JP2002060311A - Soft lining material composition for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a soft lining material composition for dentistry, hardly being discolored after a long-term use, being soft and good in cushioning properties, and excellent in properties to be ground and polished. SOLUTION: This soft lining material composition for dentistry comprises (A) a polyorganosiloxane having at least one alkenyl group bonded to a silicon atom in one molecule, (B) an organohydrogenpolysiloxane having hydrogen atoms bonded to silicon atoms only at both the terminals of a molecular chain, (C) an organohydrogenpoly siloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule, (D) a hydrosilylation catalyst and (E) an inorganic filler, and is regulated so that the total amount of the hydrogen atoms bonded to the silicon atoms present in the components (B) and (C) may be 1-10 per one alkenyl group in the component (A), and the number of the hydrogen atoms bonded to the silicon atoms in the component (B) may be at least 20% of the hydrogen atoms bonded to the silicon atoms in the components (B) and (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft dental lining composition used as a lining material for a resin floor of a denture or a mucosal surface of a metal floor, and more particularly to a method for alleviating pain of a denture patient. The present invention also relates to a soft dental lining material composition which is used for the purpose of improving the adsorptivity of dentures, is soft, has excellent curability and machinability, and does not discolor for a long time.

[0002]

2. Description of the Related Art In a patient who has been wearing a denture for a long period of time, if the bone becomes thin or the mucous membrane becomes thin, the denture base is made of a hard material such as resin or metal, so that the occlusal occlusion may occur. The sinking of the denture at times can hit around the highest point of the bone, causing pain. In patients with heavy perioss, the alveolar bone is raised, or the alveolar bone is absorbed and the chin support is lowered. In such a case, excessive burden pressure is applied to the protruding portion of the alveolar bone during occlusion, resulting in pain.

In order to alleviate and prevent the occurrence of such symptoms, it is necessary to relieve the mucosa-contacting surface of the denture base with a soft material, that is, a soft dental lining material, so as to mitigate the impact during occlusion. . As such a silicone-based dental soft lining material, Japanese Patent Application Laid-Open No. 8-291017 discloses a composition excellent in maintaining long-term viscoelasticity using a combination of hydrophobized fine silica powder and fused silica. Have been. Also, JP-A-10-226613
Japanese Patent Application Publication No. JP-A-2003-133873 discloses a composition containing a polyorganosilsesquioxane filler and having excellent color resistance and machinability.

However, there has been a problem that these silicone-based soft lining materials have poor cushioning properties as a lining material. Further, when used for a long period of time, there is a problem that the discoloration due to the additional catalyst and the adhesive strength to the denture base become small, and the lining material peels off from the denture base. Furthermore, since the cutting property was poor, it was difficult to correct the shape after curing, and the denture was likely to be incompatible.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a dental soft lining material which does not discolor even when used for a long period of time, is soft, has good cushioning properties, and has excellent grinding and polishing properties for shape correction. It is intended to provide a composition. It should be noted that JP-A-10-2
JP-A-59111 discloses a composition having excellent properties such as elastic distortion and permanent distortion using a bifunctional chain extender in combination with a crosslinking agent as a dental impression material. However, this composition
It is intended for precise molding for making dentures, and is not used for a long time in the oral cavity, and it is the main object of the present invention about the adhesion to the denture base, the cutting property, etc. Does not mention at all.

[0006]

The present inventors have conducted intensive studies and found that the composition described below has a short curing time, is soft, has excellent cushioning properties, has good grinding and polishing properties, and has a long life. And found that the color did not change, and completed the present invention.

That is, the present invention relates to (A) a compound having at least one alkenyl group bonded to a silicon atom in one molecule;
Polyorganosiloxane having a viscosity at 5 ° C. of 0.05 to 1000 Pa · s: 100 parts by weight, (B) having hydrogen atoms bonded to silicon atoms only at both molecular chain terminals, and having a viscosity at 25 ° C. of 0.2
Diorganopolysiloxane of 001 to 1.0 Pa · s, (C) 1
At least three hydrogen atoms bonded to silicon atoms in the molecule
An organohydrogenpolysiloxane having a viscosity of 0.001 to 1.0 Pa · s at 25 ° C., (D) a hydrosilylation reaction catalyst: an effective amount, and (E) an inorganic filler: 5 to 100.
Parts by weight, wherein the total amount of hydrogen atoms bonded to silicon atoms present in the component (B) and the component (C) is 1 to 10 per alkenyl group in the component (A), The number of hydrogen atoms bonded to the silicon atoms in the component (B) is the component (B) and the component (C)
A soft dental lining composition is provided, wherein the composition is at least 20% of the hydrogen atoms bonded to silicon atoms present in the component.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Component (A)] The component (A) in the present invention is the main component (base polymer) of the present composition, and its main chain is basically composed of repeating diorganosiloxane units. Is generally a linear diorganopolysiloxane blocked with a triorganosiloxy group, but may have a branched structure in a part of the molecular chain. It is a polyorganosiloxane containing therein at least one, preferably two or more alkenyl groups bonded to silicon atoms. Specific examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group,
A lower alkenyl group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as a hexenyl group and a heptenyl group, is exemplified, and is preferably a vinyl group. The bonding position of the alkenyl group is not particularly limited, and may be at the end of the molecular chain and / or at the side chain of the molecular chain.
It is preferably contained in an amount of about 0.1 mol%, particularly about 0.1 to 5 mol%. Specific examples of the organic group other than the silicon-bonded alkenyl group in the component (A) (that is, an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom) include a methyl group, an ethyl group, and a propyl group. Alkyl groups such as butyl, pentyl and hexyl groups; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group 3,3,
Examples thereof include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably about 1 to 8 carbon atoms, such as halo-substituted alkyl groups such as 3-trifluoropropyl group and 3-chloropropyl group. Of these, a methyl group is preferred because of ease of synthesis.

The viscosity of the component (A) is from 0.05 to 1 at 25 ° C.
000Pa · s (Pascal · second), preferably 0.1-100Pa · s
Is selected from the range. The siloxane skeleton of the polyorganosiloxane of the component (A) may be linear, cyclic, branched, or a mixture thereof, but is preferably substantially linear.

[Component (B)] The component (B) in the present invention comprises:
Like the component (A), it constitutes the main component of the composition of the present invention and has silicon-bonded hydrogen atoms only at both ends of the molecular chain (that is, contains two SiH groups in one molecule). ), 2
It is preferably a linear diorganopolysiloxane having a viscosity at 5 ° C. of 0.001 to 1.0 Pa · s. In the diorganopolysiloxane of the component (B), the organic group bonded to the silicon atom other than the hydrogen atom includes, among the unsubstituted or substituted monovalent hydrocarbon groups exemplified in the component (A), those other than the alkenyl group. The same may be mentioned, and a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are particularly preferable. As the diorganopolysiloxane of the component (B), a dimethylpolysiloxane capped with dimethylhydrogensiloxy groups at both ends represented by the following formula is particularly preferred.

H (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ Si 0] xSi (CH ₃ ) ₂ H In the formula, x is a value such that the magnitude of the viscosity falls within the above range. The component (B) is used to increase the molecular chain length of the component (A) to a high molecular weight, and gives the present composition good cutting strength. In addition, a high curing speed can be provided to reduce the amount of an additional catalyst which causes discoloration.

[Component (C)] The component (C) in the present invention comprises 1
At least three hydrogen atoms bonded to silicon atoms in the molecule
It is an organohydrogenpolysiloxane having a viscosity of 0.001 to 1.0 Pa · s at 25 ° C. The hydrogen atom bonded to the silicon atom (that is, the SiH group) undergoes an addition reaction with the alkenyl group of the component (A) and serves as a crosslinking agent. As the organic group bonded to the silicon atom in the component (C) (that is, an unsubstituted or substituted monovalent hydrocarbon group),
Among the above-mentioned examples of the component (A), the same as those other than the alkenyl group can be mentioned, and a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are particularly preferable. The molecular structure of component (C) may be linear, branched, cyclic, or a three-dimensional network. Examples of such an organohydrogenpolysiloxane include methylhydrogenpolysiloxane in which both ends of a molecular chain are blocked with a trimethylsiloxy group, and dimethylsiloxane / methylhydrogensiloxane in which both ends of a molecular chain are blocked with a trimethylsiloxy group. Dimethyl siloxane / methyl hydrogen siloxane / methyl phenyl siloxane copolymer in which both ends of molecular chains are blocked with trimethylsiloxy groups, dimethyl polysiloxane / methyl hydrogen in which both ends of molecular chains are blocked with dimethyl hydrogen siloxy groups Siloxane copolymer, copolymer consisting of (CH ₃ ) ₂ HSiO _1/2 units and SiO ₂ units, (CH ₃ ) ₂ HSiO _1/2 units and S
Copolymers comprising iO ₂ units and (C ₆ H ₅ ) SiO _3/2 units, and mixtures comprising two or more of these organopolysiloxanes are exemplified.

Here, the total amount of hydrogen atoms (ie, SiH groups) bonded to the silicon atoms present in the component (B) and the component (C) is determined by the alkenyl group bonded to the silicon atom in the component (A). One to ten, preferably one to five. The number of hydrogen atoms bonded to silicon atoms in the component (B) is at least 20 mol% of the total amount of hydrogen atoms bonded to silicon atoms present in the components (B) and (C),
Usually, it is 20 to 80 mol%, preferably 30 to 70 mol%.

[Component (D)] As the hydrosilylation reaction catalyst of the component (D) in the present invention, an alkenyl group bonded to a silicon atom in the component (A) and a alkenyl group in the components (B) and (C) are used. Si
Any catalyst may be used as long as it has an action of accelerating the addition reaction (hydrosilation) with the H group. For example, at least one kind of platinum selected from a platinum-based catalyst, a palladium-based catalyst and a rhodium-based catalyst may be used. Group metal catalysts are preferred, and more specifically, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxane or acetylene compounds; tetrakis (triphenylphosphine) palladium; Chlorotris (triphenylphosphine) rhodium and the like can be mentioned, and a platinum compound is particularly preferable. (D)
The component is required as an effective amount as a catalyst, and specifically, usually, the amount of the catalyst metal element is 0.01 to 100 ppm with respect to the total amount of the component (A), the component (B) and the component (C), Preferably O.02 ~
It is blended at a rate of 50 ppm. If the amount of the component (D) is too small, the curing reaction may not proceed sufficiently. If the amount is too large, the physical properties of the cured product may be impaired or the cured product may be discolored.

[Component (E)] The inorganic filler as the component (E) in the present invention has been conventionally used as a filler for the purpose of reinforcing silicone rubber, adjusting viscosity, improving heat resistance, and the like. Well-known ones can be used.
Examples of such an inorganic filler include fumed silica, precipitated silica, silica fine powder such as crystalline silica,
Spherical fused silica, quartz powder, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide,
Calcium oxide, calcium hydroxide, calcium aluminate, hydrotalcites, calcium carbonate, magnesium carbonate, and the like are used, and one or more of these can be used.

The type of the silica fine powder is not particularly limited. For example, the silica fine powder has a specific surface area of 50 m ² / g by a BET method.
The above (usually 50 to 400 m ² / g, preferably 100 to 300 m ² / g) precipitated silica, fumed silica, reinforcing fillers such as calcined silica, and the average particle diameter is 50 μm or less, particularly 0.1 to 20 μm Non-reinforcing fillers such as crushed quartz (crystalline silica) and diatomaceous earth are used. As the fused silica, those having an average particle size of 0.1 to 40 μm are used.

The above-mentioned inorganic filler may be used as it is, or may be one which has been treated with a surface treating agent to make the surface hydrophobic. Examples of the surface treatment agent that imparts hydrophobicity to the inorganic filler include organosilane, organosilazane, organocyclopolysiloxane, diorganopolysiloxane, and organohydrogenpolysiloxane.

In order to make the cured product translucent and give a sense of unity with the gums, it is preferable to use at least one selected from hydrophobic precipitated silica, fumed silica and fused silica.

[Other Components] In addition to the above components (A) to (E), the composition of the present invention may contain a reaction control agent, if necessary. Any known reaction control agent can be used as long as it controls the addition reaction.
-Methyl-1-butyn-3-ol, 3,5-dimethyl-1-
Acetylene compounds such as hexyl-3-ol and phenylbutynol; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3-divinyl-tetramethyldisiloxane Alkenyl siloxanes, etc .; triazole compounds, such as benzotriazole; phosphine compounds, mercapto compounds, etc., which can be contained in trace or small amounts. Further, various components such as a coloring agent can be blended as required.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 Ingredient (A): 75 parts by weight of a dimethylpolysiloxane blocked at both ends with a vinyl group having a viscosity of 100 Pa · s at 25 ° C. and 25 parts by weight of a dimethylpolysiloxane blocked at both ends with a viscosity of 0.6 Pa · s at 25 ° C. Component (B): dimethylpolysiloxane having a silicon-bonded hydrogen atom at both ends of the molecular chain having a viscosity of 0.018 Pa · s at 25 ° C. (silicon-bonded hydrogen atom content = 0.13% by weight) 3.7
Parts by weight, component (C): molecular chain end having a viscosity of 0.15 Pa · s at 25 ° C.
And 2.2 parts by weight of a methylhydrogenpolysiloxane having a silicon-bonded hydrogen atom in the side chain of the molecule (silicon-bonded hydrogen atom content = 0.38% by weight), component (D): chloroplatinic acid and divinyltetramethyldisiloxane 20 ppm based on the total amount of components (A) to (C) using platinum as the complex, and component (E): hydrophobic precipitated silica 20 having a specific surface area of 42 m ² / g and an average particle diameter of 4 μm treated with dimethylpolysiloxane. The composition A was obtained by mixing 0.01 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane as a controlling agent by weight. However, the molar ratio of the total amount of the SiH groups in the component (B) and the component (C) to the silicon-bonded vinyl group in the component (A) is 1.7, and in the component (B) and the component (C), The ratio of the SiH groups in the component (B) to the total amount of the SiH groups was 37 mol%.

The obtained composition A was subjected to a curing end time, a hardness test, and a grinding / polishing test as follows, and the results are shown in Table 1. (a) Curing end time This composition was kneaded for 30 seconds and filled in a metal ring (inner diameter: 24 mm, height: 8 mm) on an acrylic plate. Then 1
A 50 g Vicker needle (needle diameter: 3 mm) was gently dropped from the surface of the sample, and the time when the penetration became 1 mm or less from the surface was defined as the curing end time. (b) Hardness test A kneaded product of this composition was placed in a metal ring (inner diameter: 24 mm, height: 8
mm), sandwiched between acrylic plates on the top and bottom, and immersed in water at 37 ° C. After 30 minutes, the mold was taken out of the water and the hardness was measured with a durometer A. (C) Grinding / polishing test After preparing a sample similar to the hardness test, grinding and polishing at the silicone point, if the surface is smooth, ○,
If the surface was in a crumpled state, it was evaluated as x. (d) Discoloration test After preparing a sample similar to the hardness test, place it in a dryer at 80 ° C.
It was left for a day and the degree of discoloration was observed. When the external appearance was almost the same as the initial appearance, it was evaluated as ○.

Example 2 Component (A): 75 parts by weight of a dimethylpolysiloxane blocked at both ends with a vinyl group having a viscosity of 100 Pa · s at 25 ° C., and a dimethylpolysiloxane blocked at both ends with a viscosity of 0.6 Pa · s at 25 ° C. 25 parts by weight, component (B): dimethylpolysiloxane having a silicon atom-bonded hydrogen atom at both ends of the molecular chain having a viscosity of 0.018 Pa · s at 25 ° C. (silicon atom-bonded hydrogen atom content = 0.13% by weight) 3.7
Parts by weight, component (C): (CH ₃ ) ₂ HSiO having a viscosity at 25 ° C. of 0.045 Pa · s
0.8 parts by weight of methylhydrogensiloxane resin containing silicon-bonded hydrogen atoms, comprising 58 mol% of _1/2 unit and 42 mol% of SiO ₂ unit, component (D): a complex of chloroplatinic acid and divinyltetramethyldisiloxane As platinum metal, 20 ppm based on the total amount of components (A) to (C), and component (E): 20 weight% of hydrophobic precipitated silica treated with dimethylpolysiloxane having a specific surface area of 42 m ² / g and an average particle diameter of 4 μm. And 0.01 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane as a control agent. However, the molar ratio of the total amount of the SiH groups in the components (B) and (C) to the silicon atom-bonded vinyl groups in the component (A) is 1.6, and in the components (B) and (C), The ratio of the SiH groups in the component (B) to the total amount of the SiH groups was 40 mol%. The same test as in Example 1 was performed on the obtained composition B. The results are shown in Table 1.

Example 3 Component (A): 75 parts by weight of a dimethylpolysiloxane blocked at both ends with a vinyl group having a viscosity of 100 Pa · s at 25 ° C., and a dimethylpolysiloxane blocked at both ends with a viscosity of 0.6 Pa · s at 25 ° C. 25 parts by weight, component (B): dimethylpolysiloxane having a silicon atom-bonded hydrogen atom at both ends of a molecular chain having a viscosity of 0.018 Pa · s at 25 ° C. (silicon atom-bonded hydrogen atom content = 0.13% by weight) 4.0
Parts by weight, component (C): molecular chain end having a viscosity of 0.15 Pa · s at 25 ° C.
And 2.1 parts by weight of methylhydrogenpolysiloxane having a silicon-bonded hydrogen atom in the side chain of the molecule (silicon-bonded hydrogen atom content = 0.38% by weight), component (D): chloroplatinic acid and divinyltetramethyldisiloxane 20 ppm based on the total amount of components (A) to (C) using platinum metal as the complex, and component (E): 7 parts by weight of hydrophobic fumed silica having a specific surface area of 120 m ² / g treated with hexamethyldisilazane; 30 parts by weight of fused quartz having an average particle diameter of 7 μm and 0.01 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane as a control agent were mixed to obtain composition C. Obtained. However, the molar ratio of the total amount of the SiH groups in the component (B) and the component (C) to the silicon-bonded vinyl group in the component (A) is 1.7, and in the component (B) and the component (C), The ratio of the SiH groups in the component (B) to the total amount of the SiH groups was 39 mol%. The same test as in Example 1 was performed on the obtained composition C.
The results are shown in Table 1.

Comparative Example 1 A composition D was obtained in the same manner as in Example 1 except that 2.6 parts by weight of the component (C) was used except for the component (B). However, the molar ratio of the SiH group in the component (C) to the silicon-bonded vinyl group in the component (A) was 1.3. The same test as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 2 A composition E was obtained in the same manner as in Example 3 except that 2.6 parts by weight of the component (C) was used except for the component (B). However, the molar ratio of the SiH groups in the component (C) to the silicon-bonded vinyl groups in the component (A) was 3.0. The same test as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 3 Except for the component (B), 2.6 parts by weight of the component (C) was used, and platinum chloride corresponding to 80 ppm of the total amount of the components (A) to (C) as platinum metal was used. Except for using the complex of acid and divinyltetramethyldisiloxane, all were blended according to Example 1 to obtain composition F. However, the molar ratio of the SiH group in the component (C) to the silicon-bonded vinyl group in the component (A) is 1.3.
Met. The same test as in Example 1 was performed, and the results are shown in Table 1.

[0027]

[Table 1]

[0028]

As described above, the soft dental lining material composition of the present invention has a short curing time, is soft, has good grinding and polishing properties, and has no discoloration over a long period of time. Therefore, when the dental soft lining material composition of the present invention is used, for example, as a lining material for a denture base, it has good cushioning properties and adhesion, does not discolor over a long period of time, and is suitable for patients. Can be provided.

Continued on the front page (72) Inventor Masaya Arakawa 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term (reference) 4C089 AA03 BA13 BE11 CA08

Claims (2)

[Claims] (A) a molecule having at least one alkenyl group bonded to a silicon atom in one molecule, and having a viscosity at 25 ° C. of 0.0
Polyorganosiloxane having a viscosity of 5 to 1000 Pa · s: 100 parts by weight, (B) a diorgano having a hydrogen atom bonded to a silicon atom only at both ends of a molecular chain and having a viscosity at 25 ° C. of 0.001 to 1.0 Pa · s. Polysiloxane, (C) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule and having a viscosity at 25 ° C. of 0.001 to 1.0 Pa · s, (D) a hydrosilylation reaction catalyst : Effective amount, and (E) an inorganic filler: containing 5 to 100 parts by weight, wherein the total amount of hydrogen atoms bonded to silicon atoms present in the component (B) and the component (C) is (A) The number of hydrogen atoms bonded to silicon atoms in component (B) is 1 to 10 per alkenyl group in component, and the number of hydrogen atoms bonded to silicon atoms present in component (B) and component (C) is A soft dental lining composition comprising at least 20% of hydrogen atoms. 2. The method according to claim 1, wherein (E) the inorganic filler is a hydrophobic precipitated silica,
The dental soft lining material composition according to claim 1, wherein the composition is at least one selected from hydrophobic fumed silica and fused silica.