JP3248766B2 - Soft lining material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorosilicone-based soft lining material used for a mucosal surface of a resin denture base.

[0002]

2. Description of the Related Art Many denture patients, particularly complete dentures, are elderly patients, and the alveolar ridge generally has a remarkable bone resorption, and the occlusal force per unit area increases. The alveolar ridge mucosa also becomes thin due to senile atrophy, so that the impact of occlusal and mastication pressures is transmitted directly to the alveolar bone without being reduced. Further, the thin mucous membrane sandwiched between the hard resin denture base and the hard alveolar bone is squeezed every time it bites, and is damaged, causing damage.

[0003] In such difficult cases, if a resin denture base is manufactured using only a commonly used methyl methacrylate resin, good results cannot be obtained in maintaining, stabilizing and supporting the denture. Therefore, it is necessary to cover the resin denture base mucosa surface with a soft material or a soft lining material to compensate for the lost viscoelasticity of the ridge ridge mucosa and to provide cushioning to alleviate the impact at the time of occlusion. In other words, the purpose of lining with a soft material is to overcome various obstacles caused by the hard material of the denture base pressing on the mucosa below the floor.

Conventionally, soft lining materials used clinically include (meth) acrylic acid ester polymers, fluororesins, polyolefin resins, silicone rubbers and the like. For temporary use, denture stabilizers (so-called denture stabilizers) are used.

However, a soft material such as a (meth) acrylic acid polymer lacks chemical stability in the oral cavity, and hardens or becomes brittle within a few months, and cannot be used for a long period of time. Fluorine-based lining materials are also poor in viscoelasticity, and a sufficient cushioning effect is not expected. The polyolefin-based lining material has a lot of practical problems because the polymerization temperature is high and the resin denture base may be deformed, and a plurality of adhesives and a dedicated heater are required and the operation is complicated. Silicone rubber-based lining material is a relatively stable material, but it still swells in organic solvents such as oil and ethanol, and its chemical stability, such as acid resistance and oil resistance, such as its strength decreases in an acidic atmosphere. Not enough.

[0006] As for the denture stabilizer, the longer the period of use, the higher the consistency and the lower the plasticity. As a result, the purpose of improving the maintenance, stability and support of the denture base by improving the compatibility and marginal sealing properties of the incompatible denture cannot be sufficiently fulfilled, and in many cases the oral tissue is damaged. In addition, since the compression stress is small and the elasticity is poor, the cushioning effect against the occlusal pressure is not sufficient, and this has caused the recurrence of pain in the oral mucosa.

[0007]

As described above, the soft lining material for the denture base provided so far has a decrease in physical properties in a short period of use, and the period of use in the oral cavity is short and satisfactory. Not only does the cushioning effect not exist,
The method of use was complicated and many were not suitable for practical use. For this reason, a soft lining material having appropriate viscoelasticity and having no deterioration in physical properties has been desired. Particularly with the aging society, such a soft lining material has been strongly demanded.

[0008]

The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, by using fluorosilicone rubber for the matrix, they have excellent acid resistance and oil resistance, and can be used for a long time. This led to the development of a soft lining that could be used across the board.

That is, the present invention relates to the following (A):

[0010]

Embedded image

[However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶
And R ⁷ are the same or different alkyl groups or phenyl groups having 1 to 8 carbon atoms, R is an alkylene group having 2 to 10 carbon atoms, R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms, m
And n are m ≧ 0, n ≧ 1, 10 ≦ m + n ≦ 1000
0, an integer satisfying n / (m + n) ≧ 0.05], a vinyl group-containing fluorosilicone represented by the formula (B), wherein at least 3 hydrogen atoms bonded to silicon atoms in the molecule
Having organohydrogenpolysiloxane,
A soft lining material comprising (C) a filler and (D) a platinum catalyst.

The component (A) vinyl group-containing fluorosilicone represented by the above general formula used in the present invention comprises:
Component (B) is a main component which becomes a rubber elastic body by being crosslinked by an organohydrogenpolysiloxane (hereinafter abbreviated as SiH siloxane), and serves as a main component for exhibiting acid resistance and oil resistance.

In the above formula, R ^{1 to} R ⁷ are an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group and an octyl group, or a phenyl group, which may be the same or different. In order to obtain good rubber elasticity, a lower alkyl group or a phenyl group is preferred. Furthermore, within the same molecule, R ³ ,
R ⁴ and R ⁵ may each be different alkyl groups or phenyl groups, R may be different alkylene groups, and R ^f may be different perfluoroalkyl groups. That is, for example, R
^In some embodiments, 3 takes a methyl group and a phenyl group in the same molecule.

Further, in the above general formula,

[0015]

Embedded image

A structural unit;

[0017]

Embedded image

The structural unit does not necessarily mean that m and n structural units are connected continuously.
That is, it is only necessary that each structural unit is bonded in an arbitrary order (random), but that m and n total units are present in the molecule in total.

In the above formula, R is an alkylene group having 2 to 10 carbon atoms. Those having 0 or 1 carbon atoms are difficult to synthesize. From the viewpoint of easy availability of raw materials, those having a lower alkylene group such as an ethylene group are preferable. R ^f has 1 to 1 carbon atoms.
And 8 is a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. A lower perfluoroalkyl group is preferable from the viewpoint of easy availability of raw materials and good rubber elasticity.

In order to obtain good rubber elasticity as a whole, (m + n) in the above general formula is preferably 10 or more and 1000 or more.
Must be 0 or less. When (m + n) is less than 10, the obtained elastic body is too hard and brittle, so that 1
When it is larger than 0000, the obtained elastic body becomes too soft, and thus is not suitable as a soft lining material. In addition, in order to exhibit good acid resistance and oil resistance as a whole, it is necessary that n / (m + n) is 0.05 or more in the same general formula. If n / (m + n) is less than 0.05,
The effect of the perfluoroalkyl group is not sufficiently exhibited, and good acid resistance and oil resistance are not exhibited.

The typical examples of the vinyl group-containing fluorosilicone used in the present invention are specifically shown as follows:

[0022]

Embedded image

(Where Ph represents a phenyl group) and the like. As described above, the order of bonding of the above-mentioned compounds and each of the repeating structural units in Examples and Comparative Examples described later is completely arbitrary.

The SiH siloxane in the present invention is a component which functions to crosslink the above-mentioned vinyl group-containing fluorosilicone to form a rubber elastic body. In order to react with the vinyl group-containing fluorosilicone to form a crosslinked structure, at least three hydrogen atoms bonded to a silicon atom are required. If the number is less than 3, a crosslinked structure is not obtained and a rubber elastic body cannot be obtained.

The SiH siloxane is desirably compatible with the vinyl group-containing fluorosilicone. More specifically, when the value of n / (m + n) of the vinyl group-containing fluorosilicone represented by the general formula is 0.2 or less, the molecular structure of the SiH siloxane is at least from the following units. Shows compatibility if configured.

[0026]

Embedded image

Wherein R ⁸ and R ⁹ are the same or different and represent an alkyl group having 1 to 8 carbon atoms or a phenyl group;

[0028]

Embedded image

Wherein R ¹⁰ and R ¹¹ are the same or different and represent an alkyl group having 1 to 8 carbon atoms or a phenyl group;

[0030]

Embedded image

(Where R ¹² represents an alkyl group having 1 to 8 carbon atoms or a phenyl group) On the other hand, when the value of n / (m + n) of the vinyl group-containing fluorosilicone is larger than 0.2, the SiH siloxane Is at least

[0032]

Embedded image

(Wherein R ¹³ represents an alkyl group or phenyl group having 1 to 8 carbon atoms, R represents an alkylene group having 2 to 10 carbon atoms, and R ^f represents a perfluoroalkyl group having 1 to 8 carbon atoms) If it is not included, the compatibility is lost. If the vinyl group-containing fluorosilicone is not compatible with the SiH siloxane, the reactivity becomes poor and it is difficult to obtain a good rubber elastic body.

Specific examples of the SiH siloxane used in the present invention are as follows.

[0035]

Embedded image

And the like. In the case of the SiH siloxane in the above-described examples and comparative examples, the bonding order of each repeating structural unit in the molecule is completely arbitrary, similarly to the vinyl group-containing fluorosilicone.

In the present invention, the blending amounts of the vinyl group-containing fluorosilicone and the SiH siloxane vary greatly depending on the molecular weight. Usually, one vinyl group in the vinyl group-containing fluorosilicone is replaced by a silicon atom in the SiH siloxane. What is necessary is just to mix | blend so that the number of bonded hydrogen atoms may be 1-3. If the proportion is too small, the curability becomes insufficient, and if it is too large, the obtained elastic body becomes brittle or excess hydrogen atoms bonded to silicon atoms remain, so that the stability over time of the elastic body decreases.

The total amount of the vinyl group-containing fluorosilicone and the SiH siloxane of the present invention is suitably 20 to 95% by weight based on the total amount of the vinyl group-containing fluorosilicone, the SiH siloxane and the filler. When the amount is less than 20% by weight, the obtained elastic body has poor rubber elasticity, and when the amount is more than 95% by weight, the strength of the obtained elastic body is insufficient, and both provide a good soft lining material. Can not.

The component (C) filler used in the present invention comprises:
As long as they do not inhibit the hydrosilylation reaction, inorganic powders, organic powders, organic-inorganic composite powders, and the like can be used, or a mixture of these can be used. Typical examples include silica powder such as ground quartz, fused silica, wet silica and dry silica, fluorocarbon resin powder such as polytetrafluoroethylene and povinylidene fluoride, carbon black, glass fiber, and ground polymer. , Powder polymers, composite fillers (crushed composites of inorganic oxide and polymer), and the like.

The amount of the filler is suitably from 5 to 80% by weight based on the total amount of the vinyl group-containing fluorosilicone, the SiH siloxane and the filler. If the amount is less than 5% by weight, the strength of the obtained elastic body becomes insufficient, and
If the amount is larger, the obtained elastic body has poor rubber elasticity, and it is impossible to obtain a good soft lining material.

As the component (D) platinum catalyst used in the present invention, any one used in a usual hydrosilation reaction can be used. For example, chloroplatinic acid, an alcohol-modified product thereof, platinum catalyst Vinyl siloxane complexes and the like can be mentioned. In order to enhance the storage stability, a material having a small amount of chloro, such as a vinyl siloxane complex of platinum, is preferable.

The amount of the platinum catalyst may be in the range of 0.1 to 1000 ppm in terms of platinum based on the total weight of the vinyl group-containing fluorosilicone and the SiH siloxane. When the amount is less than 0.1 ppm, the crosslinking reaction between the vinyl group-containing fluorosilicone and the SiH siloxane does not proceed sufficiently. When the amount is more than 1000 ppm, it is difficult to control the crosslinking reaction.

In the soft lining material composition of the present invention, other additives may be added as far as the physical properties are not significantly reduced. Examples of such additives include a reaction inhibitor, an ultraviolet absorber, a plasticizer, a pigment, an antioxidant, and an antibacterial agent.

The composition of the present invention usually comprises a fluorosilicone containing a vinyl group, a filler, a platinum catalyst and, if necessary, an excipient containing additives, an SiH siloxane, a filler, and optionally a vinyl. It is generally prepared as a two-package type comprising a group-containing fluorosilicone and an additive containing an additive.

The preparation method does not differ from the known preparation method of, for example, a dental rubber-based impression material composition. That is, by weighing the necessary components from the vinyl group-containing fluorosilicone, the SiH siloxane, the filler, the platinum catalyst and the additive in an appropriate amount, and kneading the mixture with a general kneader such as a kneader until the mixture becomes uniform, the paste-like state is obtained. A composition can be obtained.

The method of using the soft lining material of the present invention can be a known direct lining method. That is, just before use, two types of pastes of the former and the latter are weighed and kneaded in an appropriate amount, put on the back of the denture, and held until fully cured in the oral cavity of the patient. After curing, remove from the oral cavity and remove excess part.

[0047]

The soft lining material obtained by the present invention has an appropriate elasticity after curing, becomes an elastic body having excellent chemical stability such as acid resistance and oil resistance, and is suitable as a soft lining material. Used.

[0048]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Table 1 shows vinyl group-containing fluorosilicone used in the following Examples and Comparative Examples, and Table 2 shows SiH siloxane.

[0050]

[Table 1]

[0051]

[Table 2]

In the examples and comparative examples, the evaluation of the soft lining material composition was performed by the following method, and the same sample was measured or evaluated three times and the average value was recorded.

(1) Shore A hardness A required amount of each of the pastes A and B is taken, kneaded, and filled into a polytetrafluoroethylene (hereinafter abbreviated as PTFE) mold having a hole of 9 mm in diameter and 12 mm in length. At 37 ° C. in air. After curing, the resin is taken out of the mold, left in the air at 37 ° C. for 24 hours, and measured with a Shore A hardness meter.

(2) Tensile strength, elongation First and second pastes are each taken in a required amount, and after kneading, a 2 mm thick PT having a hole in the shape of a required dumbbell-shaped test piece is obtained.
The mold was filled in an FE mold and sufficiently cured in air at 37 ° C. After curing, the resin was taken out of the mold, allowed to stand in the air at 37 ° C. for 24 hours, and then subjected to an autograph (manufactured by Shimadzu Corporation) at a crosshead speed of 10 mm / min. Measure the tensile strength and elongation at cutting. The size of the parallel part of the dumbbell-shaped test piece is 10 mm in length and 5 mm in width.

(3) Acid Resistance Test The elastic body prepared in the above (1) and (2) was immersed in 5N hydrochloric acid at 60 ° C., and the Shore A hardness, tensile strength and elongation after 4 weeks were measured according to the above-mentioned test methods. Measure.

(4) Oil Resistance Test Take the required amount of paste for each of A and B,
The mold was filled in a PTFE mold having a hole of mm × 10 mm × 2 mm, and was sufficiently cured in air at 37 ° C. After curing,
After being taken out of the mold and left in the air at 37 ° C. for 24 hours, the length, width and thickness are measured. 3 each elastic body
It is immersed in a salad oil or ethanol at 7 ° C., taken out after 24 hours, and measured again vertically, horizontally and thickness, and the degree of swelling is determined as the volume after swelling when the initial volume is set to 100.

Examples 1 to 10 and Comparative Examples 1 to 4 Materials having the respective compositions shown in Table 3 were kneaded with a kneader.
A paste was prepared. A test was performed using each paste according to the above evaluation method. Table 4 shows the results.

[0058]

[Table 3]

[0059]

[Table 4]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-215770 (JP, A) JP-A-1-301609 (JP, A) JP-A-55-38172 (JP, A) JP-A-55-38172 21919 (JP, A) JP-A-4-134011 (JP, A) JP-A-59-144708 (JP, A) JP-A-2-276809 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 6/093 A61C 13/02

Claims (1)

(57) [Claims] (A) General formula (1) [However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different alkyl groups having 1 to 8 carbon atoms or phenyl groups, and R is an alkylene group having 2 to 10 carbon atoms. , R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms, m and n are
≧ 0, n ≧ 1, 10 ≦ m + n ≦ 10000, n / (m +
n) an integer satisfying ≧ 0.05], a vinyl group-containing fluorosilicone represented by the formula (B): an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule, (C) A soft lining material comprising a filler and (D) a platinum catalyst.