bond, By using together with a (meth) acrylate compound having no urethane bond, the cured product is further given elasticity. However, the hardness of the cross-linked polyurethane powder affects the physical properties of the dental composition, and polyurethane powder that does not have cross-linking is suitable because the polymer tends to swell in the monomer and storage stability deteriorates. Therefore, it is necessary to select a crosslinked polyurethane powder suitable for the intended physical properties.

  In the present invention, in order to achieve suitable physical properties and operability of the dental adhesive composition, the average particle diameter of the filler is preferably in the range of 1 to 1000 μm, and in the range of 2 to 100 μm. It is more preferable that it is in the range of 3 to 20 μm. When the value is below the lower limit of the numerical range, it is difficult to handle the powder. On the other hand, when the value exceeds the upper limit, the surface of the polymer may be roughened.

  The average particle size is measured by measuring a particle sample with a laser diffraction particle size distribution analyzer (for example, SALD-2100 manufactured by Shimadzu Corporation), and measuring the measured cumulative volume 50% particle size as the average particle size of the sample. And

  The filler (B) exhibiting the flexibility is used in an amount of preferably 1 to 99 (more preferably 5 to 50, still more preferably 10 to 30)% by weight, with the composition of the present invention as 100% by weight. The When the value is below the lower limit of the numerical range, flexibility is not sufficiently exhibited. On the other hand, when the value exceeds the upper limit, the fluidity of the composition is lowered and the operability is remarkably deteriorated. By using the filler (B) that exhibits flexibility in such an amount, the dental adhesive composition of the present invention provides toughness and flexibility that cannot be achieved by the component (A) alone, and resists external stress. become able to.

  The crosslinked polyurethane powder will be specifically described below. Specific examples of cross-linked polyurethane powders include Negami Kogyo's Art Pearl “JB-800T”, “P-800T”, “C-800”, “U-600T”, “RZ-600T”, “RY”. -600T "," RT-600T "," RX-600T "," RW-600T ", and the like. These powders can be used alone or in combination of two or more. “RZ-600T”, “RY-600T”, “RT-600T”, “RX-600T” and “RW-600T”, which have an ethylenic double bond capable of radical polymerization with the matrix, are the strength of the cured product. From the viewpoint of

The double bond remaining in the organic substance constituting the filler is defined by a double bond equivalent (m · mol / kg) which is the number of millimoles of double bond per kg. In the present invention, preferably 200 to 6000 ( More preferably, it is 500-3000, More preferably, it is 1000-1800) m * mol / kg. When the value is below the lower limit of the numerical range, the effect of improving the strength of the cured product by the double bond cannot be sufficiently obtained, and when the value exceeds the upper limit, the coloring property becomes a problem, which is not preferable.
Further, as described above, when there are double bonds remaining in the organic material constituting the filler, the maximum point stress in the bending test increases.

However, if there are double bonds remaining in the organic matter constituting the filler, if the filler is hard, the elastic modulus becomes too large and the resistance to repeated bending tests may decrease, so the flexibility of the filler And the amount of double bonds is appropriately selected in view of the combination of polymerizable monomers.
This crosslinked polyurethane powder can be produced from the polyfunctional polyol (I) and the polyfunctional isocyanate component (II).

  As the polyfunctional polyol (I), polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, polyurethane polyol, aromatic polyol (phthalic acid polyol), epoxy polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol And polyolefin polyol.

  A plurality of polyol components may be used in combination, and when a trifunctional or higher functional compound is used in combination, the degree of crosslinking of the polyurethane powder can be increased. Moreover, the polyfunctional polyol (I) has higher flexibility of the urethane powder as the mass average molecular weight is larger.

  When polyether polyol is used as the polyol component, the glass transition temperature of the obtained crosslinked polyurethane powder is −35 ° C. or lower, and the flexibility in the low temperature range is high. The glass transition temperature is the temperature at the midpoint of the temperature range where the glass transition occurs as measured by a differential scanning calorimeter (DSC).

  In the method for producing a crosslinked polyurethane powder using the polyester polyol (A) as a polyol component, the crosslinked polyurethane having a low glass transition temperature (specifically, a glass transition temperature of −50 ° C. or lower) and excellent flexibility even in a low temperature range. A powder can be obtained. Moreover, it has excellent heat resistance despite its low glass transition temperature.

In addition, even if the glass transition temperature is about −10 ° C. or less, sufficiently practical flexibility is exhibited.
Among various polyols, polycarbonate polyols or aromatic polyols are preferred in terms of improving hydrolysis resistance.
When a polyfunctional polyol is used, the degree of crosslinking of the crosslinked polyurethane powder can be increased, and the elastic recovery property can be increased.
Examples of the polyfunctional polyol include a trifunctional polycaprolactone-based polyol.
The polyfunctional polyol has higher flexibility as the mass average molecular weight is larger.

  The number average molecular weight of the polyol component is preferably 500 or more, and more preferably 2000 or more. If the number average molecular weight of the polyol component is 500 or more, the glass transition temperature becomes clear and the OH value becomes low, so that the blending amount can be increased. Therefore, a crosslinked polyurethane powder having higher flexibility can be obtained.

  The number average molecular weight of the polyol component is preferably 10,000 or less, more preferably 6000 or less, and even more preferably 4000 or less. If the number average molecular weight is within the above range, the polyol component can be easily obtained.

  In addition, the polyol component was used as a single product as another polyol, that is, a polyol, in a range where the glass transition temperature of the resulting crosslinked polyurethane powder does not become excessively high (a range in which the glass transition temperature does not exceed −10 ° C.). In some cases, a polyol having a glass transition temperature exceeding −10 ° C. may be contained. For example, polycarbonate polyol, acrylic polyol, polyurethane polyol, aromatic polyol (phthalic acid polyol) and the like can be mentioned.

  Examples of the polyol component include a high molecular weight polyol (hereinafter referred to as a macro polyol), a low molecular weight polyol, and the like. Macropolyol is a polyol having a number average molecular weight of 400 to 10,000.

  The polyester polyol can be obtained by a known esterification reaction, that is, a condensation reaction between a polybasic acid and a polyhydric alcohol, a transesterification reaction between an alkyl ester of a polybasic acid and a polyhydric alcohol, or the like.

  Examples of the polybasic acid or its alkyl ester include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid, for example, fatty acids such as hexahydrophthalic acid and tetrahydrophthalic acid. Cyclic dicarboxylic acids, for example, aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, or the like, or dialkyl esters thereof (for example, C 1-6 alkyl esters) or acid anhydrides thereof Or a mixture thereof.

  The polybasic acid preferably includes an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, or orthophthalic acid, and more preferably includes the combined use of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid.

  Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 2-methyl-1,3-propanediol, 1,5- Pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, alkane (carbon number 7 to 22) diol, 2, 6-dimethyl-1-octene-3,8-diol, cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, bisphenol A or water Alkylated bisphenol A Oxide adducts, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, hexaoxypropylene glycol, etc. Diols such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, 2, Triols such as 2-bis (hydroxymethyl) -3-butanol and other aliphatic triols (8 to 24 carbon atoms), for example, tetramethylol Tan, D- sorbitol, xylitol, D- mannitol, polyols having four or more hydroxyl groups, such as D- mannitol, or mixtures thereof, and the like.

  Examples of the polyhydric alcohol also include polyhydroxy compounds containing an anionic group. Examples of the anionic group include a betaine structure-containing group such as a carboxyl group, a sulfonyl group, a phosphate group, and a sulfobetaine. Preferably, a carboxyl group is mentioned. Examples of such a polyhydroxy compound containing a carboxyl group as an anionic group include polyhydroxyalkanoic acids such as dimethylolacetic acid, dimethylollactic acid, dimethylolpropionic acid, and dimethylolbutanoic acid.

The polyhydric alcohol is preferably a diol.
Preferably, the polyester polyol includes a polyester polyol having a ring structure in the molecule, such as a polyester polyol obtained by a reaction between a polybasic acid containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid and a polyhydric alcohol containing a diol. It is done.

A polyester polyol obtained by reacting 3-methyl-1,5-pentanediol and adipic acid is a preferred example.
The polyether polyol is, for example, an alkylene oxide having a low molecular weight polyol as an initiator (for example, an alkylene oxide having 2 to 5 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, or oxetane compound). Can be obtained by ring-opening homopolymerization or ring-opening copolymerization. Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-propylene copolymer, and polyoxytetramethylene glycol (polytetramethylene ether glycol).

  The polycarbonate polyol can be obtained, for example, by reacting phosgene, dialkyl carbonate, diallyl carbonate, alkylene carbonate, or the like in the presence or absence of a catalyst using a low molecular weight polyol (described later) as an initiator. it can.

  In addition, the polyurethane polyol is a polyester polyol, polyether polyol and / or polycarbonate polyol obtained as described above, in a ratio in which the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) exceeds 1, By making it react, it can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, or a polyester polyether polyurethane polyol.

  Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups in the molecule and another monomer copolymerizable therewith. It is done. Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, poly Examples thereof include hydroxyalkyl maleate and polyhydroxyalkyl fumarate. Further, as another monomer copolymerizable with these, for example, (meth) acrylic acid (hereinafter referred to as (meth) acrylic acid as a generic term for acrylic acid and methacrylic acid), (meth) acrylic Alkyl acid (1 to 12 carbon atoms), maleic acid, alkyl maleate, fumaric acid, alkyl fumarate, itaconic acid, alkyl itaconic acid, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2 -Isocyanate-2-propyl) -α-methylstyrene, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like. The acrylic polyol can be obtained by copolymerizing these monomers in the presence of a suitable solvent and a polymerization initiator.

  Examples of the epoxy polyol include an epoxy polyol obtained by a reaction between a low molecular weight polyol (described later) and a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.
As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

  As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing fluorine compound such as tetrafluoroethylene or chlorotrifluoroethylene is used as another copolymerizable monomer. Examples include coalescence.

Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.
The hydroxyl equivalent of the macropolyol is, for example, 200 to 5000, and preferably 250 to 4000.

Moreover, the number average molecular weight of a macropolyol is 400-10000, for example, Preferably it is 500-8000.
The number average molecular weight of the macropolyol can be calculated from a known hydroxyl value measurement method such as an acetylation method or a phthalation method, and the number of functional groups of the initiator or the raw material.

  The low molecular weight polyol is a polyol having a number average molecular weight of less than 400, and examples thereof include the polyhydric alcohols described above. For example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol , 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, alkane (carbon number 7 to 22) diol, diethylene glycol, trioxyethylene glycol, tetra Oxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, hexaoxypropylene glycol Low molecular weight diols such as Le, such as polyhydroxy acids such as dimethylolpropionic acid.

These polyol components can be used alone or in combination of two or more.
The polyfunctional isocyanate component (II) may be any of yellowing type, non-yellowing type, and hardly yellowing type. Specific examples of the isocyanate component (II) include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Isocyanurate compounds (trifunctional) or uretdione compounds (bifunctional) formed from the above diisocyanate monomers can also be used. Moreover, terminal isocyanate group polyisocyanate (For example, adduct type polyisocyanate, biuret type polyisocyanate, etc.) can also be used as polyfunctional isocyanate component (II).

The polyisocyanate prepolymer refers to a reaction product of isocyanate or diisocyanate and polyol having a reactive isocyanate group at the terminal.
For example, various aliphatic diisocyanates or alicyclic diisocyanates such as 1,5-tetrahydronaphthalene diisocyanate, 4-cyclohexylene diisocyanate, and dimer acid diisocyanate may be used. When a bifunctional terminal isocyanate urethane prepolymer is used, thermoplastic urethane particles are obtained, and when a bifunctional or higher terminal isocyanate urethane prepolymer is used, three-dimensionally crosslinked urethane particles are obtained. These isocyanates can be used alone or in combination of two or more.

  Examples of the polyisocyanate component include aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.

  Aromatic polyisocyanates include, for example, 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 4,4'-toluidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl ether Aromatic diisocyanates such as diisocyanates are mentioned.

  Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), Examples include araliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene.

  Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexyl. Methane diisocyanate or mixture thereof (H12MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixture thereof (hydrogenated xylylene diisocyanate, H6XDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane Examples thereof include alicyclic diisocyanates such as diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

  Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2,4,4. -Or aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate.

  In addition, as the polyisocyanate component, a multimer (for example, dimer, trimer, pentamer, heptamer, etc.) of the above polyisocyanate component, for example, the above polyisocyanate component or multimer, Biuret modified product produced by reaction with water, allophanate modified product produced by reaction with monool or polyhydric alcohol (described later), oxadiazine trione modified product produced by reaction with carbon dioxide, and low molecular weight Examples include polyol modified products produced by reaction with polyol (described later).

These polyisocyanate components can be used alone or in combination of two or more.
Preferred examples of the polyisocyanate component include araliphatic polyisocyanates and alicyclic polyisocyanates, and more preferred examples include XDI, IPDI, H12MDI, and H6XDI.

  The molar ratio (NCO / OH) between the isocyanate component and the polyol component is preferably 1-20. If the molar ratio of the isocyanate component to the polyol component is 1 or more, the unreacted polyol component hardly remains, and if it is 20 or less, the amount of soft segments in the crosslinked polyurethane powder increases and the glass transition temperature is clear. Appear in

  Moreover, when the viscosity of a suspension becomes high and it becomes difficult to handle, it is preferable to mix | blend a dilution solvent with a crosslinked polyurethane powder raw material. The dilution solvent may be any solvent that does not inhibit the polymerization reaction.

Moreover, a catalyst may be contained in the crosslinked polyurethane powder raw material. Examples of the catalyst include dibutyltin dilaurate.
Moreover, in order to improve various physical properties of the obtained crosslinked polyurethane powder, the crosslinked polyurethane powder raw material may contain an ultraviolet absorber, an antioxidant, a metal powder, a fragrance and the like.

The water to which the crosslinked polyurethane powder raw material is added contains a suspension stabilizer.
The suspension stabilizer is not particularly limited as long as it is generally used in suspension polymerization, and may be organic or inorganic. Specific examples of the suspension stabilizer include cellulose-based water-soluble resins such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylates, polyethylene glycol, polyvinylpyrrolidone, polyacrylamide, and tertiary phosphoric acid. Examples include salts. These may be used individually by 1 type and may use 2 or more types together.

  A surfactant may be used in combination with the suspension stabilizer. The surfactant used in combination with the suspension stabilizer may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  The addition amount of the suspension stabilizer is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the crosslinked polyurethane powder raw material. When the addition amount of the suspension stabilizer is within the above range, the average particle diameter of the crosslinked polyurethane powder can be easily adjusted to a range of 1 to 1000 μm suitable as a filler.

  On the other hand, when the amount of the suspension stabilizer is more than 30 parts by mass, the average particle size tends to be smaller than 1 μm, and the viscosity of the suspension tends to be high, so that solid-liquid separation and washing are difficult. It is in. Further, when the amount of the suspension stabilizer is less than 1 part by mass, the particles tend to aggregate and the particle diameter tends to be larger than 1000 μm.

  The amount of water for dissolving or dispersing the suspension stabilizer is preferably 30 to 1000 parts by mass of water with respect to 100 parts by mass of the crosslinked polyurethane powder raw material. If the amount of water is 30 parts by mass or more, the cross-linked polyurethane powder raw material can be stably dispersed, and if it is 1000 parts by mass or less, the production amount of the cross-linked polyurethane powder per suspension polymerization is sufficient. Can be secured.

A method for producing such a crosslinked polyurethane powder will be described.
Specifically, a cross-linked polyurethane powder raw material is dispersed in water and reacted to prepare a cross-linked polyurethane powder suspension (hereinafter referred to as cross-linked polyurethane powder preparation step), and the cross-linked polyurethane powder suspension is solidified. And a step of liquid separation (hereinafter referred to as a post-treatment step).

[Crosslinked polyurethane powder preparation process]
In the case of a polyester polyol, a bifunctional one is mainly used, but trifunctional or higher ones may be used in combination. When trifunctional or higher functional compounds are used in combination, the crosslinking degree of the crosslinked polyurethane powder can be increased.

The preferable example of the manufacturing method of the crosslinked polyurethane powder used suitably by this invention is demonstrated.
This method for producing a crosslinked polyurethane powder has a step of reacting an isocyanate component with a polyol component to obtain a terminal isocyanate group prepolymer as a crosslinked polyurethane powder raw material (hereinafter referred to as a prepolymer preparation step), if necessary. When the prepolymer preparation step is included, the crosslinked polyurethane powder raw material becomes a terminal isocyanate group prepolymer and water, but a polyol component may be added if necessary. When there is no prepolymer preparation step, the crosslinked polyurethane powder raw material is an isocyanate component, a polyol component and / or water.

  A cross-linked polyurethane powder raw material is dispersed in the form of particles in water containing a suspension stabilizer and reacted to prepare a cross-linked polyurethane powder suspension (hereinafter referred to as a bead preparation step), and a cross-linked polyurethane powder suspension. And a step of separating the liquid into solid and liquid (hereinafter referred to as a post-treatment step).

  In particular, if the molar ratio of isocyanate component to polyol component (NCO / OH) is 2, a terminal isocyanate group prepolymer having isocyanate groups at both ends of the polymer can be easily obtained.

  In order to disperse the crosslinked polyurethane powder raw material into particles after adding it to water containing a suspension stabilizer, a stirring method is usually employed. The stirring speed at that time is preferably adjusted appropriately so that the droplets containing the crosslinked polyurethane powder raw material have a predetermined particle diameter.

After the adjustment of the particle diameter of the droplets is completed, the mixture is heated to a temperature of 30 to 90 ° C., and the crosslinked polyurethane powder raw material is reacted for 1 to 6 hours to perform suspension polymerization. In this suspension polymerization, when a terminal isocyanate group prepolymer is contained, a urea bond is formed by the reaction of this with water, so that polyurethane can be obtained. By this suspension polymerization, a crosslinked polyurethane powder suspension can be obtained.
After the crosslinked polyurethane powder preparation step, a post-treatment step is performed in the same manner as in the first embodiment to collect the crosslinked polyurethane powder.

[Post-processing process]
In the solid-liquid separation in the post-processing step, for example, filtration or centrifugation is applied.
Washing and drying are preferably performed after the solid-liquid separation.
In washing, the separated and recovered crosslinked polyurethane powder is further washed with water or the like to remove the suspension stabilizer remaining in the crosslinked polyurethane powder.

  In the drying, for example, a heat drying method, an airflow drying method, a vacuum drying method, an infrared drying method, or the like is applied. For example, when the heat drying method is applied, the drying temperature is preferably 40 to 110 ° C., and the drying time is preferably 2 to 40 hours.

  When the suspension is solid-liquid separated and washed, the suspension may be treated with an enzyme such as cellulose-degrading enzyme that decomposes the suspension stabilizer, polyvinyl alcohol-degrading enzyme, or a reagent such as hypochlorite. Good. By treating with the reagent, the viscosity of the suspension can be lowered to facilitate the solid-liquid separation operation, and the washing can be easily performed.

Polymerizable monomer (A)
The monomers used in the composition of the present invention are classified and defined as follows.
Attributes of whether or not to have a urethane bond: U,
Multi-functional attribute: M,
Attributes having or not having an acidic group: S,
Attribute of whether or not it is a (meth) acrylate type: R,
And having attribute X (∋U, M, S, R): X ₁
If no: X ₀
Either good case (corresponding to the union of the former two in the set-theoretic): X _*
% By weight of monomer Y based on 100% by weight of all monomers: Y ^%
And

For example, U ₀ M ₁ S _* R ₁ ^% does not have a urethane bond when the total monomer is 100% by weight, is polyfunctional, and does not limit the presence or absence of acidic groups. Weight of (meth) acrylate monomer %.

Further, considering the strict balance of the whole, it is as follows.
U ₁ M _* S _* R _* ^%, which is the weight% of the urethane monomer (A1) when the total monomer is 100% by weight, is preferably 1 to 99 (more preferably 10 to 70, and still more preferably 30). -70)% by weight. If the value falls below the lower limit of the numerical range, the strength decreases. If the value exceeds the upper limit, the strength increases and the flexibility is impaired.

U _* M ₁ S _* R _* ^%, which is the weight% of the polyfunctional monomer (A2) based on 100% by weight of all monomers, is preferably 1 to 99 (more preferably 10 to 99, still more preferably 50). ~ 99) wt%. If the value falls below the lower limit of the numerical range, the strength decreases. If the value exceeds the upper limit, the strength increases and the flexibility is impaired.

_{U * M * S 1 R *} % is the weight percent of the monomer having an acidic group at the time of the total monomer as 100% by weight (A3) is preferably 0.1 to 99 (more preferably 0.1 20, more preferably 1 to 10)% by weight. If the value falls below the lower limit of the numerical range, the adhesiveness decreases, and if the value exceeds the upper limit, the water resistance deteriorates.
The monomer of the present invention will be described in further detail as follows.

(U ₁ M ₁ S ₀ R ₁ : Polyfunctional (meth) acrylate compound not having an acidic group having a urethane bond)
The (U ₁ M ₁ S ₀ R ₁ ) component blended in the dental adhesive composition of the present invention is a polyfunctional (meth) acrylate compound having a urethane bond. The (meth) acrylate compound in the (U ₁ M ₁ S ₀ R ₁ ) component is a (meth) acryloyl group (hereinafter referred to as (meth) acryloyl as a generic term for acryloyl and methacryloyl) in the molecule. For example, it can be easily synthesized by subjecting a compound having an isocyanate group (—NCO), which will be described later, to a (meth) acrylate compound having a hydroxyl group (—OH).

  Examples of the compound having an isocyanate group include hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate and the like.

  Examples of the (meth) acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. 10-hydroxydecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin mono (meth) acrylate, N-hydroxyethyl (meth) Acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, bisphenol A diglycidyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2,2-bis [4- [3 (Meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol tri (meth) acrylate, dipentaerythritol tri Or hydroxy (meth) acrylate compounds, such as tetra (meth) acrylate, can be mentioned. In the dental adhesive composition of this invention, (A) component can be used individually or in combination of 2 or more types.

U ₁ M ₁ S ₀ R ₁ ^% is preferably used in the range of 1 to 99 (more preferably 10 to 80, still more preferably 20 to 70) wt%. If the value falls below the lower limit of the numerical range, the strength decreases. On the other hand, if the value exceeds the upper limit, the strength is high and the flexibility is impaired. By using the component (U ₁ M ₁ S ₀ R ₁ ) in such an amount, the dental adhesive composition of the present invention gives the effect of imparting toughness and flexibility to the cured product after the polymerization reaction, Provides resistance to external stress.

(U ₀ M _* S ₀ R ₁ : (meth) acrylate compound having no urethane group and no acidic group)
The (U ₀ M _* S ₀ R ₁ ) component blended in the dental adhesive composition of the present invention is a (meth) acrylate compound having no urethane bond. As the compound that can be used as such a (U ₀ M _* S ₀ R ₁ ) component, a known polymerizable monomer can be used. Examples of such polymerizable monomers include α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, maleic acid, itaconic acid and other esters, (meth) acrylamide Or (meth) acrylamides such as (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives, and the like. Of these, (meth) acrylic acid esters and (meth) acrylamides are preferred from the viewpoint of good polymerizability.

Examples of such polymerizable monomers are shown below.
Monofunctional monomer: Monofunctional monomers having one polymerizable group include methyl (meth) acrylate, iso-butyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2 -(N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (Me ) Acrylate, N- methylol (meth) acrylamide, N- hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, (meth) acryloyloxydodecyl pyridinium bromide, and the like.

  Bifunctional monomer: Examples of the bifunctional monomer having two polymerizable groups include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl. Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxy Propyl (meth) acrylate, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, 1,8- Bis [3- (meth) acryloyloxy-2- Droxypropyl] triethylene glycol diether, 1,3-bis [3- (meth) acryloyloxy-2-hydroxypropyl] glycerin diether, pentaerythritol di (meth) acrylate, 2,2,4-trimethylhexamethylene Bis (2-carbamoyloxyethyl) di (meth) acrylate and the like can be mentioned.

Trifunctional or higher monomer: Trifunctional or higher monomer having three or more polymerizable groups includes trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethanetri (Meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, dipenta Examples include erythritol hexa (meth) acrylate.
In the dental adhesive composition of the present invention, the above (U ₀ M _* S ₀ R ₁ ) component can be used alone or in combination of two or more.

The above U ₀ M _* S ₀ R ₁ ^% is preferably used in the range of 1 to 99 (more preferably 5 to 80, still more preferably 10 to 50) wt%. If the value falls below the lower limit of the numerical range, the strength decreases. On the other hand, if the value exceeds the upper limit, the strength is high and the flexibility is impaired. By using the (U ₀ M _* S ₀ R ₁ ) component in such an amount, the dental adhesive composition of the present invention effectively acts on long-term physical property stability of the cured product after the polymerization reaction. The basic characteristics regarding the physical properties of the dental adhesive composition of the present invention are established by using the monomer within the above range.

(U ₀ M ₀ S ₁ R _* : a compound having at least one acidic group and polymerizable group in the molecule, not having a urethane bond and not polyfunctional)
The (U ₀ M ₀ S ₁ R _* ) component blended in the dental adhesive composition of the present invention is a polymerizable compound having at least one acidic group and polymerizable group in the molecule. As the polymerizable group in this (U ₀ M ₀ S ₁ R _* ) component, a radical polymerizable group is preferably used, and vinyl group, vinyl cyanide group, acryloyl group, methacryloyl group, acrylamide group, methacrylamide Examples include groups. Examples of the acidic group include a carboxyl group, a phosphoric acid group, a thiophosphoric acid group, a sulfonic acid group, and a sulfinic acid group. Alternatively, a substance that substantially functions as an acidic group, such as an acid anhydride group of a carboxyl group, which easily decomposes under practical conditions to become the acidic group is regarded as an acidic group.

In the present invention, examples of the polymerizable compound having a carboxyl group, which is a specific example of the (U ₀ M ₀ S ₁ R _* ) component, include α-unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid. A vinyl aromatic ring compound such as 4-vinylbenzoic acid; a linear hydrocarbon group exists between the (meth) acryloyloxy group such as 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and the carboxylic acid group; Carboxylic acid compound; (Meth) acryloyloxyalkylnaphthalene (poly) carboxylic acid such as 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid; 4- (meth) acryloyloxymethyl trimellitic acid, 4- (meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxybutyl trimellitic acid, etc. (Meth) acryloyloxyalkyl trimellitic acid; 4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid and other compounds further containing a hydroxyl group; 2,3-bis (3,4-dicarboxyl Compounds having carboxybenzoyloxy such as benzoyloxy) propyl (meth) acrylate (hereinafter referred to as (meth) acrylate as a generic term for acrylate and methacrylate); N, O-di (meth) acryloyltyrosine, O- ( N- and / or O-position substitution such as (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, O- (meth) acryloylphenylalanine, N, O-di (meth) acryloylphenylalanine Mono or di (meth) acrylic Royl amino acid; N- (meth) acryloyl-4-aminobenzoic acid, N- (meth) acryloyl-5-aminobenzoic acid, 2- or 3- or 4- (meth) acryloyloxybenzoic acid, 4- or 5- (Meth) acryloyl compound of benzoic acid having a functional substituent such as (meth) acryloylaminosalicylic acid; addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride, 2-hydroxyethyl (meth) Hydroxy such as addition reaction product of acrylate and maleic anhydride or 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride Addition reaction product of alkyl (meth) acrylate and unsaturated polycarboxylic anhydride; 2- (3,4-dicarboxybenzoyl Xyl) -1,3-di (meth) acryloyloxypropane, N-phenylglycine or an adduct of N-tolylglycine and glycidyl (meth) acrylate, 4-[(2-hydroxy-3- (meth)) (Carboxylobenzoyloxy) and (meth) acryloyl such as acryloyloxypropyl) amino] phthalic acid, 3- or 4- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid Examples thereof include compounds having oxy. Of these, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and 4- (meth) acryloyloxyethyl trimellitic acid are preferably used.

  A group having at least one hydroxyl group bonded to a phosphorus atom and a functional group that can be easily converted to the group in water, for example, a phosphate ester group having one or two hydroxyl groups (acid phosphate group) Can be preferably exemplified. Examples of the polymerizable monomer having such a group include 2- (meth) acryloyloxyethyl acid phosphate, 2- and / or 3- (meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl. (Meta) such as acid phosphate, 6- (meth) acryloyloxyhexyl acid phosphate, 8- (meth) acryloyloxyoctyl acid phosphate, 10- (meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate ) Acryloyloxyalkyl acid phosphate; bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [2- or 3- (meth) acryloyloxypropyl] acid phosphate, etc. (Meth) acryloyloxy such as an acid phosphate having two or more (meth) acryloyloxyalkyl groups; 2- (meth) acryloyloxyethylphenyl acid phosphate, 2- (meth) acryloyloxyethyl-p-methoxyphenyl acid phosphate An acid phosphate having an aromatic ring such as an alkyl group and a phenylene group or a hetero atom such as an oxygen atom can be used. The compound which substituted the phosphate group in these compounds by the thiophosphate group can also be illustrated. Of these, 2- (meth) acryloyloxyethyl acid phosphate can be preferably used.

  Examples of polymerizable monomers having a sulfonic acid group or a functional group that can be easily converted into sulfonic acid group in water include 2-sulfoethyl (meth) acrylate, 2- or 1-sulfo-1- or 2-propyl (meth) ) Sulfoalkyl (meth) acrylate such as acrylate, 1- or 3-sulfo-2-butyl (meth) acrylate; 3-bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo- Compounds having an atomic group containing a hetero atom such as halogen or oxygen in the alkyl part such as 2-propyl (meth) acrylate; 1,1-dimethyl-2-sulfoethyl (meth) acrylamide, 2-methyl-2- ( A compound that is acrylamide instead of the acrylate such as (meth) acrylamidepropanesulfonic acid; Examples thereof include vinyl aryl sulfonic acids such as 4-styrene sulfonic acid and 4- (prop-1-en-2-yl) benzene sulfonic acid. Of these, 4-styrenesulfonic acid can be preferably used. These compounds can be used alone or in combination of two or more.

U ₀ M ₀ S ₁ R _* ^% is preferably used in the range of 0.1 to 99 (more preferably 0.1 to 20, still more preferably 1 to 10)% by weight. When the value is below the lower limit of the numerical range, the adhesiveness is lowered. On the other hand, when the value exceeds the upper limit, the water resistance is deteriorated. By using the compound having at least one acidic group and polymerizable group in the molecule (U ₀ M ₀ S ₁ R _* ) in such an amount, the dental adhesive composition of the present invention can be adhered to an adherend. It shows good adhesiveness to hard tissues represented by the tooth.

(C) Polymerization initiator The (C) component mix | blended with the dental adhesive composition of this invention is a polymerization initiator. The polymerization initiator includes a known polymerization initiator such as a thermal polymerization initiator, a room temperature polymerization initiator, or a photopolymerization initiator, and a desired polymerization initiator to be blended in the dental adhesive composition of the present invention. A photopolymerization initiator (C2) that can be cured only by irradiation with light is sometimes preferred. As the photopolymerization initiator, a photosensitizer alone or a combination of a photosensitizer and a photopolymerization accelerator can be used.

  As photosensitizers, α-diketone compounds such as benzyl and camphorquinone, α-naphthyl, p, p′-dimethoxybenzyl, pentadione, 1,4-phenanthrenequinone, naphthoquinone, diphenyltrimethylbenzoylphosphine oxide and other ultraviolet light These are known compounds that are excited by light or visible light to initiate polymerization, and one kind or a mixture of two or more kinds may be used. Among these, acylphosphine oxides such as camphorquinone and diphenyltrimethylbenzoylphosphine oxide or derivatives thereof are particularly preferably used.

  Further, when using a photopolymerization initiator, it is preferable to use a photopolymerization accelerator in combination. Examples of the photopolymerization accelerator used here include p-toluenesulfinic acid or an alkali metal thereof; N, N-dimethylaniline, N, N-diethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, pN, N-dimethylaminobenzoic acid, pN, N-diethylaminobenzoic acid , Ethyl pN, N-dimethylaminobenzoate, ethyl pN, N-diethylaminobenzoate, methyl pN, N-dimethylaminobenzoate, methyl pN, N-diethylaminobenzoate, pN , N-dimethylaminobenzaldehyde, 2-N-butoxyethyl p-N, N-dimethylaminobenzoate, 2-N-butoxyethyl pN, N-diethylaminobenzoate, pN , N-dimethylaminobenzonitrile, pN, N-diethylaminobenzonitrile, pN, N-dihydroxyethylaniline, p-dimethylaminophenethyl alcohol, N, N-dimethylaminoethyl methacrylate, triethylamine, tributylamine, tri Tertiary amines such as propylamine and N-ethylethanolamine; secondary amines such as N-phenylglycine and alkali metal salts of N-phenylglycine; Acids, malic acid, combinations with 2-hydroxypropanoic acid; barbituric acids such as 5-butylaminobarbituric acid, 1-benzyl-5-phenylbarbituric acid; benzoyl peroxide, di-tert-butyl peroxide, etc. Of organic peroxides. As a photopolymerization accelerator, you may use 1 type chosen from these, or 2 or more types mixed. In particular, nitrogen atoms are directly bonded to aromatics such as ethyl pN, N-dimethylaminobenzoate, 2-N-butoxyethyl pN, N-dimethylaminobenzoate, N, N-dimethylaminoethyl methacrylate, and the like. Secondary amines such as tertiary aromatic amines or aliphatic tertiary amines having a polymerizable group such as N, N-dimethylaminoethyl methacrylate, N-phenylglycine, and alkali metal salts of N-phenylglycine Is preferably used.

  The (C) polymerization initiator is preferably 0.001 to 5 (more preferably 0.05 to 2 and still more preferably 0.05 to 1) by weight based on 100% by weight of the total composition of the present invention. Used in the range of%. If the value falls below the lower limit of the numerical range, the curing rate decreases. On the other hand, if the value exceeds the upper limit, the curing rate becomes too fast and the operability deteriorates. Moreover, the compounding quantity of a polymerization accelerator will not be limited if photocuring performance is accelerated | stimulated, However, Usually, it is used in 5-1000 weight% with respect to 100 weight% of photoinitiators.

  In addition, as a polymerization initiator used by this invention, it is preferable to use a photoinitiator as mentioned above, However, A thermal polymerization initiator and a normal temperature polymerization initiator can also be utilized. Specific examples are shown below.

  As the thermal polymerization initiator, organic peroxides, diazo compounds and the like can be preferably used. When the polymerization is to be performed efficiently in a short time, a compound having a decomposition half-life at 80 ° C. of 10 hours or less is preferable. Examples of the organic peroxide include diacyl peroxides such as acetyl peroxide, isobutyl peroxide, decanoyl peroxide, benzoyl peroxide, and succinic acid peroxide; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxide Peroxydicarbonates such as dicarbonate and diallylperoxydicarbonate; Peroxyesters such as tert-butylperoxyisobutyrate, tert-butylperoxyneodecanate, cumeneperoxyneodecanate; acetylcyclohexylsulfonyl Examples include peroxide sulfonates such as peroxides.

  As the diazo compound, 2,2′-azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (4-methoxy-2,4-dimethoxyvaleronitrile) And 2,2′-azobis (2-cyclopropylpropionitrile) and the like. In particular, benzoyl peroxide and 2,2′-azobisisobutyronitrile are more preferable. In addition, a redox initiator that initiates polymerization at around room temperature by combining an organic peroxide and a reducing agent such as a tertiary amine can also be used.

  The thermal polymerization initiator, the room temperature polymerization initiator, or the photopolymerization initiator may be used in combination.

(D) Stabilizer The component (D) can be used in the dental adhesive composition of the present invention as desired. Component (D) includes an ultraviolet absorber such as 2-hydroxy-4-methylbenzophenone, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,5-ditertiary butyl-4-methylphenol, a discoloration inhibitor, Components such as antibacterial materials, coloring pigments, and other conventionally known additives can be optionally added as necessary.

(E) Dye and / or Pigment If necessary, the (E) dye and / or pigment may be added to the dental adhesive composition of the present invention. Examples of such dyes and / or pigments include Phloxine BK, Acid Red, Fast Acid Magenta, Phloxine B, Fast Green FCF, Rhodamine B, Basic Fuchsin, Acid Fuchsin, Eosin, Ethithrosin, Safranine, Rose Bengal, Bemel, Gentian Purple, Examples include copper chlorophyll soda, laccaic acid, fluorescein sodium, cochineal and perilla, talc, titanium white and the like. These dyes and / or pigments can be used alone or in combination of two or more.

  In order to ensure the flexibility of the composition of the present invention, the breaking energy is preferably 35 (more preferably 65, still more preferably 85) mJ or more, and the elastic modulus is preferably 2.6 ( More preferably 1.7, still more preferably 1.2) GPa or less.

  In order for the composition of the present invention to be used as a rocking tooth fixing adhesive or the like, an effective adhesive strength to the tooth is required. Although it is not particularly limited, after immersion in water at 37 ° C. overnight (16 hours) or alternately in a water bath of 5 ° C. and 55 ° C. for 20 seconds each, repeated 5000 times (heat cycle), The tensile bond strength at a crosshead speed of 2 mm / miN is preferably 1 (more preferably 3, more preferably 6) MPa or more.

  Such a dental adhesive composition according to the present invention can be used as a fixing material used in a method for fixing a tooth that has been shaken due to periodontal disease or the like to an adjacent tooth (such a technique is referred to as a fixed tooth fixing method). It is. Such a fixing material can be applied to the fixed tooth fixation by a known method, and for example, a writing method or the like can be adopted. In the brush stacking method, a ball-shaped resin mud is produced by including the fixing material according to the present invention in a small brush, and this resin mud is used as an adhesive material by placing it on the adherend surface or where the resin mud is to be built. It has the advantage that the bonding operation can be completed easily and in a short time.

〔Example〕
Next, the dental adhesive composition of the present invention will be specifically described in Examples, but the present invention is not limited to these Examples. Abbreviations are as follows:
UDMA: Di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate (Shin Nakamura Chemical Co., Ltd.)
2.6E: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (the average number of ethoxy groups is 2.6) (Shin Nakamura Chemical Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.)
MDP: 10-methacryloyloxydecyl dihydrogen phosphate (Wako Pure Chemical Industries, Ltd.)
4-MET: 4- (Meth) acryloyloxyethyl trimellitic acid (Sun Medical Co., Ltd.)
JB-800T: Product name Art pearl, crosslinkable polyurethane powder (6 μm, refractive index: 1.49 ultra soft grade, 10% micro compressive strength 1.56 MPa Negami Industrial Co., Ltd.)
P-800T: Product name Art pearl, crosslinkable polyurethane powder (6 μm, refractive index: 1.53 soft grade, 10% fine compression strength 1.80 MPa Negami Industrial Co., Ltd.)
C-800: Product name Art pearl, crosslinkable polyurethane powder (6 μm, refractive index: 1.51 standard grade, 10% compression reaction force 2 MPa, 30% compression reaction force 5.2 MPa, Negami Industrial Co., Ltd.)
RT-600T: Product name Art pearl, crosslinkable polyurethane powder (10 μm, refractive index: 1.52, hard grade, double bond equivalent 2900, Negami Industrial Co., Ltd.)
RZ-600T: Product name Art pearl, crosslinkable polyurethane powder (10 μm, refractive index: 1.54 soft grade, double bond equivalent 600-700, 10% micro compressive strength 5.30 MPa Negami Industrial Co., Ltd.)
RW-600T: Product name Art pearl, crosslinkable polyurethane powder (10 μm, refractive index: 1.51 soft grade, double bond equivalent 2900, 10% fine compression strength 2.01 MPa, Negami Industrial Co., Ltd.)
M-4003: Product name High Pearl, PMMA powder (10% fine compression strength 27.40 MPa Negami Industrial Co., Ltd.)
2000B: Product name Tospearl, silicone powder (6 μm, Tanac Co., Ltd.)
MBP-8: Product name Techpolymer, cross-linked polymethyl methacrylate powder (8 μm, 10% micro compression strength 30.60 MPa high pore volume grade, Sekisui Chemical Co., Ltd.)
ARX-15: Product name Techpolymer, cross-linked polymethacrylic acid ester powder (15 μm, rubber elastic grade, Sekisui Chemical Co., Ltd.)
W-450A: Product name: Metablene, polymethyl methacrylate / acrylic rubber core shell polymer powder (Mitsubishi Rayon Co., Ltd.)
HE-3040: Product name Flow beads, polyethylene powder (12 μm, Sumitomo Seika Co., Ltd.)
CQ: Camphorquinone (Wako Pure Chemical Industries, Ltd.)
DTMPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Sigma Aldrich Japan Co., Ltd.)
DMABA-BE: 4- (dimethylamino) benzoic acid 2-butoxyethyl (Tokyo Chemical Industry Co., Ltd.)
MEHQ: 4-methoxyphenol (Wako Pure Chemical Industries, Ltd.)
BHT: Dibutylhydroxytoluene (Tokyo Chemical Industry Co., Ltd.)

"Solubility test"
After adding 1 g of filler and 20 g of acetone to a 30 mL glass bottle and stirring for 24 hours at room temperature, the solid matter was collected by filtration, washed with 10 g of acetone, dried at 60 ° C. for 4 hours under reduced pressure, and the weight was measured. .
The ratio of the solid content remaining without being dissolved (the weight of the remaining solid content after immersion after drying of the solvent / the weight before immersion) was defined as the insoluble content of acetone. The results are shown in Table 1.

  Table 2 shows the composition of the dental adhesive compositions used in Examples 1 to 10 and Comparative Examples 1 to 7. In Comparative Example 1, a commercially available rocking tooth fixing adhesive (G-Fix, GC Corporation) was used according to the product instruction manual. Moreover, the composition except the filler which expresses the softness | flexibility mix | blended with Examples 1-10 was used for the comparative example 2. FIG.

"3-point bending test"
In the dental adhesive composition of the present invention, it is desired that the cured body that has been polymerized and reacted with the tooth has excellent toughness against external stress. Therefore, since it was considered that the fracture energy and the elastic modulus were more important than the maximum point stress obtained from the test results, the fracture energy was 48 to 110 mJ and the elastic modulus was 0.9 to 2 GPa.

Examples 1 to 10 and Comparative Examples 1 to 5 were filled in a 2 × 2 × 25 mm mold, and then pressed with a polypropylene film and a glass plate, and irradiated with light (Alphalite II, Morita Co., Ltd.) for 180 seconds. A cured product for a point bending test was obtained and immersed in water at 37 ° C. overnight. After being immersed overnight, this cured body was subjected to a three-point bending test at a crosshead speed of 1.0 mm / min using a precision universal testing machine (Autograph AG-IS, Shimadzu Corporation). (N = 10)
Table 2 shows the rupture energy, maximum point stress, and elastic modulus of each of Examples 1 to 10 and Comparative Examples 1 to 5.

"Repeated bending test"
In the dental adhesive composition of the present invention, it is desired that the cured product that has been polymerized and reacted with the tooth has excellent toughness and durability against external stress. Therefore, the three-point bending test was repeated 10 times with the same test piece, and it was determined that it did not break more than 3 times. Examples 1 to 10 and Comparative Examples 1 to 5 were filled in a 2 × 2 × 25 mm mold, and then pressed with a polypropylene film and a glass plate, and irradiated with light (Alphalite II, Morita Co., Ltd.) for 180 seconds. A cured product for a point bending test was obtained and immersed in water at 37 ° C. overnight. After immersion overnight, this cured product was subjected to the same 3-point bending test at a crosshead speed of 1.0 mm / min and a stroke length of 3.0 mm using a precision universal testing machine (Autograph AG-IS, Shimadzu Corporation). The test was repeated 10 times on a piece, and the resistance to repeated bending test was determined by the number of times of bending test.
Table 2 shows the maximum point stress, elastic modulus, and resistance to repeated bending test during each repeated bending test of Examples 1 to 10 and Comparative Examples 1 to 5.

"Tensile adhesion test"
Polish the bovine mandibular teeth with water # 180 emery paper under water injection, scrape the flat enamel surface for adhesion, wash with water and dry, then apply etching material (high viscosity red / manufactured by Sun Medical Co., Ltd.) to the tooth surface. After 30 seconds, it was washed with water and dried. The surface was masked with an adhesive tape to define a circular adhesive area with a diameter of 4.8 mm. Then, after applying the paste mixed using each composition of the example to the adhesive tooth surface and irradiating with LED light with PENCURE 2000 for 10 seconds and curing, the acrylic rod was made by Super Bond (manufactured by Sun Medical Co., Ltd.). ) And planted in pressure contact. The composition of Comparative Example 1 was used in accordance with the product instruction manual. The cured sample was immersed in water overnight at 37 ° C., or alternately immersed in a water bath at 5 ° C. and 55 ° C. for 20 seconds for 5000 seconds each (heat cycle), then Autograph AG-IS (Shimadzu Corporation) ) Was used to evaluate the tensile bond strength at a crosshead speed of 2 mm / min. (N = 10)
Table 3 shows the tensile bond strengths of Examples 4 and 5 and Comparative Example 1.

[result]
From Table 2, it was found that Comparative Examples 1 to 5 and 7 deviated from the set range. Further, in Comparative Example 6, the operability was remarkably deteriorated due to the filler being dissolved in the monomer. From this, the dental adhesive composition of the present invention has a resistance to repeated bending tests in a range that cannot be achieved with commercially available swaying tooth fixing adhesives. It was found that the toughness of the cured product was greatly affected.
In the dental adhesive composition of the present invention, the cured body after the polymerization reaction has excellent toughness with respect to external stress, so that it is possible to expect a smooth treatment of oscillating teeth.

Claims (15)

  A dental adhesive composition comprising a polymerizable monomer (A), wherein the composition obtained by polymerizing the polymerizable monomer (A) has a repeated bending test resistance of 3 times or more. Sex composition.   The dental adhesive composition according to claim 1, comprising a filler (B) that exhibits flexibility.   The dental adhesive composition according to claim 2, wherein the filler (B) exhibiting flexibility has a reaction force of 25 MPa or less when compressed by 10%.   When the filler (B) exhibiting flexibility is immersed in acetone at room temperature for 24 hours, the ratio of the solid content that remains without being dissolved (the weight of the residual solid content after solvent drying after immersion / before immersion) The dental adhesive composition according to claim 2 or 3, wherein the weight) is 30% by weight or more.   The dental adhesive composition according to any one of claims 2 to 4, wherein the filler (B) exhibiting flexibility includes a crosslinked polymer.   The dental adhesive composition according to any one of claims 2 to 5, wherein the filler (B) exhibiting flexibility includes an ethylenic double bond or an isocyanate group.   The dental adhesive composition according to any one of claims 2 to 6, wherein the filler (B) exhibiting flexibility includes a carboxylic acid group, a phosphoric acid group, an amino group, and a hydroxyl group.   The dental adhesive composition according to any one of claims 2 to 7, wherein the filler (B) exhibiting flexibility contains a urethane polymer.   The dental adhesive composition according to any one of claims 1 to 8, wherein the polymerizable monomer (A) contains a urethane monomer (A1).   The dental adhesive composition according to claim 1, wherein the polymerizable monomer (A) includes a polyfunctional monomer (A2).   The dental adhesive composition according to any one of claims 1 to 10, wherein the polymerizable monomer (A) contains an acidic group-containing monomer (A3).   The dental adhesive composition according to claim 11, wherein the monomer (A3) having an acidic group is a carboxylic acid, phosphoric acid, and / or sulfonic acid monomer.   Furthermore, the polymerization initiator (C) is contained, The dental adhesive composition in any one of Claims 1-12 characterized by the above-mentioned.   The dental adhesive composition according to claim 13, wherein the polymerization initiator is a photopolymerization initiator (C2).   The rocking tooth fixing material which consists of a dental adhesive composition in any one of Claims 1-14.