JPS61161207A - Coating material composition for denture base - Google Patents

Abstract

PURPOSE:The titled composition having improved fitting properties and good durability, consisting of a fluorine-contained copolymer obtained from a fluoroolefin, an alkylvinyl ether, a hydroxyalkylvinyl ether, and another comonomer as an active ingredient. CONSTITUTION:The titled composition consisting of a fluorine-contained copolymer obtained by copolymerizing 40-60mol% fluoroolefin with 5-45mol% alkylvinyl ether as a flexibility imparter, 3-15mol% hydroxyalkylvinyl ether, and 0-3mol another comonomer as an active ingredient. This composition makes the most of merits of denture base made of an elastic elastomer, and can provide a denture base which has improved staining properties with improvement in durability and hydrophobic nature, and can keep stability of dimensional accuracy and appreciation of color tone for a long period.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a coating material composition for denture bases.

(Conventional technology) Traditionally used acrylic resin back denture base.

Although polysulfone denture bases are relatively durable and stain resistant, they have no elasticity and are hard, making them uncomfortable to wear, and they have poor adsorption properties.
It has the disadvantage of poor occlusal properties. For this reason, attempts have been made to soften the contact by using a soft rubber-like material in the parts that come into contact with the gums and the small oral cavity.

Denture bases made of polyurethane elastomer, which has high strength and excellent wear resistance, are now being used.This denture base has strong resistance to mechanical deformation and bending, provides a comfortable fit, and has good adhesion and occlusal properties in the oral cavity. With its superior properties, it has greatly improved the drawbacks of previous denture bases.

[Problems to be Solved by the Invention] However, polyurethane elastomer mm floors lack durability due to hydrolytic deterioration in the oral cavity, and because of their low hydrophobicity, they tend to absorb and penetrate dirt, causing discoloration. That is, due to the low hydrophobicity of the denture base surface, problems still remain, such as 1. Contaminants enter the interior together with water, and only the water escapes, leaving only the contaminants.

Therefore, the zero adjustment of the present invention has, for example, excellent fitability based on the elasticity of a polyurethane elastomer denture base, and its good adsorption and occlusal properties, but also water resistance, hydrophobicity, and chemical resistance. The object of the present invention is to provide a coating material composition for a denture base that can eliminate the above-mentioned problems. The denture base material is not limited to polyurethane elastomer, but if the denture base coating material itself, which is rich in soft elasticity, has poor flexibility, the soft elasticity of the incisal angle will be canceled out, so the coating is not recommended. The material itself must also have appropriate flexibility. The coating material of the present invention also takes into consideration this flexibility.

Means for Solving Problem C) The composition of the present invention for achieving the above object contains 40 to 60 thymol of fluoroolefin as a main ingredient.

5 to 45 mol of alkyl ether as a softening agent;
It consists of 3 to 15 moles of hydroxyalkyl vinyl ether. In a preferred embodiment, the composition of the present invention contains other copolymerizable comonomers (
(Details will be described later). The present invention will be explained in further detail below. The main agent and (7) fluoroolefins are hydrolysis resistant and chemical resistant.

It is an essential component for exhibiting hydrophobic C (that is, stain resistance), but when its content is less than 40 molar arcs,
On the other hand, if the amount exceeds 60 mol, the above-mentioned properties cannot be exhibited appropriately, and the solubility in the solvent is impaired.

As the fluoroolefins, perfluoroolefins are preferred, and tetrafluoroethylene and chlorotrifluoroethylene are preferably used alone or in combination.

As the alkyl vinyl ether, those having an alkyl group having 2 to 6 carbon atoms are preferably used. Examples include ethyl vinyl ether, n(normal)-furobyl vinyl ether, inbutyl vinyl ether, n(normal)-hexyl vinyl ether, cyclohexyl vinyl ether, and 2-chloroethyl vinyl ether, etc. Motsu vinyl ether can be used alone or in combination of two or more. When the amount of alkyl vinyl ether is less than 5 moles, it is flexible.

Solubility in solvents is impaired, and if it exceeds 45 mol, chemical resistance and stain resistance will decrease. As the k-hydroxyalkyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc. are used. If the blending amount exceeds 16 mol, it will affect the solubility of the copolymer and it will dissolve only in specific solvents such as Al
In short, there are restrictions on the coating agent base. It deteriorates the flexibility of the cured coating film, resulting in poor wearing comfort and adsorption properties as a denture base. Further, the pot life in the presence of the curing agent decreases, which is undesirable since it seriously impairs the coating operation.On the other hand, if the amount of copolymerization is less than 3 mol, the curability deteriorates.

This results in an increase in curing time and a decrease in the mechanical strength, hydrolysis resistance, chemical resistance, and stain resistance of the cured coating.

In addition, the adhesion to the polyurethane coating is also deteriorated, which is undesirable.The coating material of the present invention can be copolymerized with 0 to 30 molar arc copolymerizable comonomers other than those mentioned above. Examples of other comonomers that can be copolymerized include ethylene, propylene, and imbutylene.

Vinyl chloride, vinylidene chloride, methyl acrylate.

Fluorine-containing compounds such as ethyl acrylate, methyl methacrylate, diethyl maleate, acrylic acid, methafrylic acid, ff motuptil oleate, vinyl acetate, acrylate acetate, n-vinyl butyrate, glycidyl vinyl ether, chrycidyl methacrylate, etc. Comonomers copolymerizable with the polymer can also be used.

The fluorine-containing copolymer that is the base material of the coating material has an intrinsic viscosity of 0.05 to 2.0 C in tetrahydrofuran in an uncured state at 30°C. OdJ, / is preferably 0.07~
1.01/f/ is preferably used. Polymerization is carried out by applying a polymerization initiator or a polymerization initiation source such as ionizing radiation to carry out a copolymerization reaction by a conventionally known method such as emulsion polymerization, solution polymerization, suspension polymerization, or columnar polymerization. When coating a material according to the present invention, it may be used without a solvent if it is in liquid form, but it is generally used in a form dissolved in various solvents. Examples of solvents include toluene, xylene, n-butanol, ethyl J II butyl acetate, methyl ethyl ketone, methyl imbutyl ketone,
Ethyl Celsolve, etc., and various commercially available thinners can be used. When the denture base is made of polyurethane elastomer, it is desirable to add polyincyanate as a hardening agent to the coating material solution in order to increase the chemical adhesion between the coating material of the present invention and the denture base surface. . As this polyisocyanate, one having two or more incyanate groups in one molecule is used. For example, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate), m-phenylene diisocyanate).

? -phenylene diisocyanate), 2.4-)! JL/
2.6-) lylene diisocyanate, 1.5-naphthylene diisocyanate, 4.4'
, 4″-) Riphenylmethane triisocyanate.

4.4'-diphenylmethane diisocyanate),) luidine diincyanate, rn-xylylene diincyanate, P-xylylene diincyanate.

Polyisocyanates such as isophorone diisocyanate and lysine incyanate, and excess of the above incyanates, such as ethyne glycol, propylene glycol,
1.3-butylene glycol, neopentyl glycol, z,zta-utjfk-1,3-bentanediol, hexamethylene glycol, cyclohexane dimetatool, trimethylolpropane, hexanetriol, glycerin.

Examples include polyisocyanates with more than two functional groups obtained by addition reaction with low-molecular-weight polyols such as pentaerythritol.Among them, heat-yellowing diisocyanates such as hexamethylene diisocyanate and inholodiisocyanate and their adducts can be easily absorbed by sunlight. It is particularly advantageous in that it does not yellow. The mixing ratio of the coating material of the present invention and the polyisocyanate is preferably in the range of (hydroxyl groups in the fluorine-containing copolymer)/(isocyanate groups in the polyisocyanate) = 1/3 to 110.5 (equivalent ratio). In this case, various conventionally known catalysts can be used to promote the reaction between the coating material and the polyisocyanate. The coating film thickness is approximately 5 to 100 mm. I
Apply it once or more with a brush, dip, spray roller, etc. to a thickness of approximately L, and dry and harden at room temperature or by heating. For 2 to 4 days at room temperature, for example, 80℃ when heated
It will harden in about 15 hours. As the denture base material, an elastomer which is rich in soft elasticity in combination with the flexibility of the coating material of the present invention can be meaningfully applied. The most suitable material is polyurethane distoner. These polyurethane elastomers are obtained by reacting polyols, polyisocyanates, and optionally chain extenders, and are made using conventionally known techniques 1, such as injection into the plaster of a denture base that has been previously evacuated and loaded with a denture. , heating and curing, and demolding to form a urethane denture base with a denture. As a polyol component.

Various conventionally known products can be used, but among them poly(oxytetramethylene) glycol, which has excellent hydrolysis resistance,
Polyether polyols such as polypropylene glycol, polycarbonate polyols such as polybutylene carbonate diol, polyhexamethylene carbonate diol, 1.4-polybutadiene diol, 1.2-
Particularly preferred are polybutadiene polyols such as polybutadiene diol, polysiloxane polyols such as poly(dimethylsiloxane) diol, and copoly(dimethylsiloxane-methyphenylsiloxane) diol.

These polyols have an average molecular weight of 500 to lo, ooo
It has two or more active hydroxyl groups in the molecule and can be used alone or in combination of two or more. Various types of polyisocyanates can be used here.

Among them, non-aromatic inphoron diinsine), 1,6-hexamethylene diisosilane), which has excellent non-yellowing properties,
Preferred are hydrogenated products of 4.4'-diphenylmethane diisocyanate, hydrogenated products of tolylene diisocyanate, inpropylidene bis(4-cyclohexyl irisyanate), and the like. Also, trilene dicyane), 4.4'-
Diphenylmethane diisocyanate, xylylene diisocyanate.

1.5-naphthylene diisocyanate, toluidine diisocyanate, etc. can also be used. The above polyol and polyinsyanate usually have an NGO10H ratio of 1.
The t-terminal isocyanate is reacted in the range of 5 to 4 to produce a 1/polymer. This prepolymer is then cured by a chain extension reaction using a conventionally known chain extender such as a polyol, polyamine, alkanolamine, etc., or a mixture thereof.

It is desirable to use the chain extender in an amount such that the final NGO10H ratio is in the range of 1.0 to 1.2. Furthermore, when producing this polyurethane elastomer, pigments, hydrolysis inhibitors, catalysts for promoting the reaction of heat stabilizer 1, etc. are added singly or in combination according to conventionally known techniques.

It can also be included.

Although polyurethane elastomer is taken as an example of the denture base material in the above description, the material is not limited to this, and other soft elastic elastomers can also be used. Materials with poor elasticity, such as acrylic resin and polysulfone, are incompatible with imparting flexibility to the coating material of the present invention and should be excluded.

(Function) Fluoroolefins improve hydrolysis resistance, hydrophobicity, and chemical resistance, increasing the durability and dyeing resistance of the coating material, suppressing swelling of the denture base, stabilizing dimensional accuracy, and improving color tone. In addition to maintaining aesthetics, the use of alkyl ether and hydroxyalkyl ale as softening agents imparts appropriate flexibility to the coating material, making it easier to wear denture bases made of soft elastic elastomers. The coating material of the present invention has the above-mentioned effects because it can fully exhibit the good adsorption and bite properties without canceling them out.

In particular, while taking advantage of the advantages of soft elastic elastomer denture bases, we have improved the contamination caused by low durability and low hydrophobicity, as well as improved stability in dimensional accuracy and aesthetic color tone. It is useful for long-term maintenance of sex and has the effect of contributing to increasing the suitability of denture bases.

(Example) (Example 1) Polyhexamethylene carbonate diol (OH value 56
．． average molecular weight 2.000) 100 parts by weight at 120°C
After dehydration treatment for 1 to 2 hours under a reduced pressure of 70 Hg, 30 parts by weight of isophorone diincyanate was added to give about 80 to 80 Hg.
The reaction was carried out at 100° C. for 0.5 hours to obtain a terminal incyanate prepolymer. This prepolymer was then heated to 80~x
Add 3,3'-dichloro-4,
21 parts by weight of 4'-diaminodiphenylmethane at 120°C
Add the dissolved material and mix well, then add about 80 to 1
Defoaming was performed at 00° C. under a reduced pressure of 70 glHg for 2 to a minute. Next, the polyurethane elastomer reaction solution is poured into a denture urine plaster mold loaded with dentures and preheated to about 80°C, and 80 to 100 tons of it is placed in an oven. It was held for 16 hours. Next, the molded polyurethane elastomer denture base was removed from the plaster mold, the sprue and beams were removed, and the surface was polished to obtain a polyurethane elastomer denture base. The resulting polyurethane elastomer denture base had a Shore hardness of D50. On the other hand, the coating material of the present invention was prepared by placing 29.4 parts by weight of ethyl vinyl ether, 6.4 parts by weight of hydroxybutyl vinyl ether, 45 parts by weight of tetrafluoroethylene, in a 200 wrl autoclave equipped with a stirrer.
3 parts by weight and methyl isobutyl ketone 7 as a polymerization solvent
5tj was charged, the internal temperature was kept at 60°C, and then 0.05 parts by weight of azobisinobutyronitrile was added to it (111
A solution of methyl in butyl ketone was injected under pressure to initiate polymerization. The initial internal pressure was 20ψ, but polymerization was carried out with stirring for 4 hours while maintaining the internal temperature at 60°C until the internal pressure reached 2 Kg/CII.The resulting polymerization reaction solution was taken out and was colorless. A transparent, slightly viscous solution was obtained.The solid concentration of the solution was 488 parts by weight, and the composition of the copolymer was 52 moles of tetrafluoroethylene units, 43 moles of ethyl vinyl ether, and 5 moles of hydroxybutyl vinyl ether.
molar and intrinsic viscosity (in tetrahydrofuran at 30°C)
was o, 2a dj/g. Discard 50 parts by weight of the methyl in butyl ketone solution of the obtained neat material, add and mix 2 parts by weight of hexamethylene diisocyanate, and apply this solution to the surface of the polyurethane elastomer denture base obtained above with a brush. After air drying at room temperature for 1 hour,
Heat treatment was performed at ℃ for 3 hours.

The polyurethane elastomer denture base coated with a fluorine-containing resin obtained as described above has good flexibility even when the whole is bent or deformed, and it adheres extremely well without peeling even when the coated part is scratched with a fingernail. The properties were good. In addition, the polyurethane elastomer denture base coated with this coating material had good fit, adsorption, and occlusion properties, and there was no discoloration, peeling, or deterioration at all even after one year of use (no damage even when scratched with a fingernail).

(Example 2) The polyurethane elastomer reaction solution of C Example 1) was
The mixture was poured into a mold for producing a sheet heated to 20° C. and cured in an open environment for 16 hours at 80 to 10,013 °C, then taken out from the mold and polished on one surface to obtain a polyurethane elastomer sheet. Next, from this sheet to JIS 6301
A JIS No. 3 dumbbell described in was created. This JIS
A solution prepared by adding and mixing hexamethylene diincyanate to the coating material base liquid of (Example 5) was applied to the entire surface of the No. 3 dumbbell with a brush, and a coating with a coating thickness of 25 to 307 I was applied, and the following immersion test was performed. I made a piece. In order to clarify the effect of the coating material of the present invention, it was immersed at 60°C for 70 days. After completing the immersion test, the test piece was thoroughly washed with water and then air-dried at room temperature for 48 hours. The surface of the test piece after immersion may be discolored, and JIS
Shore hardness, tensile strength, and elongation were measured according to 6a01, and compared with the unsoaked test piece, the results showed no change in hardness, tensile strength change rate -2 arc, and elongation change rate +3 yen.
Almost no deterioration of the material was observed outside the coma volume change rate of +0.3. Further, even when the test piece was bent or deformed, there was no peeling of the rotation.

(Comparative Example 1) A polyurethane denture base was prepared in the same manner as in (Example 1) (however, the fluorine-containing resin coating was not applied).This denture base had good wearing comfort, adhesion, and occlusion. However, after 6 months of use, the color changed significantly, and it deteriorated to the point where it became brittle and broke when scratched with a fingernail.

(Comparative Example 2) A test piece made of polyurethane entomer without any coating material was prepared in the same manner as in (Example 2), and the same immersion test as in Example 2) was conducted.

After soaking, the surface of the test piece adsorbed the curry powder pigment and changed color significantly, and the Shore hardness change, tensile strength change rate, elongation rate change rate, and volume change rate were -109G and -70G, respectively.
It was observed that the material deteriorated significantly at 1-801+11.31.

- Above - Applicant Wada Precision Dental Co., Ltd. (and 2 others) Agent Patent Attorney (6235) Hidehiko Matsuno Procedural Amendment (Own ship May 10, 1985 Patent Application No. 1269 2, Invention Name: Denture base coating material composition 3, relationship with the amended person case Applicant address: 6-1-41 Nishiawaji, Higashiyodoyo-ku, Osaka Name: Wada Precision Dental Research Co., Ltd. Representative Kazu 1) Takeshi Hiro ( 4. Agent address: 550 5. Date of amendment order (voluntary) 6. Number of inventions increased by amendment None nJ-■
“Column for detailed description of the invention” 8. Contents of the amendment The following items in the description shall be amended.

(1) PL, 2. Claims 1 and 2 are amended as shown in the attached sheet.

(2) Replace the description from line 7 from the bottom of P3 to line 1 of P4 up to "The main ingredient includes ......" in the following sentence.

■ 40 to 60 mol% of fluoroolefins, 5 to 45 mol% of alkyl vinyl ethers as softening agents, 3 to 15 mol% of hydroxyalkyl vinyl ethers, and 0 to 3 mol% of other copolymerizable comonomers (however, (excluding 0).
1r □ tework'' is corrected.

(4) P4, line 4 “Content” is corrected to “solid amount A.”

(5) Replace the description [Other comonomers - omitted - as comonomers] from the second to the bottom line of P5 with the following sentence (■).

■ 0 to 30 mol% of comonomers (excluding 0)
It is copolymerized. J (6)P as a copolymerizable monomer], line 2.6 "softening agent" is corrected to "softening imparting 11JI".

9. List of attached documents (1) Scope of claims (amendment) 1 copy - or more - 2. Scope of claims (amendment) ■. 40-60% mole of fluoroolefin, 5-45% alkyl vinyl ether as a softening agent Mol%, hydroxyalkyl vinyl ether 3~Coating material composition for tooth base.

Procedural amendment (voluntary) 1. Indication of the case Patent Application No. 1269 of 1985 2. Name of the invention Coating material composition for denture base 3. Person making the amendment Relationship to the case Applicant address Nishi Higashiyodoyo-ku, Osaka City 6-1-41 Awaji Name: Wada Precision Dental Laboratory Co., Ltd. Representative: Hiroki Wada (2 others) 4. Agent address: 1-1.2-1.46, Kyomachibori, Nishi-ku, Osaka City Number of inventions increased by amendment None 7. Subject of amendment: ``Detailed description of the invention'' column and ``Claims'' column 8 of the procedural amendment filed in Item 5111.0 in 1985. Contents of the amendment 1 - The following are the contents of the amendment. to correct.

(]) Replace sentence A in paragraph 2 of supplement + E with sentence I3 below.

13 [fluoroolefin 40-60 mol%.

Flexibility: 1υ, composition: alkyl vinyl ether 5~
45 mol%, hydroxyalkyl vinyl ether 3-1
Materials for dentures 1 to 1 containing as an active ingredient a fluorine-containing copolymer obtained by copolymerizing 5 mol % and 0 to 30 mol % (excluding 0) of other copolymerizable comonomers It is a composition. ] (2. The scope of the claims is amended as shown in the attached sheet.

9. List of attached documents (1) Claims (second amendment) One or more copies.

-2, Scope of claims (second amendment) 1. 40 to 60 mol% fluoroolefin.

Alkyl vinyl ether 5-45 as a softening agent
mol%, hydroxyalkyl vinyl ether 3-15 mol% and other comonomers capable of copolymerization 0-3 mol%
(However, 0 is not included) A denture base material composition comprising a fluorine-containing copolymer obtained by copolymerizing the fluorine-containing copolymer as an active ingredient.

Claims (1)

[Scope of Claims] 1. 40 to 60% mole of fluoroolefin as main ingredient;
A coating material composition for a denture base comprising 5 to 45 mol% of an alkyl vinyl ether and 3 to 15 mol% of a hydroxyalkyl vinyl ether as a softening agent. 2. Claim 1, further comprising 0 to 3 mol% (but not including 0) of another comonomer copolymerizable with the fluorine-containing copolymer in the composition. coating material composition for denture bases.