JPH05155730A - Dental coating agent - Google Patents

Abstract

PURPOSE:To provide a dental coating agent capable of lowering the surface energy of a dental prosthesis to impart stain resistance simply by applying to its surface, having excellent adhesivity, etc., and free from toxicity to human body. CONSTITUTION:The objective dental coating agent for coating the surface of denture, denture base, dental composite resin restorative material, etc., contains a silicone oligomer having fluoroalkyl group and expressed by formula I [R1 is H or CH3; R2 and R3 are 1-4C alkyl, alkylcarbonyloxy, alkoxy or trimethylsilyloxy; RF is (CF2)n1X or group of formula II; X is H, F or Cl; (n1) and (y1) are integer of 1-10; (n2) is integer of 0-8; (m) is 0 or 1; R1 is H when (m) is 0], its hydrolyzate and/or hydrolytic condensate, e.g. the oligomer of formula III, as an active component. Since the coating agent has the properties of both fluoroalkyl group and silicone, it has excellent adhesion, water and oil repellency, stain resistance, etc., and is easily applicable to the surface of a dental prosthesis.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dental coating agent for coating the surfaces of dentures, denture bases, dental composite resin restorations, glass ionomer cements, metal floors and the like.

[0002]

2. Description of the Related Art Conventionally, the surface of a base material has stain resistance, beauty, and
A fluoroalkyl group-containing fluororesin such as a fluoroacrylate polymer is often used as a surface treatment agent that imparts water repellency, oil repellency, insulation, and mold releasability. However, the fluororesin has problems such as poor adhesion to inorganic materials such as metals, glass and cement, various plastics, and organic materials such as substrates.

In order to improve the adhesion, a fluoroalkyl group-containing silicone compound has been proposed (JP-A-59-140280). However, the above silicone-based compounds have problems that sufficient adhesion cannot be obtained and that water and oil repellency is reduced.

On the other hand, dentures used in dentistry,
Dental prostheses such as denture bases, dental composite resin restorations, glass ionomer cements and metal floors need to prevent plaque accumulation due to food residue, bacterial adhesion or adhesion.

As a method of preventing the plaque accumulation, it has been proposed that the surface energy of the prosthesis can be reduced by coating with a fluororesin so that the adhered plaque can be easily removed (“J Prosthet Den”).
t ”, vol.51, p353, 1984). Further, a dental prosthesis coated with tetrafluoroethylene polymer has been proposed (Japanese Patent Publication No. 2-38219). However, while the tetrafluoroethylene polymer can provide stain resistance to dental prostheses, the polymer coating has about 1
Since a high temperature baking step of 20 ° C. is required, it is not practical, and further, because of the high temperature baking, a dental plastic material cannot be used as a prosthesis material, and there is a problem that it is limited to a metal material. is there.

As described above, a fluororesin coating agent for lowering the surface energy of a dental prosthesis and improving the stain resistance has been proposed, but the complexity of the baking process, the poor solubility of the fluororesin, There is a problem with adhesion.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to reduce the surface energy of a dental prosthesis and to impart stain resistance to the dental prosthesis, and it is also excellent in adhesion. It is to provide a dental coating agent.

[0008]

According to the present invention, a fluoroalkyl group-containing silicon oligomer represented by the following general formula 2 (hereinafter referred to as fluorosilicon oligomer 1), its hydrolyzate, and its hydrolyzed condensate. And a dental coating agent comprising an ingredient selected from the group consisting of these mixtures as an active ingredient.

[0009]

[Chemical 2]

The present invention will be described in more detail below.

The fluoroalkyl group-containing silicon oligomer used as an active ingredient in the dental coating agent of the present invention is the fluorosilicone oligomer 1 represented by the general formula 2. In the fluorosilicone oligomer 1, production is difficult when R ₂ and / or R ₃ has 5 or more carbon atoms, and when n ₁ is 11 or more and n ₂ is 9 or more, dissolution in a solvent It cannot be used because it deteriorates Further, if y ₁ exceeds 10, production is difficult. Furthermore, it is preferable that the average molecular weight of the fluorosilicone oligomer 1 is in the range of 500 to 10,000. Also, the applicable RF in the fluorosilicone oligomer 1, that is,-(CF ₂ ) n ₁ X and the following general formula 3 are specified. Enumerated above, —CF ₃ , F (CF ₂ ) _{2
-, F (CF 2) 3} -, F (CF 2) 4 -, F (CF 2)
_{5 -, F (CF 2)} 6 -, F (CF 2) 7 -, F (CF 2) 8
_{-, F (CF 2) 9} -, F (CF 2) 10 -, HCF 2 -, H
_{(CF 2) 2 -, H} (CF 2) 3 -, H (CF 2) 4 -, H
(CF ₂ ) ₅ −, H (CF ₂ ) ₆ −, H (CF ₂ ) ₇ −, H
(CF ₂ ) ₈ −, H (CF ₂ ) ₉ −, H (CF ₂ ) ₁₀ −, C
lCF ₂ −, Cl (CF ₂ ) ₂ −, Cl (CF ₂ ) ₃ −, C
_{l (CF 2) 4 -,} Cl (CF 2) 5 -, Cl (CF 2)
_{6 -, Cl (CF 2)} 7 -, Cl (CF 2) 8 -, Cl (C
F ₂ ) ₉ −, Cl (CF ₂ ) ₁₀ −, the following chemical formulas 4, 5, 5, 6, 7, 8, 9 and 10, 11 and 12
Is.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

Specific examples of the fluorosilicone oligomer 1 which is the active ingredient of the dental coating agent of the present invention include, for example, the following general formulas 13, 14, and 15.
6, chemical formula 17, chemical formula 18, chemical formula 19, chemical formula 20, chemical formula 21, chemical formula 2
2, 23, 24, 25, 26, 27, 2
8, Chemical 29, Chemical 30, Chemical 31, Chemical 32, Chemical 33, Chemical 3
4, Chemical formula 35, Chemical formula 36, Chemical formula 37 and the like (in the formula, y ₁ represents an integer of ₁ to 10) can be preferably mentioned.

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

[0039]

[Chemical 29]

[0040]

[Chemical 30]

[0041]

[Chemical 31]

[0042]

[Chemical 32]

[0043]

[Chemical 33]

[0044]

[Chemical 34]

[0045]

[Chemical 35]

[0046]

[Chemical 36]

[0047]

[Chemical 37]

In order to produce the fluorosilicone oligomer 1, a difluoroalkanoyl peroxide represented by the following general formula 38 and a vinyl group-containing organosilicon compound represented by the following general formula 39, or the following general formula It can be produced by reacting with a methacrylic group-containing organosilicon compound represented by 40.

[0049]

[Chemical 38]

[0050]

[Chemical Formula 39]

[0051]

[Chemical 40]

RF in the difluoroalkanoyl peroxide used at this time is the fluorosilicone oligomer 1
Are the same as RF specifically listed in, specifically, for example, diperfluoro-2-methyl-3-oxahexanoyl peroxide, diperfluoro-2,5-dimethyl-3,6-dioxaperoxide. Nonanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide and the like can be preferably mentioned.

The vinyl group-containing organosilicon compound preferably includes trimethoxyvinylsilane, triethoxyvinylsilane, triisopropoxyvinylsilane, and the like, and the methacryl group-containing organosilicon compound includes 3-methacryloxypropyltrisilane. Preferred examples include methoxysilane and 3-methacryloxypropyldiethoxymethylsilane.

When the difluoroalkanoyl peroxide is reacted with the vinyl group-containing organosilicon compound or the methacryl group-containing organosilicon compound, the charged molar ratio is
Preferably 1: 1.0 to 10.0, particularly preferably 1:
The range is 1.2 to 5.0. When the molar ratio is less than 1.0, a large amount of a product is generated due to the self-decomposition of peroxide, which is industrially undesirable. When the molar ratio exceeds 10, the yield of the target fluoroalkyl group-containing organosilicon oligomer is increased. Is reduced, which is not preferable. The reaction can be carried out at room temperature, preferably from -20 ° C to 150 ° C.
C., particularly preferably in the range of 0 to 100.degree. If the reaction temperature is lower than -20 ° C, it takes a long time to carry out the reaction.
If the temperature exceeds 0 ° C, the reaction operation becomes difficult, which is not preferable. Further, the reaction time is preferably in the range of 30 minutes to 20 hours, but practically preferably in the range of 3 to 10 hours.

A solvent can be used to more smoothly carry out the reaction for preparing the fluorosilicone oligomer 1 which is the active ingredient. A halogenated aliphatic solvent is particularly preferable as the solvent, and specific examples thereof include methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, and 1,2-dibromohexa. Fluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1, 3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane and the like can be mentioned, and industrially, 1,1,2
Preference is given to trichlorotrifluoroethane. When the solvent is used, the concentration of the difluoroalkanoyl peroxide in the solvent is preferably in the range of 0.5 to 30% by weight. The product reaction product obtained can be purified by a known method such as distillation.

The hydrolyzate and hydrolyzed condensate of the fluorosilicone oligomer 1 used as an active ingredient of the dental coating agent of the present invention are obtained by converting the fluorosilicone oligomer 1 into a fluorochlorinated hydrocarbon containing water and an alkyl alcohol. It can be obtained by dissolving in a mixed solvent of 1 or an alkyl alcohol solvent containing water, and reacting at a temperature of room temperature to 200 ° C. for 0.5 to 24 hours. At this time, when the molecular weight of the fluorosilicone oligomer 1 is large, it is particularly preferable to react at 100 ° C. or lower.

As the fluorinated hydrocarbon solvent,
1,1,2-trichlorotrifluoroethane, 1,2-
Preferable examples include difluorotetrachloroethane, benzotrifluoride and the like, and examples of the alkyl alcohol solvent include ethanol, isopropanol, butanol and the like. Furthermore, the mixing ratio when these solvents are used can be appropriately selected so as to dissolve the fluorosilicone oligomer 1. The content ratio of water in the solvent is particularly preferably 1 to 30% by weight.

The fluorosilicone oligomer 1, its hydrolyzate and its hydrolyzed condensate used as active ingredients in the dental coating agent of the present invention are non-toxic compounds. Dental coating agent of the present invention, for example, the active ingredient, preferably, ethanol, methanol,
It is preferably diluted with a solvent selected from the group consisting of acetone, ether, water and a mixture thereof, and used as a solution system, and ethanol, water and the like are particularly preferable in view of the influence on the human body. If desired, nontoxic additives such as known surfactants and leveling agents can be added. The concentration of the active ingredient in the solution is preferably in the range of 0.005 to 20% by weight. If the concentration is less than 0.005% by weight, the film thickness becomes thin and the water / oil repellency is lowered, and if it exceeds 20% by weight,
Despite the increase in the film thickness, no improvement in water / oil repellency is observed, and further, the uniformity of the surface is deteriorated and peeling easily occurs, which is not preferable.

The dental coating agent of the present invention can be used by applying it on a dental prosthesis.
Examples of the coating method include a brush method, a spray method, a roll coating method, a spin coating method and a dip coating method. The coating can be performed at room temperature, but the temperature condition may be changed to adjust the formation rate, and the film thickness of the coating formed by coating is the concentration of the active ingredient at the time of coating and the coating. It can be arbitrarily changed depending on the temperature, the pulling speed in the dip coating method, the rotation speed in the spin coating method, etc., and a film can be formed with a film thickness of several angstroms to several hundreds of microns. In order to further improve the adhesion, it is desirable to perform the treatment at 40 to 80 ° C.

[0060]

The dental coating agent of the present invention has the properties of both a fluoroalkyl group and silicone, and therefore has excellent adhesion, water and oil repellency, stain resistance, etc. Can be applied to the surface of the prosthesis for
Contamination resistance can be imparted to the surface. The dental coating agent of the present invention is not toxic to the human body.

[0061]

EXAMPLES The present invention will be specifically described below based on synthesis examples and examples, but the present invention is not limited to these.

[0062]

[Synthesis Example 1] 2.3 g (15.4 mm) of trimethoxyvinylsilane
ol) containing diperfluoro-2-methyl-3-oxahexanoyl peroxide 4.8 g (7.7 mmol) 1,1,2-
Add 150 g of trichlorotrifluoroethane solution and add 3
The reaction was carried out at 0 ° C. under a nitrogen atmosphere for 5 hours. After the reaction,
The reaction solvent was removed, and the residue was purified by distillation (127 ° C / 4 mmHg), and y ₁ represented by the following structural formula 41 was 1-10.
The product in the range of 4.5 g was obtained in a yield of 4.5 g. The average molecular weight was 850.

[0063]

[Chemical 41]

[0064]

[Synthesis Example 2] Diperfluoro-2-methyl-3-peroxide
The reaction was performed according to Synthesis Example 1 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was used instead of oxahexanoyl, and y ₁ represented by the following structural formula 42 was The product, which ranged from 1 to 10, was obtained in a yield of 5.7 g. The average molecular weight was 1350.

[0065]

[Chemical 42]

[0066]

[Synthesis Example 3] Diperfluoro-2-methyl-3-peroxide
The reaction was performed according to Synthesis Example 1 except that diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide was used instead of oxahexanoyl. The yield of product was 6.5 g, with y ₁ ranging from ₁ to 10. Average molecular weight is 1
It was 720.

[0067]

[Chemical 43]

[0068]

Synthesis Example 4 Diperfluoro-2-methyl-3-peroxide
The reaction was performed according to Synthesis Example 1 except that diperfluorobutyryl peroxide was used instead of oxahexanoyl,
A product having y ₁ represented by the following structural formula 44 in the range of ₁ to 10 was obtained in a yield of 4.2 g. Average molecular weight is 710
Met.

[0069]

[Chemical 44]

[0070]

[Synthesis Example 5] Diperfluoro-2-methyl-3-peroxide
4. The reaction was carried out according to Synthesis Example 1 except that diperfluoroheptanoyl peroxide was used instead of oxahexanoyl to yield a product in which y ₁ represented by the following structural formula 45 was in the range of ₁ to 10. Obtained in 1 g. Average molecular weight is 9
It was 50.

[0071]

[Chemical 45]

[0072]

Synthesis Example 6 In 2.5 g (10.0 mmol) of 3-methacryloxypropyltrimethoxysilane, 4.2 g (6.7 mmo of diperfluoro-2-methyl-3-oxahexanoyl peroxide)
50 g of a 1,1,2-trichlorotrifluoroethane solution containing 1) was added and reacted at 30 ° C. for 5 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solvent was removed and distilled (220 ° C / 25
mmHg) to yield 3.0 g of a product represented by the following structural formula 46 in which y ₁ is in the range of ₁ to 10:
Got with. The average molecular weight was 990.

[0073]

[Chemical 46]

[0074]

[Synthesis Example 7] Diperfluoro-2-methyl-3-peroxide
The reaction was carried out according to Synthesis Example 6 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was used instead of oxahexanoyl, and y ₁ represented by the following structural formula 47 was The product, ranging from 1 to 10, was obtained in a yield of 4.1 g. The average molecular weight was 1200.

[0075]

[Chemical 47]

[0076]

Example 1 A 1 wt% solution (solvent: 95% ethanol solution) of the product synthesized in Synthesis Example 1 was prepared as a dental coating agent. A sample plate (cobalt-chromium alloy (Co-
Cr) plate (30 × 30 × 0.5 mm), polymethylmethacrylate (PMMA) plate (30 × 30) as polymer material
X 2 mm)) was dipped for 3 minutes and then dried at 60 ° C. for 60 minutes. Then, the contact angle with respect to water and dodecane was measured and used as a standard for stain resistance. As a control, the contact angle was similarly measured for each sample plate not subjected to the dip treatment. The results are shown in Table 1.

[0077]

[Examples 2 to 7] Processing similar to that in Example 1 was performed in Synthesis Examples 2 to 7.
Each of the products synthesized in 1. was carried out. The results are shown in Table 1. In addition, in order to evaluate the ease of wiping off stains when stains adhere, draw a line with lipstick on the surface that has been subjected to surface treatment, wipe off after 24 hours with absorbent cotton soaked with xylene, and wipe off the surface after the wipe. The degree of contamination was judged. The results are shown in Table 1.

[0078]

[Example 8] In order to examine the adhesion to dental prosthesis materials and the weather resistance to various solvents, each of the sample plates subjected to the dip treatment in Examples 1 to 7 was treated with 1,1,2-trichlorofluoroethane (F- 113), methyl ethyl ketone (MEK), ethyl acetate (AcOE), acetone (AcMe) after 24 hours,
The contact angle with water and dodecane was measured. The results are shown in Table 2.
Shown in.

[0079]

Example 9 When a denture treated with the dental coating agent prepared in Examples 1 and 2 was put on and actually used, adhesion of food residues and the like was remarkably prevented as compared with an untreated denture. A good fit was obtained. In addition, the denture was lightly washed under running water to remove the stains that were slightly attached.

[0080]

[Table 1]

[0081]

[Table 2]

Claims (1)

[Claims] 1. A component selected from the group consisting of a fluoroalkyl group-containing silicon oligomer represented by the following general formula 1, a hydrolyzate thereof, a hydrolyzed condensate thereof, and a mixture thereof as an active ingredient. Dental coating agent. [Chemical 1]