JP2012012333A - Coating material kit for resin tooth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material kit for a resin tooth, which is excellent in adhesion to a resin tooth, and with which a hard coat layer having outstanding abrasion resistance is formed.SOLUTION: The coating material kit for a resin tooth at least includes: a primer including (a) a polyurethane resin and (b) a solvent or a dispersion medium; and a coating material including (i) an organosilicon compound which has a reactive organic functional group and which can conduct polycondensation, (ii) a catalyst for polycondensation of the organosilicon compound, and (iii) an organic solvent.

Description

  The present invention relates to a resin tooth coating material kit.

  In the field of dental treatment in recent years, organic dental resins are frequently used as materials for restorations and fillings of living tissue and general dentures and denture bases. When dental treatment is performed using this dental resin material, at least a part of the surface of the dental resin material is exposed in the oral cavity. For this reason, a polishing operation is required so that the surface of the dental resin material has a prescribed finishing condition. However, dental resin is a material that is difficult to finish and so far, various techniques for treating the surface of the dental resin with a coating material have been proposed in order to achieve an efficient polishing operation. .

  Therefore, a proposal has been put into practical use in which a coating layer is provided on the surface of a dental resin using an organic resin coating material such as a melamine resin, an acrylic resin, or a silicone resin. Although this method can provide good gloss with a simple operation, the coating layer made of only the resin as described above has a problem that it is inferior in wear because of insufficient hardness.

  In order to solve the above-mentioned problem, a technique capable of forming a hard coat layer made of various inorganic materials has been developed. As an example, a technique for forming a hard coat layer made of amorphous carbon having properties close to diamond on the surface of an artificial tooth made of dental resin has been proposed (see, for example, Patent Document 1).

JP 2005-168936 A (Claims)

  However, the artificial tooth made of a dental resin covered with the inorganic amorphous carbon hard coat layer disclosed in Patent Document 1 has the following problems. The artificial tooth made of a dental resin covered with such an inorganic amorphous carbon hard coat layer has a certain degree of wear resistance compared to the resin artificial tooth covered with an organic resin coating layer. However, the adhesiveness of the hard coat layer to the resin tooth surface is low because the material forming the inorganic hard coat layer is hard and brittle. For this reason, a hard-coat layer will peel easily. As a result, it is difficult to drastically improve the wear resistance of the resin tooth surface.

  The present invention has been made in order to solve the above-described problems, and the object thereof is to form a hard coat layer having excellent adhesion to resin teeth and having excellent wear resistance. An object of the present invention is to provide a resin tooth coating material kit.

The above-mentioned subject is achieved by the following present invention. That is,
The resin tooth coating material kit of the present invention comprises (a) a polyurethane resin and (b) a primer containing a solvent or a dispersion medium, (i) a polycondensable organosilicon compound having a reactive organic functional group, (ii) A catalyst for polycondensation of the organosilicon compound, and (iii) a coating material containing an organic solvent.

  In one embodiment of the resin tooth coating material kit of the present invention, (a) the glass transition point of the polyurethane resin is preferably less than 37 ° C.

  In another embodiment of the resin tooth coating material kit of the present invention, (a) the polyurethane resin is preferably composed of a hard segment and a soft segment, and the soft segment is preferably derived from a polycarbonate skeleton.

  In another embodiment of the resin tooth coating material kit of the present invention, (a) the polyurethane resin is preferably an anionic water-dispersed polyurethane resin.

  In another embodiment of the resin tooth coating material kit of the present invention, (i) the organosilicon compound includes, as a reactive organic functional group, a (meth) acryloyloxy group, an amino group, an epoxy group, and a glycidoxy group. It preferably contains at least one reactive organic functional group selected.

  Another embodiment of the resin tooth coating material kit of the present invention is preferably a resin tooth coating material kit used for an inorganic filler-containing resin tooth.

  ADVANTAGE OF THE INVENTION According to this invention, the coating kit for resin teeth which can form the hard-coat layer which is excellent in the adhesiveness with respect to a resin tooth and has the outstanding abrasion resistance can be provided.

  Hereinafter, preferred embodiments of the resin tooth coating material kit according to the present invention will be described. However, the present invention is not limited to the embodiments described below.

(Resin tooth coating material kit)
The resin tooth coating material kit of this embodiment includes (a) a polyurethane resin, (b) a primer containing a solvent or a dispersion medium, (i) a polycondensable organosilicon compound having a reactive organic functional group, (ii) A catalyst for polycondensation of the organosilicon compound, and (iii) a coating material containing an organic solvent.

  Here, when the coating process is performed on the surface of the resin tooth using the resin tooth coating material kit of the present embodiment, the coating process is performed in the following procedure. First, a primer layer is formed by applying and curing a primer on the surface of the resin tooth (primer layer forming step). Next, a coating material is applied and cured on the primer layer to form a hard coat layer (hard coat layer forming step). The primer layer and the hard coat layer are laminated on the surface of the resin tooth in the above order, and the coating process is completed.

  The outermost surface of the resin tooth coated as described above is covered with a hard coat layer in which polysiloxane bonds are formed in the matrix by polycondensation of the organosilicon compound which is the main component of the coating material. Therefore, the coated resin teeth have excellent wear resistance.

  Furthermore, the resin teeth subjected to the coating treatment have the merits described below. That is, in this case, a primer layer mainly composed of a polyurethane resin exists between the hard coat layer and the resin tooth surface. And since both the resin tooth surface and a primer layer are substantially comprised from the resin component, affinity is high. Therefore, since the primer layer functions as an adhesive improvement and a buffer material, the hard coat layer has high adhesion to the resin tooth surface through the primer layer. Therefore, if the resin tooth surface is coated using the resin tooth coating material kit of the present embodiment, a hard coat layer having excellent adhesion to the resin teeth and excellent wear resistance can be formed.

  The resin tooth coated by the resin tooth coating material kit of this embodiment is a crown restoration / filling material and denture material made of a resin material. Specifically, for example, it is more than an artificial artificial tooth such as an acrylic resin tooth or a hard resin tooth containing about 20 to 50 wt% of inorganic fine powder, or a hard resin or hard resin containing about 50 to 70 wt% of inorganic particles. Further, crown restoration materials such as a hybrid type hard resin or composite resin that increase the inorganic particle content can be used, and there is no particular limitation as long as it is a known resin tooth.

  The resin tooth coating material kit of the present embodiment exhibits excellent adhesion and wear resistance, particularly with respect to hard resins and hybrid hard resins containing inorganic particles. This is presumably because polar groups such as urethane bonds show high affinity to the highly hydrophilic inorganic particles exposed from the resin surface due to the effect of hydrogen bonding. That is, silica is generally used as the inorganic particles for dental materials, and the silanol group present on the surface of the silica has a high affinity for urethane bonds. Also, the surface of silica is usually used after being surface-treated with a silane coupling material, but it is difficult to completely treat the surface, and the silanol surface remains, or the surface of the excess silane coupling material becomes an oligomer. It is thought that it works favorably for adhesion by adsorbing to the surface.

  When applying the resin tooth coating material kit of this embodiment to a resin tooth, it is preferable to pre-treat the surface of the resin tooth by an appropriate method for the purpose of improving adhesion before the application. Pretreatment achieves the objectives such as elimination of inhibitors that adhere the resin tooth surface and primer layer, strengthening the fitting force by roughening the resin tooth surface, and generating functional groups on the surface of the resin tooth To be done. The pretreatment method is not particularly limited as long as it is a known pretreatment method. Specific examples include (1) degreasing treatment with an organic solvent, (2) a base such as a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution. (3) Polishing treatment using a polishing agent, (4) Plasma treatment using atmospheric pressure plasma and low-pressure plasma, (5) Corona discharge treatment, (6 ) Flame treatment or (7) UV ozone treatment. Among these pretreatments, from the viewpoint of adhesion between the resin surface and the primer layer, it is preferable to perform a degreasing treatment with an organic solvent, a chemical treatment with an alkali, a plasma treatment, a corona discharge treatment, or a combination thereof. is there.

  Next, the detail of each component which comprises the primer and coating material which are contained in the resin tooth coating material kit of this embodiment is demonstrated.

<Primer>
The primer includes (a) a polyurethane resin and (b) a solvent or a dispersion medium. Details of each component will be described below.

(A) Polyurethane resin In the present embodiment, the polyurethane resin is a generic term for polymers having a plurality of urethane bonds in the main chain, and is usually obtained by a reaction between a compound having a plurality of isocyanate groups in the molecule and a polyol. It is done. In addition to the urethane bond, the molecule may have a structure such as urea, carbamic acid, amine, amide, allophanate, biuret, carbodiimide, uretonimine, uretdione, or isocyanurate.

  Examples of compounds having an isocyanate group that can be suitably used as a raw material for polyurethane resins include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, toluidine diisocyanate, phenylene diisocyanate, 4,4- Aromatic isocyanate compounds such as diphenyl diisocyanate, dianisidine diisocyanate, 4,4-diphenyl ether diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate; trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate , Hydrogenated 4,4-diphe Lmethane diisocyanate, hydrogenated xylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate Aliphatic isocyanate compounds such as isocyanate and bicycloheptanetriisocyanate; polycyclic compounds obtained by bonding these aromatic isocyanate compounds and / or aliphatic isocyanate compounds and compounds having active hydrogen by various methods at a charging ratio such that isocyanate groups remain. An isocyanate compound, a polyisocyanate oligomer compound, etc. are mentioned. These polyisocyanate compounds may contain one or two or more sulfur atoms or halogen atoms in the molecule, and further include modified products of the above polyisocyanates, burettes, isocyanurates, allophanates, carbodiimides, and the like. Also good.

  The polyol that can be suitably used as a raw material for the polyurethane resin may be a low molecular weight polyol, but in view of the reaction rate with the isocyanate group, a high molecular weight polyol is particularly preferable. Here, the polymer polyol corresponds to a polymer having a weight average molecular weight of 500 or more, more preferably 500 to 3000. Further, the number of hydroxyl groups contained in the polyol is preferably 2 to 6 and particularly preferably 2 to 4 from the viewpoint of maintaining good physical properties of the primer film. In addition to the polyol, a compound having an amino group or mercapto group, which is an active hydrogen group as well as a hydroxyl group, may be partially used as a raw material for the polyurethane resin to be reacted with the compound having an isocyanate group. .

  Examples of the polymer polyol include polyester polyol, polyether polyol, polyether ester polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, polyurethane polyol or a mixture thereof, or silicone polyol.

  Specific examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol. , Neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, and other glycols Polyols obtained by reacting with a mixture thereof or a mixture thereof, such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) And polyester polyols obtained by ring-opening polymerization of lactones.

  Specific examples of polyether polyols include, for example, water, ethylene glycol, propylene glycol, trimethylol propane, glycerin and other low molecular weight polyols as initiators, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and other oxirane compounds. Examples include polyether polyols obtained by polymerization.

  As specific examples of the polyether ester polyol, for example, a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or a dialkyl ester thereof or a mixture thereof is reacted with the above polyether polyol. Examples include polyether ester polyols obtained.

  As a specific example of the polyesteramide polyol, in the above polyesterification reaction, for example, an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine, or the like as a raw material is added to the raw material of the polyesterification reaction product and reacted. And the like obtained by.

  Specific examples of the acrylic polyol include polymerizable monomers having one or more hydroxyl groups in one molecule, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or the corresponding methacrylic acid derivatives thereof. Examples thereof include those obtained by copolymerizing acrylic acid, methacrylic acid or esters thereof.

  Specific examples of the polycarbonate polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1,5. -Pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol-A and hydrogenated bisphenol Examples thereof include those obtained by reacting one or more glycols selected from the group consisting of -A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like.

  Specific examples of the polyhydroxyalkane include isoprene, butadiene, or liquid rubber obtained by copolymerizing butadiene and acrylamide.

  Specific examples of the polyurethane polyol include, for example, a polyol having a urethane bond in one molecule.

  Further, a low molecular weight polyol may be mixed in addition to the above polymer polyol. Specific examples of these low molecular weight polyols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonane. Diols, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycols used in the production of polyester polyols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, Examples include methylolpropane and pentaerythritol. Furthermore, monools such as methanol, ethanol, propanols, butanols, 2-ethylhexanol, lauryl alcohol, stearyl alcohol can be used in combination.

  The polyurethane resin (a) in the present embodiment is preferably a thermoplastic polyurethane elastomer. As the thermoplastic polyurethane elastomer, those having an elongation measured in accordance with JISK7311 of 100% or more, more preferably 350 to 800% are used. Such a thermoplastic polyurethane elastomer is usually composed of a hard segment which is a crystalline cohesive component composed of urethane bonds and a soft segment which is an amorphous component composed of the above-described polymer polyol. . Such a thermoplastic polyurethane elastomer can change various physical properties by the balance of segmentation of a hard segment and a soft segment. By the presence of such a primer layer mainly composed of a thermoplastic polyurethane elastomer, the adhesion to a coating material described later can be further improved.

  Moreover, in this Embodiment, it is preferable to employ | adopt (a) polyurethane resin whose glass transition point (Tg) is less than 37 degree | times. The primer layer formed from such a polyurethane resin not only has high adhesion to the base material of the resin teeth, but also has flexibility in the oral environment and can enhance the action of buffering external impacts. it can. Also, a glass transition point (Tg) that is too low can adversely affect durability. For this reason, the (a) polyurethane resin having a glass transition point (Tg) in the range of −50 to 10 degrees is more preferable, and the (a) polyurethane resin having a glass transition point (Tg) in the range of −30 to −20 degrees. Is most preferred. The glass transition point (Tg) can be obtained from the tan δ peak temperature in the dynamic viscoelasticity measurement.

  Moreover, in this Embodiment, it is preferable that the soft segment which comprises (a) polyurethane resin originates in a polycarbonate polyol frame | skeleton. When such a polyurethane resin is employed, the adhesion to the coating material described later can be improved due to the large number of functional groups involved in hydrogen bonding, and the hydrolysis resistance of the formed primer layer can be improved. It can also improve the performance. Furthermore, when (a) the polyurethane resin has a skeleton derived from polycarbonate polyol, the glass transition point (Tg) can be easily within the above range.

  (A) Since the polyurethane resin itself is a high-viscosity resin, it is usually used by dissolving in a solvent or dispersing in a dispersion medium from the viewpoint of operability. However, from the viewpoint of environmental protection and safety, an aqueous dispersion system in which (a) the polyurethane resin is uniformly dispersed in water is preferable. In the case of an aqueous dispersion, since a uniform coating film can be formed, it is preferable that the dispersed particle size is small. Specifically, the average particle size of the dispersed particles is preferably 0.1 μm or less, and 0.05 μm or less. Particularly preferred. Further, the content of the (a) polyurethane resin in the primer is not particularly limited, but is 2 to 100 parts by mass, more preferably 10 to 45 parts by mass with respect to 100 parts by mass of the solvent or dispersion medium. preferable.

  Examples of water dispersion methods include forced emulsification type, self-emulsification type, and water-solubilization type, but good coating properties (small dispersion particle size) and easy control of coating thickness (thin film coating possible) ) And water resistance (long-term durability in the oral cavity) are preferred.

  (A) In order to use the polyurethane resin as a self-emulsifying type, it is preferable that the polyurethane resin has a group or an atomic group having a surface active action introduced therein to enhance its emulsifiability. Here, the group or atomic group having a surface active action is a group or atomic group having a high affinity for water, and is particularly limited as long as it is a group or atomic group capable of emulsifying the polyurethane resin in water. Although not preferred, preferred groups or atomic groups include anionic interfaces such as sulfonyl groups, carboxyl groups, or structures (atomic groups) in which they are alkali metal salts, alkylamine salts, or amine salts. A group or an atomic group having an active action; a group having a nonionic surface active action such as a hydroxyl group or a polyalkylene glycol group; an amino group or an alkylamino group, or a structure in which they are sulfonates or alkylsulfonates ( And a group or an atomic group having a cationic surface active action such as an atomic group). Among them, the anionic surface active action is achieved because of the ease of reducing the dispersed particle size, the high hydrophilicity, the high stability of the emulsion and the durability of the final product. A group or an atomic group having an alkylamine salt of a carboxylic acid is preferably introduced into the polyurethane resin structure (a).

(B) Solvent or Dispersion Medium Usually, water or an organic solvent is used for the primer as a solvent or dispersion medium for uniformly dissolving or dispersing (a) the polyurethane resin. Here, as water, distilled water or deionized water that does not substantially contain impurities harmful to storage stability and medical components is preferably used. The organic solvent is preferably volatile. The volatile organic solvent means an organic solvent having volatility at normal temperature. Here, the “volatile” means that the boiling point at 760 mmHg (101.32 KPa) is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. In addition, when adjusting a primer, when water is contained, when using a volatile organic solvent as a solvent or a dispersion medium, it is suitable for the said volatile organic solvent to show water solubility. This is because compatibility with water can be ensured. Here, “water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 ml or more. Examples of the volatile organic solvent include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, and the like. A plurality of these volatile organic solvents can be used as needed. Considering toxicity to the living body, ethanol, isopropyl alcohol and acetone are preferable as the volatile organic solvent. The blending amount of the solvent or the dispersion medium is not particularly limited as long as (a) the uniformity of the polyurethane resin can be secured when adjusting the primer.

  In addition, the primer of the present invention may contain other components as long as the effects of the present invention are not significantly inhibited. Examples of other components include fillers such as inorganic fine particles, resins other than polyurethane resins, surfactants, antioxidants and the like.

<Coating material>
The coating material contains at least (i) a polycondensable organosilicon compound having a reactive organic functional group, (ii) a catalyst for polycondensation of the organosilicon compound, and (iii) an organic solvent. In addition to these components, (v) other components such as (i ′) a polycondensable organosilicon compound having no reactive organic functional group and (iv) an inorganic oxide sol are included as necessary. It may be.

(I) Organosilicon compound capable of polycondensation As the coating material, (i) a polycondensable organosilicon compound having a reactive organic functional group is used, but if necessary, (i ′) a reactive organic functional group. A polycondensable organosilicon compound having no group can also be used in combination. Both (i) a polycondensable organosilicon compound having a reactive organic functional group and (i ′) a polycondensable organosilicon compound having no reactive organic functional group (I) an organosilicon capable of polycondensation Collectively referred to as a compound. Here, from the viewpoint of ensuring the hardness of the hard coat layer, the blending ratio of the organosilicon compound capable of polycondensation (I) contained in the coating material (that is, the sum of components (i) and (i ′)) is: 30 mass parts or more are preferable with respect to 100 mass parts of hard coat layers finally formed, the range of 30-80 mass parts is more preferable, and the range of 35-65 mass parts is further more preferable. By setting the blending amount of the organosilicon compound capable of polycondensation to 30 parts by mass or more, the occurrence of cracks in the hard coat layer can be reliably suppressed.

  Further, the blending ratio of (i) the polycondensable organosilicon compound having a reactive organic functional group contained in the coating material is preferably 30 parts by mass or more with respect to 100 parts by mass of the finally formed hard coat layer. The range of 30-80 mass parts is preferable, and the range of 30-60 mass parts is more preferable. By setting the blending ratio to 30 parts by mass or more, the reactive organic functional group and the silanol group of the organosilicon compound or the silanol group generated by hydrolyzing the organosilicon compound react to crosslink the hard coat layer. The density can be increased. In addition, the presence of the reactive organic functional group moderately moderates the stiffening caused by polycondensation of the organosilicon compound, imparts an appropriate elasticity to the hard coat layer, and can suppress the occurrence of cracks in the hard coat layer. Moreover, since the content rate of the reactive organic functional group which reduces the hardness of a hard-coat layer can be moderately suppressed by making a compounding ratio into 79.5 mass parts or less, the outstanding abrasion resistance can be ensured.

  The (I) polycondensable organosilicon compound used for the coating material is a known organosilicon compound used for forming a hard coat layer, particularly a hard coat layer for the purpose of ensuring abrasion resistance and scratch resistance. Available without restrictions. As such an organosilicon compound, usually, an organosilicon compound having a silanol group and various alkoxysilanes that hydrolyze to produce a silanol group can be used.

  In the present specification, as the “reactive organic functional group”, a reactive group that causes a chemical bond with a silanol group can be suitably employed. Specifically, electrophilic functional groups such as isocyanate groups such as epoxy groups, glycidoxy groups, oxetane groups; basic functional groups such as amino groups and quaternary ammonium salts; (meth) acryloyloxy groups, allyl groups, ethynyls And a functional group having an unsaturated hydrocarbon group formed by an addition reaction, such as a group, a vinyl group, a styryl group, and an allyloxy group. Among these, a (meth) acryloyloxy group, an amino group, an epoxy group, and a glycidoxy group are preferable from the viewpoint of reactivity with a silanol group and storage stability. Furthermore, among the reactive organic functional groups, an amino group is most preferable because it causes dehydration condensation and forms an amide bond having a high binding strength. Further, when the reactive organic functional group is the unsaturated hydrocarbon group, the polymerization reaction of the unsaturated hydrocarbon group is also performed, so that the crosslink density of the hard coat layer can be further increased.

  Examples of such (i) polycondensable organosilicon compounds having a reactive organic functional group include compounds represented by the following general formula (1), and those obtained by partially or fully hydrolyzing these compounds: Alternatively, a partially condensed product is preferably used.

General formula: (1) R ¹ R ² _a Si (OR ³ ) _(3-a)

In the formula, R ¹ and R ² may each independently have a substituent, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or An aryl group having 5 to 20 carbon atoms, at least one of R ¹ and R ^{2 has} a reactive organic functional group as a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; And a and b are integers of 0 or 1.

Incidentally, ^{R 1} and ^{R 2} in the general formula (1) may have each independently substituent, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, carbon atoms 2 -20 alkenyl group or aryl group having 5 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, hexyl Group, heptyl group, octyl group, decyl group, dodecyl group, octadecyl group, octenyl group, dococenyl group and other alkyl groups; cyclobutyl group, cyclohexyl group, cyclopentyl group and other cycloalkyl groups; propenyl group, 1-butenyl group, etc. An alkenyl group; aryl groups such as a phenyl group, a benzyl group, and a naphthyl group can be exemplified. Examples of these substituents include halogen atoms such as fluorine, chlorine and bromine; alkyl groups such as methyl and ethyl; methoxy, hydroxyl, aldehyde, cyano, mercapto and the above-mentioned reactive organics. Mention may be made of functional groups.

R ³ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include an n-butyl group, a t-butyl group, a pentyl group, and a hexyl group.

  In general formula (1), a is an integer of 0 or 1, but a is preferably 0 from the viewpoint of obtaining a hard coating layer with high hardness.

  Specific examples of the organosilicon compound represented by the general formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltri (β-methoxy-ethoxy) silane, allyltrimethoxysilane, γ-acrylic. Roxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-2 (aminoethyl) 3-aminopropyl Propyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, p-styryltrimethoxysilane, 3-isocyanatopropyltriethoxysilane , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy And cyclohexyl) ethyltrimethoxysilane and those partially or fully hydrolyzed or partially condensed.

From the viewpoint of improving adhesion to the primer layer, strain resistance, or crosslinking density, at least one of R ¹ and R ² is a (meth) acryloyloxy group, amino group, epoxy group, as a reactive organic functional group. And organosilicon compounds having groups selected from glycidoxy groups are preferred. These organosilicon compounds may be used alone or in combination of two or more.

  In addition, (i) a polycondensable organosilicon compound having a reactive organic functional group, in addition to the compound represented by the above general formula (1) and derivatives thereof, a compound represented by the following general formula (2), In addition, in these compounds, it is also preferable to use a partially or fully hydrolyzed or partially condensed product.

General _{^{formula: (2) X {SiR 4}} c (OR 5) 3-c} 2

In the formula, each R ⁴ may independently have a substituent, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 5 carbon atoms. An aryl group having ˜20, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X is a divalent organic residue or an oxygen atom, and at least one selected from R ⁴ and X is It has a reactive organic functional group as a substituent, and c is an integer of 0-2.

As R ⁴ in the general formula (2), the same groups as those described as R ¹ and R ² in the general formula (1) can be preferably used. In addition, as R ⁵ in the general formula (2), the same groups as those described as R ^{3 in the} general formula (1) can be preferably used.

  X in the general formula (2) is a divalent organic residue or an oxygen atom. The structure of the organic residue is not particularly limited, and can be used without any limitation as long as it is a group capable of bonding two silicon atoms having one or more alkoxy groups. The structure may have bonds other than carbon-carbon bonds such as ether bond, ester bond, amide bond, amino bond, urethane bond, thioether bond, sulfonyl bond, and oxa group (ketone carbon). May be included.

  Specific examples of the divalent organic residue represented by X include alkylene groups having 1 to 15 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and a butylene group; or a group represented by the following chemical formula ( However, in the following chemical formula, m, n and l are each an integer of 0 to 10), and these groups include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group and the like Alkyl groups; methoxy groups, hydroxyl groups, aldehyde groups, cyano groups, mercapto groups, groups substituted with the above-described reactive organic functional groups, and the like can be exemplified.

  In addition, although c in General formula (2) is an integer of 0-2, it is preferable that it is 0 or 1 from a viewpoint of obtaining a hard-coat layer with high hardness.

  In the resin tooth coating material kit of this embodiment, in addition to (i) a polycondensable organosilicon compound having a reactive organic functional group, (i ′) an organosilicon compound having no reactive organic functional group is used. Can be added. For example, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, n- Propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexylmethyldimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldimethoxysilane, n-octyldimethylmethoxysilane, n-octylmethyldiethoxysilane, n- Siltrimethoxysilane, n-decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, n-octadecyltrimethoxysilane, n -Octadecyltriethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecylmethyldiethoxysilane, n-octadecyldimethylmethoxysilane, isooctyltrimethoxysilane, 7-octenyltrimethoxysilane, triethoxysilylundecanal, trifluoro Propyltrimethoxysilane, perfluorooctylethyltriethoxysilane, γ-chloropropyltrimethoxysilane, and some or all of them hydrolyzed or partially condensed Things.

  In the resin tooth coating material kit of this embodiment, (i) a polycondensable organosilicon compound having a reactive organic functional group having an epoxy group and a glycidoxy group as the reactive organic functional group When is used, another epoxy compound may be used in combination from the viewpoint of increasing the crosslink density of the hard coat layer. As such an epoxy compound, a known epoxy compound can be used without any limitation. The epoxy compound here refers to a compound having an epoxy group without having a silanol group or an alkoxyl group unlike a polycondensable organosilicon compound having a reactive organic functional group. Specific examples of the epoxy compound include 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and the like. These epoxy compounds may be used in combination of two or more.

  In the resin tooth coating material kit of the present embodiment, (i) the reactive organic functional group of the polycondensable organosilicon compound having a reactive organic functional group is a (meth) acryloyloxy group or an allyl group. In the case of using a polycondensable organosilicon compound having a functional group having an unsaturated hydrocarbon such as ethynyl group, vinyl group, styryl group, etc., from the viewpoint of increasing the crosslink density of the hard coat layer, other radical polymerizable monomers are used. A monomer may be used in combination. As such radically polymerizable monomer, known ones can be used without any limitation, but (meth) acrylate-based monomers are preferred.

(Ii) Catalyst for polycondensation of organosilicon compound In the resin tooth coating material kit of this embodiment, (I) for the purpose of accelerating the polymerization of an organosilicon compound capable of polycondensation, the coating of the organosilicon compound in the coating material is performed. A condensation catalyst is added. Examples of the catalyst include (I) alkali metal alkoxide, acid, basic compound, perchlorate, acetylacetonate complex having a function of hydrolyzing and condensing an alkoxysilyl group contained in a polycondensable organosilicon compound. Any known compounds such as organic metal salts can be used without any limitation.

Here, as the alkali metal alkoxide, those represented by the following general formula (3) are preferably used.

General formula: (3) M ¹ OR ⁷
(M ¹ : alkali metal, R ⁷ : alkyl group)

Here, in the general formula (3), a known alkali metal can be used as M ¹ , and lithium and sodium are particularly preferable. The alkyl group represented by R ^7, preferably an alkyl group having from 1 to 10 carbon atoms, in particular methoxide, ethoxide is preferred. Specific examples of the alkali metal alkoxide represented by the general formula (4) include lithium methoxide and lithium ethoxide. Since the alkali metal alkoxide represented by the general formula (3) is a solid, it is preferable to use it by dissolving an alkali metal alkoxide such as methanol in a solvent capable of dissolving it when preparing the coating material. At this time, the solvent can be appropriately selected as long as it becomes a co-solvent.

Acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acids having a carboxyl group such as acetic acid and propionic acid, or cupric chloride, aluminum chloride, ferric chloride, titanium chloride, and chloride. Examples include Lewis acids such as zinc and antimony chloride. Among these, hydrochloric acid, sulfuric acid, and the like are preferably used from the viewpoint of storage stability and hydrolyzability of the coating material. In addition, when adjusting the coating material, when using the solution which melt | dissolved these catalysts, it is preferable that the density | concentration shall be in the range of about 0.01-5 mol / l.

Basic compound Examples of the basic compound include ammonia, methylamine, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide and the like. Among these, sodium hydroxide and potassium hydroxide are preferably used from the viewpoint of storage stability and hydrolyzability of the coating material. In addition, when adjusting the coating material, when using a solution in which these catalysts are dissolved, the concentration is preferably within a range of about 0.01 to 5 mol / l.

Perchlorate Examples of perchlorate include magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate. From the viewpoint of curability, ammonium perchlorate is preferred.

Acetylacetonate Complex An acetylacetonate complex may be appropriately deposited from known compounds in consideration of physical properties such as solubility in a coating material, storage stability of the coating material, and hardness of the coating film. Specific examples thereof include Li (I), Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III ), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV), V (IV ) And the like as the central metal atom. From the viewpoint of curability, an acetylacetonate complex having Al (III), Fe (III), or Li (I) as a central metal is particularly preferable. These acetylacetonate complexes may be used alone or in combination of two or more without any problem.

Organic Metal Salt Examples of the organic metal salt include organic metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, and divalent carboxylates as described later. As the metal salt of the organic acid, a divalent carboxylic acid salt may be used. Specific examples of the carboxylic acid constituting the divalent tin carboxylate include linear saturated fatty acids such as undecanoic acid, lauric acid, and tridecyl acid; monoene unsaturated such as undecylenic acid, lindelic acid, and tuzuic acid Fatty acids: Polyene unsaturated fatty acids such as linoleic acid, linolenic acid, stearidonic acid, arachidonic acid, 4,8,12,15,18-eicosapentaenoic acid, docosahexaenoic acid, etc .; Branching of isoacid, anteisoic acid, etc. Fatty acids; Fatty acids having triple bonds such as taliphosphoric acid and stearic acid; Alicyclic carboxylic acids such as naphthenic acid and malvalic acid having 11 or more carbon atoms; Oxygenated fatty acids such as sabinic acid and 2-hydroxytetradecanoic acid And dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, and sebacic acid.

  Moreover, you may use together an amine compound as a catalyst activity promoter which raises the catalyst activity of bivalent tin carboxylate more.

  Specific examples of this amine compound include aliphatic primary amines such as methylamine, ethylamine, propylamine and isopropylamine; aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine and diethanolamine. Amines; N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, triethanolamine, tri (isopropanol) amine, tri (2-hydroxybutyl) amine, tri Aliphatic tertiary amines such as allylamine, tribenzylamine and trihexylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; aniline, laurylaniline and tolu Aromatic primary amine compounds such as gin; aromatic secondary amine compounds such as N-methylaniline and N-methyl-p-toluidine; N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, p -Aromatic amines such as tertiary amine compounds such as amyl dimethylaminobenzoate, but are not limited thereto. These amine compounds may be used alone or in combination of two or more.

  Two or more of the above polymerization catalysts may be used in combination as long as the effect is exhibited. Moreover, the blending amount of the polymerization catalyst is not particularly limited, but is preferably in the range of 0.01 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the finally formed hard coat layer. It is more preferably within the range of ~ 3.0 parts by mass.

(Iii) Organic solvent (iii) The organic solvent used in the resin tooth coating material kit of the present embodiment is a polycondensable organosilicon compound shown in (I), an epoxy compound blended as necessary, (Ii) A known organic solvent can be used without any limitation as long as it dissolves the polycondensation catalyst for the organosilicon compound and has volatility. Examples of such organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and n-pentanol; methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, Esters such as methyl acetoacetate, ethyl acetoacetate, and ethyl lactate; dioxane, tetrahydrofuran, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol Mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono -n- butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethers such as dioxane; acetone, acetylacetone, diacetone alcohol, methyl ethyl ketone, ketones such as methyl isobutyl ketone. These organic solvents may be used alone, but it is preferable to use a mixture of two or more kinds for the purpose of controlling the physical properties of the coating material. In addition, organic solvents having low compatibility with water such as halogenated hydrocarbons such as methylene chloride; hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene, and xylene are also compatible with water as described above. If it is used as a mixed solvent that is compatible with water as a whole by mixing with a high organic solvent, it can be used.

  Among these organic solvents, (I) the polycondensable organosilicon compound and (ii) good solubility of the organosilicon compound in the polycondensation catalyst, the ease of volatility when forming the hard coat layer, and the hard From the viewpoint of smoothness during the formation of the coat layer, alcohols, ethers, and ketones are preferably used. In particular, methanol, isopropanol, t-butanol, acetylacetone, diacetone alcohol, ethylene glycol monoisopropyl ether, and the like are used. Is preferred.

(Iii) Although the compounding quantity of an organic solvent is not specifically limited, Usually, the range of 100-2000 mass parts is preferable with respect to 100 mass parts of solid content of a coating material, and the range of 150-1000 mass parts is more preferable.

(Iv) Inorganic oxide sol In order to further increase the hardness and consolidation of the hard coat layer, (I) In addition to polycondensable organosilicon compounds, silica sol and other metal oxides with a composition based on silica sol You may use together inorganic oxide sols, such as a silica type sol containing a physical component. What is necessary is just to determine suitably the compounding quantity of the inorganic oxide sol contained in a coating material according to the desired physical property etc. according to the objective of the coating layer finally obtained. Specifically, even if the blending amount is too much, (I) the blending amount of the organosilicon compound capable of polycondensation is reduced and causes cracks, so that the finally formed hard coat layer 100 mass The amount is preferably 70.5 parts by mass or less based on parts. Compared to the case where no inorganic oxide sol is used at all, from the viewpoint of obtaining a sufficient hardness improvement and consolidation improvement effect, 20.5 to 70 mass with respect to 100 mass parts of the finally formed hard coat layer. The range of parts is more preferable, and the range of 35 to 65 parts by mass is particularly preferable.

(V) Other components In adjusting the coating material, water can be used as other components. Here, (I) the polycondensable organosilicon compound used as the coating material is alkoxysilane, and (ii) when an acid catalyst is used as the polycondensation catalyst for the organosilicon compound, it is included in the coating material. It is preferable that the molar ratio of the alkoxy group is about 0.1 to 3 times.

<Packaging form>
Although the packaging form of the primer and the coating material constituting the resin tooth coating material kit of the present embodiment is not particularly limited, for example, the primer may be a form in which each component is mixed in one package, In this case, the mixing operation is not required at the time of use, which is efficient.

  On the other hand, since the coating material deteriorates with time in a packaging form in which (I) an organosilicon compound capable of polycondensation and (ii) a catalyst for polycondensation of an organosilicon compound coexist, these two components are usually separated. It is particularly preferable to store in two or more packages and mix and use in one solution immediately before the coating process. Specifically, (I) packaging of components other than the polycondensable organosilicon compound and the catalyst to be blended as necessary, and (ii) packaging of the organosilicon compound polycondensation catalyst, the latter being usually A solution dissolved in water is preferable. When two or more of these primers or coating materials are packaged, each member is separated and stored in a single container having two chambers partitioned by a membrane, and the partition is removed before use. It is also very efficient to mix these members in one liquid.

<Resin tooth coating method>
If the resin tooth coating material kit of this embodiment described above is used, the coating process can be performed on the surfaces of various resin teeth. In this case, the surface portion of the resin tooth may be subjected to the coating treatment as it is, but the surface portion of the resin tooth may be subjected to a pretreatment such as a polishing treatment before the coating treatment is performed. preferable. This makes it possible to achieve objectives such as elimination of inhibitors that adhere the resin tooth surface to the primer layer, strengthening the fitting force by roughening the resin surface, and generating functional groups on the resin surface. The primer layer can be reliably formed with good adhesion to the surface.

  Then, a primer layer forming step for forming a primer layer by applying and curing a primer on the surface of these resin teeth, and a hard coat layer forming for forming a hard coat layer by applying and curing a coating material on the cured primer layer Through the steps, the surface of the resin tooth can be coated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples.

  First, adherends and abbreviations used in Examples and Comparative Examples, primers and abbreviations thereof, coating material preparation methods and abbreviations, appearance evaluation methods after coating treatment, and toothbrush wear test methods will be described.

(1) Adherent and its abbreviation <Adherent>
R1 (resin tooth without inorganic filler): Acrylic resin tooth SR ANTARIS (Ivoclar Vivadent)
R2 (resin tooth containing inorganic filler): 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane 70 parts by weight, triethylene glycol dimethacrylate 15 parts by weight, 1,6-bis (methacrylethyloxycarbonylamino)- 2,2-4-trimethylhexane 15 parts by weight, camphorquinone 0.4 parts by weight, dimethylaminobenzoic acid ethyl ester 0.4 parts by weight, hydroquinone monomethyl ether 0.1 parts by weight, spherical silica zirconia (average particle size 0. 4 μm) 240 parts by weight and fine-particle silica titania (average particle size 0.07 μm) 160 parts by weight were mixed and crushed, and the surface treated with γ-methacryloyloxypropyltrimethoxysilane was thoroughly kneaded in a mortar. And defoaming the hybrid hard resin composition It was produced. Filled into a Teflon (registered trademark) mold of 10 × 10 × 2 mm, photopolymerization 2 minutes (light irradiator Pearl Cure Light, manufactured by Tokuyama Dental), heat polymerization 100 ° C. 15 minutes (heated polymerizer Pearl Cure Heat, manufactured by Tokuyama Dental) ) To obtain a polymerized cured product.

(2) Primer and its abbreviation <Primer>
P1 to P7 are used in Examples, and are primers in which a polyurethane resin is a main component, and the polyurethane resin is dispersed in a dispersion medium in which water is a main component and an organic solvent is partially used together. Each polyurethane resin is a thermoplastic polyurethane elastomer composed of a hard segment which is a crystalline cohesive component composed of urethane bonds and a soft segment which is an amorphous component composed of a polymer polyol. is there.
P1: Superflex 420 (Daiichi Kogyo Seiyaku), Polyol resin polyol skeleton (carbonate), anionic, average particle size 0.01 μm, glass transition point (Tg) = − 10 ° C., elongation 290%, non-volatile 32% by mass
P2: Superflex 150 (Daiichi Kogyo Seiyaku Co., Ltd.), Polyol skeleton of polyurethane resin (ester / ether type), anionic, average particle size 0.07 μm, glass transition point (Tg) = 40 ° C., elongation 330%, Non-volatile content 30% by mass
P3: Evaphanol HA-50C (manufactured by Nikka Chemical), polyurethane resin polyol skeleton (carbonate), anionic, average particle size 0.09 μm, glass transition point (Tg) = − 25 ° C., elongation 450%, non-volatile 35% by mass
P4: Superflex 650 (Daiichi Kogyo Seiyaku), Polyurethane resin polyol skeleton (carbonate), cationic, average particle size 0.01 μm, glass transition point (Tg) = − 17 ° C., elongation 340%, non-volatile 26% by mass
P5: Hydran WLS-213 (manufactured by DIC), polyurethane resin polyol skeleton (carbonate type), anionic, average particle size 0.05 μm, glass transition point (Tg) = − 15 ° C., elongation 400%, nonvolatile content 35 mass%
P6: Adekabon titer HUX401 (manufactured by ADEKA), polyol resin skeleton (ester / acrylic), anionic, average particle size 0.2 μm, glass transition point (Tg) = 7 ° C., elongation 220%, nonvolatile content 37% by mass
P7: Superflex E2500 (manufactured by Daiichi Kogyo Seiyaku), polyurethane resin polyol skeleton (ester), nonionic properties, average particle size 0.96 μm, glass transition point (Tg) = 42 ° C., elongation 360%, nonvolatile content 45% by mass

P8 is a primer used in the comparative example.
P8: Tokso Ceramics Primer (manufactured by Tokuyama Dental)

(3) Coating material preparation method and its abbreviation <Coating material>
C1: 220 g of γ-glycidoxypropyltrimethoxysilane and 467 g of tetraethoxysilane were mixed. While sufficiently stirring this solution, 200 g of 0.05N hydrochloric acid aqueous solution was added, and stirring was continued for 5 hours after the addition was completed. Next, 1.5 g of a silicone surfactant (trade name L-70001, manufactured by Nippon Unicar Co., Ltd.), 6.0 g of Al (III) acetylacetonate, 540 g of t-butyl alcohol, 590 g of dioxane, methanol-dispersed silica sol (Nissan) 1000 g of Chemical Industry Co., Ltd. (solid content concentration: 30 wt%) was mixed, stirred for 5 hours, and aged overnight to obtain a coating material.
C2: Gamma-methacryloyloxypropyltrimethoxysilane 220 g and tetraethoxysilane 467 g were mixed. While sufficiently stirring this solution, 200 g of 0.05N hydrochloric acid aqueous solution was added, and stirring was continued for 5 hours after the addition was completed. Next, 1.5 g of a silicone surfactant (trade name L-70001, manufactured by Nippon Unicar Co., Ltd.), 6.0 g of Al (III) acetylacetonate, 540 g of t-butyl alcohol, 590 g of dioxane, methanol-dispersed silica sol (Nissan) 1000 g of Chemical Industry Co., Ltd. (solid content concentration: 30 wt%) was mixed, stirred for 5 hours, and aged overnight to obtain a coating material.
C3: resin coating material [urethane acrylate Ebecryl 230 (manufactured by Daicel Cytec) 30 parts by weight, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane 25 parts by weight, triethylene glycol dimethacrylate 15 Part by weight, 30 parts by weight of methyl methacrylate, 1 part by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide]

(4) Appearance evaluation method after coating treatment After coating treatment, the surface properties of the obtained sample are visually observed to form a uniform and glossy coating layer (including primer layer and hard coat layer). A that is not uniform, but gloss is B, and C that is not glossy and has poor appearance.

(5) Method of toothbrush abrasion test It is possible to fill 14 toothbrushes arranged in parallel with a 50% water slurry of toothpaste paste (white and white, made by Lion), and press the sample obtained at 400 g load from above. A sample was attached to a toothbrush wear tester, and a toothbrush wear test was performed under conditions of a stroke of 10 cm and a cycle of 10,000 times. The residual ratio (0 to 100%) of the hard coat layer after the test was visually evaluated.

Example 1
Pretreatment: The surface of the adherend R1 shown in Table 1 was polished with # 1500 water-resistant abrasive paper and then ultrasonically washed with distilled water for 5 minutes. Phosphoric acid etching was performed for 20 seconds with Tokuyama etching gel (manufactured by Tokuyama Dental Co., Ltd.) and washed with distilled water for 20 seconds.

  Coating treatment: First, the surface of the adherend R1 was thoroughly dried by air blow. Subsequently, the adherend R1 was dipped in the primer P1 shown in Table 1 and pulled up, dried by air blow, and further heat-treated at 100 ° C. for 5 minutes using pearl cure heat. Next, the adherend R1 was dipped in the coating material C1 shown in Table 1 and pulled up, dried by air blow, and heated at 110 ° C. for 2 hours using pearl cure heat. This was used as a sample for appearance and wear resistance evaluation.

(Examples 2 to 12)
Resin tooth coating material kits comprising combinations of primers and coating materials shown in Table 1 were prepared. Subsequently, various samples for evaluation were produced in the same manner as in Example 1 using these resin tooth coating material kits.

(Comparative Examples 1 and 2)
Pretreatment: The surfaces of the adherends R1 and R2 shown in Table 1 were polished with # 1500 water-resistant abrasive paper, and then ultrasonically washed with distilled water for 5 minutes. Phosphoric acid etching was performed for 20 seconds with Tokuyama etching gel (manufactured by Tokuyama Dental Co., Ltd.) and washed with distilled water for 20 seconds.

  Coating treatment: Each of the adherends R1 and R2 was dipped in the coating material C1 shown in Table 1 and pulled up, dried by air blow, and heated at 110 ° C. for 2 hours using pearl cure heat. This was used as a sample for appearance and wear resistance evaluation.

(Comparative Example 3)
Resin tooth coating material kits comprising combinations of primer P8 and coating material C1 shown in Table 1 were prepared. Subsequently, various samples for evaluation were produced in the same manner as in Example 1 using these resin tooth coating material kits.

(Comparative Example 4)
Using the resin coating material C3 as a coating material, various evaluation samples were prepared in the same manner as in Example 1 in a mode in which no primer was used.

  Table 1 shows the types and combinations of primers and coating materials used in the coating process in each of the above Examples and Comparative Examples. In addition, the appearance and wear resistance of the coated samples obtained in each Example and Comparative Example were evaluated. The results are shown in Table 1.

(Comparative Example 5)
After polishing the surface of the adherend R2 with # 1500 water-resistant polishing paper, polishing is performed under water pouring with an abrasive material Soflex Superfine (manufactured by 3M-ESPE) for 1 minute, so that the glossy surface properties are achieved without coating. It was. Next, when this was used as a sample for evaluation of wear resistance, a toothbrush wear test was performed.

Claims (6)

A primer comprising (a) a polyurethane resin, and (b) a solvent or dispersion medium;
(I) a polycondensable organosilicon compound having a reactive organic functional group, (ii) a catalyst for polycondensation of the organosilicon compound, and (iii) a coating material comprising an organic solvent;
A resin tooth coating material kit comprising:   The resin tooth coating material kit according to claim 1, wherein the glass transition point of the polyurethane resin is less than 37 ° C.   The resin tooth coating material kit according to claim 1 or 2, wherein (a) the polyurethane resin is composed of a hard segment and a soft segment, and the soft segment is derived from a polycarbonate skeleton. Material kit.   The resin tooth coating material kit according to any one of claims 1 to 3, wherein (a) the polyurethane resin is an anionic water-dispersed polyurethane resin. .   The resin tooth coating material kit according to any one of claims 1 to 4, wherein (i) the organosilicon compound has a (meth) acryloyloxy group, an amino group, an epoxy as a reactive organic functional group. A resin tooth coating material kit comprising a group and at least one reactive organic functional group selected from glycidoxy groups.   A resin tooth coating material kit for use in an inorganic filler-containing resin tooth according to any one of claims 1 to 5.