JPS6391308A - Plastic dental surface coating composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition containing a mixture consisting of a polyfunctional monomer having a specific number or more of (meth) acryloyloxy groups and monofunctional monomer having cyclic ether bond in the side chain and a visible ray polymerization initiator. CONSTITUTION:The titled composition obtained by blending 100pts.wt. monomer consisting of 70-95wt% compound expressed by formula I (at least 4 of X are CH2=CHCOO- and the rest are -OH; m is 1-4; R is H or CH3) and 30-5wt% compound expressed by formula II or III (R1 is 2-3C alkylene; m and n are 0-5; x is 1-6; y is 0-4; z is 0-6) with 0.01-40pts.wt. visible ray polymerization initiator consisting of an aromatic mercaptocarboxylic acid, alpha-diketone and amine having a polymerizable unsaturated group. Plastic dentures having improved abrasion resistance, aesthetic feeling, etc., are readily obtained from the composition at a low cost. Surface characteristics are improved by coating the dentures with the composition and curing the composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a surface plugging composition for a plastic dental denture or denture base (hereinafter referred to as denture or denture base' (+ -Sometimes simply called dentures.

), and more specifically, it relates to applying a treatment to plastic dentures that improves the aesthetic appearance and prevents the growth of bacteria in the surface water.

[Prior Art] Plastic dentures have attracted attention and have been adopted because they have advantages over porcelain dentures and the like in that they are easier to manufacture and can be placed relatively low. However, dentures made of plastic, for example dentures made of polymethyl methacrylate or polycarbonate, have a lower surface gloss than porcelain dentures, and are easily scratched during use or by abrasion with a toothbrush or fingernail. is,
It has been pointed out that problems include a decrease in the gloss of the surface and roughness, which deteriorates the aesthetic appearance and further worsens the feeling of wearing the denture. As a method for improving such defects, a method has been proposed in which a curable composition comprising a polyfunctional acrylate or methacrylate compound and a photosensitizer is applied and cured with ultraviolet rays to make a denture.

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However, since this method involves photopolymerization using ultraviolet rays, it is harmful to the human body, is too fragile to be used directly in the oral cavity, and has a slow curing speed. Moreover, it has essential drawbacks in terms of curing performance, such as a low curing depth. Furthermore, capital investment is expensive. Therefore, there has been a desire for a plastic denture that has excellent adhesion to base materials with excellent surface hardness, wear resistance, and aesthetic appearance.

With the aim of creating a plastic denture that meets the above-mentioned needs, the inventors of the present invention have conducted extensive studies and found that the following features have been added to the surface of the plastic denture, particularly in areas where hardening treatment or maintaining aesthetics is required. By adopting a method of applying a curable composition and then curing with visible light, the above-mentioned problems of the conventional technology can be solved, and the composition can be used directly in the oral cavity and has excellent curing characteristics and hardened surface properties. It has been found that it is possible to obtain plastic dentures.

[Means for solving problems]

The plastic dental coating composition of the present invention has the following general formula! ! (In the formula, at least four of X are OH, -0ROOO- groups, and the remainder is -OB. fcm is a positive integer from 1 to 4. R represents a hydrogen atom or a methyl group.) 70 to 95 parts by weight of at least 1 Mi polyfunctional monomer having 4 or more acryloyloxy groups and/or methacryloyloxy groups in one molecule represented by the following general formula (I[)... ... (n) or general formula [phase] ... code] (The symbol in the above formula or ■ represents an Alkirev group with 2 or 3 carbon atoms, and m and n are positive numbers of 0 to 5. Expressed as an integer, it takes a value that satisfies the formula m+n≧2t-.However, m and n do not take Ot- at the same time; ) represents a positive integer from 0 to 6.
A monomer mixture consisting of 30 to 5 parts by weight of at least one monofunctional monomer having a cyclic ether bond in the side chain represented by (the number of acryloyloxy groups and/or methacryloyloxy groups is 25 or more), and an aromatic mercaptocarboxylic acid based on 100 parts by weight of the monomer mixture;
It is cured by visible light containing 01 to 40 parts by weight of a visible light polymerization initiator α01 to 40 parts by weight consisting of an amine containing α-diketono and a polymerizable unsaturated group.

The composition of the present invention is applied to the parts of dentures that require hardening and is cured. 70 to 95 parts by weight of at least 18 polyfunctional monomers having an acryloyloxy group and/or memecryloxy group; at least one polyfunctional monomer having a cyclic ether bond in the side chain represented by the above general formula 10> or 0; Monofunctional monomer 30
~5'M parts, and the number of (meth)acryloyloxy groups calculated from the molar fraction in the monomer mixture is 25 or more.

If the number of fc (meth)acryloyloxy groups calculated from the mole fraction in the monomer mixture is 25, it is not preferable because the excellent Afc surface hardness and wear resistance targeted by the present invention cannot be obtained. .

The polyfunctional monomer represented by the above general formula is crosslinked and cured to form a crosslinked and cured polymer that exhibits excellent wear resistance and hardness. It has the characteristic that it exhibits very good polymerization activity when irradiated with visible light even in an air atmosphere that is susceptible to polymerization inhibition effects.

Examples of polyfunctional monomers represented by the general formula (17) include dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol intermediate saacrylate, dipentaerythritol tetraacrylate, Pentaerythritol hexamethacrylate, tripentaerythritol tetraacrylate, tripentaerythritol tetramethacrylate, tribentaerythritol penmeacrylate, tripentaerythritol pentamethacrylate, tripene, taerythritol hexaacrylate, tripentaerythritol 1 taacrylate, tripentaerythritol Among these monomers, dipentaerythritol polyester acrylate is one of the most common monomers. It is particularly preferable because of its excellent polymerization activity in air and ease of handling due to its low viscosity.These monomers can be used alone, or they can be used in a mixture of 2s or more. You can.

The proportion of the polyfunctional monomer represented by the general formula is preferably 70 to 95 parts by weight, particularly preferably 75 to 93 parts by weight, based on 100 parts by weight of the monomer mixture. If the proportion of the polyfunctional monomer in the general formula is less than 70 parts by weight, sufficient surface hardness and abrasion resistance of the coating will not be obtained;
If the weight is exceeded, cracks may occur easily.

In addition, the monofunctional monomer which currently has an ether bond in the side chain represented by the general formula Although these specific monomers do not show sufficient polymerization activity even when used in combination with monomers, when used in combination with a polyfunctional monomer represented by general formula C1) in a specific ratio. Even if a hardening treatment is performed by irradiating visible light in an air atmosphere, the hardness exhibits the same properties as in an inert gas atmosphere.

In addition, the cured coating consisting of the monomers in the general formula and the general formula (n) or [phase] is particularly excellent in the effect of improving the wear resistance rather than the surface hardness, and also improves the smoothness of the coating. It also has an excellent effect of improving the brittleness of the film.

Examples of the monofunctional monomer represented by general formula (It) or [phase] include tetrahydrofurfuryl acrylate, 2-tetrahydrofurfuroxy-ethyl acrylate, 2-
Tetrahydrofurfluoxypropyl acrylate, tetrahydrofurfluoxy-diethylene glycol acrylate, tetrahydrofurfluoxy-dipropylene glycol acrylate, 2÷tetrahydro-3-furanoxy÷ethyl acrylate, 2÷tetrahydro-3-
7 ranoxy ÷ propyl acrylate, tetrahydro-3
-7 ranoxydiethylene glycol acrylate, tetrahydro-3-furanoxy-dipropylene glycol acrylate, tetrahydro-2-pyranyl acrylate, 2+tetrahydro-2-pyranmethoxychetyl acrylate, 2+tetrahydro-2-pyranmethoxy ÷
Propyl acrylate, tetrahydro-2-pyranmethoxy-diethylene glycol acrylate, tetrahydro-2-pyranmethoxy-dipropylene glycol acrylate, 2÷tetrahydro-4-pyranoxychetyl acrylate, 2+tetrahydro-4-pyranoxy÷propyl acrylate, tetrahydro- 4-pyranoxy-
Diethylene glycol acrylate, tetrahydro-4
Examples include -pyranoxypropylene glycol acrylate, but preferably those having a boiling point of 200° C. or higher and a molecular weight of 350 or lower.

If the boiling point is less than 200°C, the amount of evaporation during application is large, making it difficult to obtain dentures of constant quality. If the monomer has a molecular weight exceeding 350, the surface hardness and abrasion resistance of the resulting cured film will be slightly reduced. These monomers can be used alone or in combination of 2'a or more.

The monofunctional monomer represented by general formula (n) or [phase] is
It is used in an amount of 30 to 5 parts by weight, preferably 25 to 7 parts by weight, in 100 parts by weight of the monomer mixture. When the proportion of the monofunctional monomer represented by the general formula (1) or (g) exceeds 30 parts by weight, it may be necessary to increase the effect when used in combination with the polyfunctional monomer represented by the general formula. Otherwise, when visible light is irradiated in air, the surface hardness and abrasion resistance of the cured film obtained will be slightly insufficient. On the other hand, if the proportion of these used is less than 5 parts by weight, the resulting cured film will become brittle and easily cracked by the slightest impact. The viscosity of the mixture with the polyfunctional monomer cannot be effectively lowered, and the smoothness of the coating is also slightly reduced.

In addition to the specific monomers represented by (■) and [phase] in the above general formula, there are also monomers that can be crosslinked and cured, such as poly(meth)acrylate of pentaerythritol, trimethylolpropane triacrylate, Trimethylolethane triacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate,
Pentaglycerol triacrylate, hentaglycerol trimethacrylate), 1,4-butanediol diacrylate, 1,6-hexanesiol dimethacrylate, triethylene glycol dimethacrylate, etc., but these monomers When irradiated with visible light in air, it shows no polymerization activity at all, or even when used in combination with a polyfunctional monomer represented by general formula C1), it shows no combined effect at all. Some of them, such as pentaerythritol poly(meth)azilylate, have a certain degree of polymerization activity in the air when exposed to visible light, but unlike the polyfunctional monomers shown in the general formula, It also has poor polymerization activity and does not show any effect when used in combination with the polyfunctional monomer.

For surface-hardened dentures, especially when smoothness and smoothness of the treated surface are required, the following general formula ω OH is added to 100 parts by weight of the monomer mixture.

m and n are 1.2, 3. The positive integer of ... is 1
, and X and y are 0.1, 2, 3. Takes the value of... R5 represents a hydrogen atom, an alkyl group, an acyl group or an aryl group. ) or the following general formula bacterium CH.

Ashi, m and n are 1, 2, 3. ..., and X and y are numbers of 0.1, 2, 5 degrees, etc., and 2 is a positive integer from 1 to 5 from 0 to jHs. - is -8i-OH3, hydrogen atom, alkyl group, 0H
.

It represents an acyl group or an aryl group, and R7 represents a hydrogen atom, an alkyl group, an aryl group, or an aryl group. ) at least 18 of the silicone surfactant represented by α
It is preferable to add a part of 0001 to zO weight.

As the silicone surfactant represented by the general formula ① or (V), those whose molecular structure does not consist of polydimethylsiloxane units and whose part is modified with polyoxyfulkylene 7 groups are used. . The degree of modification is at least 181 oxyfulkylene groups -0CHsOH, - or - per 1 unit of methylsiloxane group 0HI(SiO)4-.
It is preferable that 00B, OH-OH3, etc. are bonded within the range of α1 to 110 units. In addition, ester groups, mercapto groups, hydroxyl groups, and amino groups may be contained per unit of siloxane group as long as they are less than α1 unit.

If the degree of modification by 7 oxyalkylene groups relative to methylsiloxa 7'1f51 units is less than 01, the smoothness of the film will be worse than if a large amount of silicone surfactant is added, and if the degree of modification exceeds 110. The smoothness of the coating also decreases.

The amount of silicone surfactant to be added is preferably α0001~ZO][negative part with respect to 100 parts by weight of the total amount of the monomer mixture. If it exceeds this value, the smoothness of the film will become poor.

Specific examples of the aromatic mercaptocarboxylic acid used as the visible light polymerization initiator of the present invention include 0-lm- or p-
Mercaptobenzoic acid, 0-lm- or p-merc-1 tophenylacetic acid, 0-lm- or p-mer ηbutophenyl 7
0 pionic acid, 0-, m- or p-mercaptophenylbutyric acid, mercaptobenzoic acid, hydroxyl +
Examples include da-p-JIJI/caftobenzoic acid, kuamino-yogai/, Fl/7tobenzoic acid, and chloro-mercaptobenzoic acid. Particularly preferred aromatic mercaptocarboxylic acids include tI o-mercaptobenzoic acid, m-mercaptobenzoic acid, and p-mercaptobenzoic acid.

The α-diketones are not particularly limited and all can be used, including can-7-arquinone, benzyl, acetylbenzoyl, acenaphthenequinone, α-naphthyl, dichlorobenzyl, biacetyl, β-su7tyl, benzoin, α- Naphthoin and β-naphthoin are preferred. Among them, Kan7-arkynones are the most preferred.

Examples of amines containing a polymerizable unsaturated group include dimethylamine ethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, allylamine, methallylamine, diallylamine, dimethallylamine, triallylamine,
trimethallylamine/N,N-dimethyllylamine,
Examples include N-methyldiallylamine, N-7'robildiarylamine, NN, N'N'-tetraallyl 1,4-diaminobutane, and the like. A particularly preferred compound is diethylaminoethyl methacrylate.

It is essential to use these visible light polymerization initiator systems in combination with the above three components, and if even one component is missing, the desired performance will not be achieved. iT2m4-proverbial punishment plus thousands of teeth, tF] product cannot be obtained. For example, when aromatic mercaptocarboxylic acid is lacking, the adhesion to the substrate is significantly reduced. In addition, when α-diketone is missing, the curing speed in particular decreases significantly. Furthermore, when the amine containing the polymerizable unsaturated group is missing, the surface hardness is significantly reduced.

From this point of view, the total amount of the visible light polymerization initiator used in the present invention is from a001 to 40 parts by weight, preferably from a001 to 40 parts by weight, based on 100 parts by weight of the monomer mixture.
The amount of the aromatic mercaptocarboxylic acid, the α-diketone, and the amine containing the polymerizable unsaturated group is preferably in the range of α01 to 15 parts by weight, respectively.

The above are the essential components of rIL of the composition of the present invention, but in order to improve the painting workability for dentures, the flexibility of the film, impact resistance and other properties, toluene, xylene, acetone, methylene chloride, chloroform An organic solvent such as ethyl acetate or the like can be used as a diluent in the rigid recombinant material in an amount of up to 95 parts by weight or approximately 1°. The amount of diluent added is adjusted depending on the required film performance or coating workability of the curable composition.

Furthermore, the composition of the present invention may contain colorants, polymerization inhibitors (e.g., hydroquinone, methoxybenzophenone, methylphenol, hydroquinone monomethyl ether, etc.), oxidation stabilizers, ultraviolet absorbers (e.g., benzophenone, etc.), pigments, etc., as necessary. (e.g. iron oxide, titanium oxide, etc.)
A dye or the like may also be added.

As the visible light for curing the composition of the present invention, light having a wavelength of 3500 to 8000 A emitted from a halogen lamp, a xenon lamp, a mercury lamp, a fluorescent lamp, etc. can be used.

Irradiation with visible light can be carried out under an inert gas such as nitrogen, argon, carbon dioxide, etc., which is advantageous since it can be done in an empty atmosphere. Moreover, when the curable composition used in the present invention is cured under an inert gas, the adhesion of the film may become slightly unstable, or the film may have microcracks. It is most preferable to cure by full irradiation with visible light.

Methods such as brush coating, spray coating, and dip coating are used to apply the curable composition to dentures, and the thickness of the cured film to be applied is usually in the range of 0.1 μm to 1 μm. .

FIG. 1 shows a cross-sectional view of a denture in which a coating layer (2) made of the curable composition of the present invention is formed on the entire surface of a plastic denture base material (1) and is hardened. The cross-sectional view shows a case in which a coating layer is formed only on the surface of the repaired part (3), which has been filled with a filling in the damaged part of a plastic denture.The third problem is that the denture (5) is attached to the denture base (4). A perspective view is shown in which a hardened surface layer of gold is coated on the surface of the set.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.

In addition, the water absorption rate of the denture in the example is JlBT6506
The surface hardness was measured by leadlight hardness, and the abrasion resistance was measured by the method shown below.

(1) Using an abrasion tester equipped with a wear-resistant nylon toothbrush that can be moved back and forth, an abrasion test was conducted 50,000 times using a toothpaste based on dibasic calcium phosphate as an anti-friction agent. Ta. The obtained samples were evaluated by visual judgment as follows.

O: Almost no scratches Δ: Some scratches ×; Significant scratches i) Insert several strips vertically and horizontally into the adhesive cross-linked cured coating at intervals of one bait at the coating cutting line that reaches the substrate. , and commercially available cellophane tea 1″Ik
: Press and peel off rapidly using the upper blade to see how the cross-linked cured film has peeled off from the base material.

◎: If the cross-linked cured film does not peel off even after performing the adhesion peel test on the same spot 5 times in a row O: The cross-linked cured film does not peel off the first time and 9 is 2 to 5
In the following cases: x: When the crosslinked cured film peeled off from the first time Examples 1 to 3. Comparative Examples 1 to 6 15 parts dipentaerythritol tetraacrylate 30 parts dipentaerythritol pentaacrylate 30 parts dipentaerythritol hexaacrylate 25 parts tetrahydrofurfuryl acrylate Visible light polymerization initiator (compounds listed in Table 1 and amounts added) ) was uniformly applied to a polymethyl memethacrylate resin denture using a brush. Next, the visible light irradiator (manufactured by 3M, trade name: 5OFT-LUX) was placed so that the distance between the light irradiation surface and the surface to which the above-mentioned visible light curable composition was applied was 3 cm, and then for 2 minutes. Irradiated with visible light.

Table 1 shows the performance evaluation results of the obtained cured coating films.

As is clear from Table 1, it can be seen that the visible light curable composition according to the present invention has superior properties as a plastic dental restorative member compared to the comparative example of Mi yakugo.

Example 4 Visible light in nitrogen gas! A denture was manufactured using exactly the same method as in Example 1, except for lAt-irradiation. The results are shown in Table 2.

Comparative Example 7 The procedure was exactly the same as in Example 1 except that 55 parts of dipentaerythritol pentaacrylate, 20 parts of pentaerythritol tetraacrylate, 10 parts of 1,6-hexanediol diacrylate, and 15 parts of methyl acrylate were used as the monomer mixture. dentures were manufactured. The results are shown in Table 2.

Comparative Example 8 A denture was surface hardened in the same manner as in Example 1, except that 100 parts of dipentaerythritol pentaacrylate was used as the monomer. The results obtained are shown in Table 2.

Table 2 Example 5 25 parts of Zippe, 1 part of thiosalicylic acid, 5 parts of camphori-quinoa, 5 parts of dimethylaminoethyl methacrylate, and 01 part of the following silicone thread surfactant were added to the hardened part of a polycarbonate denture base. The curable composition was uniformly applied with a brush.

Next, a visible light irradiator (manufactured by 3M Company, product name: 0PTrL)
The area to be cured was irradiated with visible light for 2 minutes, with the distance between the light irradiated surface of UX) and the above-mentioned next-visual photocurable composition coated surface being 3-.

Table 3 shows the performance evaluation results of the nine cured coating films obtained.

Silicone surfactant: However, 23 n72 m + n = 3 Comparative Example 9 Same as Example 1 except that 85 parts of pentaerythritol tetraacrylate and 15 parts of 1,6-hexanediol diacrylate were used as the mono-11 mixture. Then, it was applied to the parts of the polycarbonate denture base that needed to be hardened, and a surface hardening treatment was performed. The results obtained are shown in Table 3.

Comparison 1fil 10 Apply to the hardening area of polycarbonate denture base in the same manner as in Example 1, except that 85 parts of trimethylolpropane trimethacrylate and 15 parts of 1,6-hexanediol diacrylate were used as the monomer mixture. The surface hardening treatment (1j) was carried out. The results obtained are shown in Table 3.

Table 3 [Effects of the Invention] By using the composition of the present invention, plastic dentures with excellent wear resistance, smoothness, impact resistance, and aesthetic appearance can be manufactured easily and at a lower cost.

In addition, the plastic dentures coated and cured with the m-compound of the present invention have better performance such as surface hardness and wear resistance than conventionally developed plastic dentures, and the water absorption rate does not increase after treatment. It does not cause the growth of bacteria and has an extremely wide range of uses.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views of the denture according to the present invention, and FIG. 3 shows the denture set on the denture base according to the present invention,
It is a perspective view when a hardened surface layer is provided on the surface, and in the figure, 1 is a plastic denture base material, 2 is a hardened surface layer, 3 is a repair part, 4 is a denture base, and 5 is a denture. Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, at least 4 of X are CH_2=ORCOO-
group, and the rest are -OH groups. Moreover, m is an integer of 1 to 4. R represents a hydrogen atom or a methyl group. ) at least 70 to 95 parts by weight of a polyfunctional monomer having four or more acryloyloxy groups and/or methacryloyloxy groups in the molecule, and the following general formula (II) or the following: General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 in the above formula (II) or (III) represents an alkylene group having 2 or 3 carbon atoms, m and n are 0 to 5 Represents a positive integer and takes a value that satisfies the formula m+n≧2.However, m and n cannot both be 0 at the same time.x is a positive integer from 1 to 6, y is a positive integer from 0 to 4, and z represents a positive integer from 0 to 6. (The number of acryloyloxy groups and/or methacryloyloxy groups calculated from the molar fraction in the monomer mixture is 25 or more), and aromatic mercaptocarboxylic acid, α based on 100 parts by weight of the monomer mixture.
- A plastic dental surface coating composition containing 0.01 to 40 parts by weight of a visible light polymerization initiator consisting of a diketone and an amine containing a polymerizable unsaturated group. 2. The plastic dental surface coating composition according to claim 1, wherein the α-diketone is camphorquinone. 3. The dental surface coating composition according to claim 1 or 2, wherein the amine containing a polymerizable unsaturated group is dimethylaminoethyl methacrylate. 4. Any one of claims 1, 2, or 3, wherein the aromatic mercaptocarboxylic acid is o-mercaptobenzoic acid (thiosalicylic acid), m-mercaptobenzoic acid, or P-mercaptobenzoic acid. The plastic dental surface coating composition described in . 5. The amount of aromatic mercaptocarboxylic acid, α-diketone, and amine containing a polymerizable unsaturated group in the monomer mixture 1
The plastic dental surface coating composition according to claim 1, wherein the amount is 0.01 to 15 parts by weight per 00 parts by weight. 6. The following general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・(IV) (In the formula, x is ▲mathematical formula). , chemical formulas, tables, etc. ▼ where m and n are positive integers of 1, 2, 3, etc., and x and y are numbers of 0, 1, 2, 3, etc. , and the formula 0
．． A value satisfying 1<(xn+yn)/2m≦10 is taken. R_5 represents a hydrogen atom, an alkyl group, an acyl group, or an aryl group. ) or the following general formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V) (In the formula, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and m and n are 1 , 2, 3, ..., x and y are numbers 0, 1, 2, 3, ..., and z is 0 or a positive integer from 1 to 5. Representation, formula 0.1≦(xn+yn)/(2m+n)≦
Satisfy 10. R_6 represents a hydrogen atom, an alkyl group, an acyl group, or an aryl group, and R_7 represents a hydrogen atom, an alkyl group, an acyl group, or an aryl group. ) At least one silicone surfactant represented by 0
．． The plastic dental surface coating composition according to claim 1, additionally comprising from 0.0001 to 2.0 parts by weight.