JP3095615B2 - Silicone soft lining coating 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 coating material for imparting lubricity to the surface of a silicone-based soft lining material.

[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. Since the alveolar ridge mucosa is also thinned by senile atrophy, 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 (acrylic resin), good results cannot be obtained for maintenance, stability and support of the denture. Therefore, it is necessary to cover the resin denture base mucous membrane surface with a soft material and a soft dental lining material to compensate for the lost viscoelasticity of the ridge ridge mucous membrane and to provide cushioning to alleviate the impact during 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.

As this soft lining material, a silicone rubber-based lining material containing silica particles as a reinforcing material has been used as a relatively excellent lining material, but one of the problems is that it cannot be cut. That is, there is a point that the shape cannot be corrected after the lining. Accordingly, the present inventors have conducted intensive studies with the aim of developing a silicone rubber-based soft lining material having machinability, and have employed a polyorganosilsesquioxane particle which is a silicone resin powder as a filler to improve machinability. And have already proposed a cutable silicone-based soft lining material filled with the polyorganosilsesquioxane particles.

[0005]

Although the silicone-based soft lining material having the above-mentioned machinability proposed by the present inventors has good machinability, there is a new problem that the cut surface is not smooth. Was found. The problem caused by the fact that the cut surface of the silicone-based soft lining material is not lubricated is that not only is the tongue with a particularly sensitive sensation in the human body bad, but also food residues etc. tend to adhere. Therefore, there is a possibility that the plaque may be a source of plaque.

[0006]

In general, silicone rubber is used by filling a silica-based powder such as fumed silica or precipitated silica as a reinforcing material. This is because the intermolecular force of the polysiloxane in the silicone rubber is usually very weak, and the mechanical strength such as tear strength and tensile strength is small. Therefore, the use of the curable silicone rubber-based composition containing no reinforcing material has been limited to the use of a release material and a release material as disclosed in JP-A-60-190458.

The present inventors have conducted intensive studies to solve the above-mentioned problems of the silicone-based soft backing material. As a result, a hydrosilylation reaction-curable silicone composition having a specific viscosity diluted with a volatile solvent as required. When the product is used as a coating material, it can simultaneously satisfy good application operability and sufficient mechanical strength after curing, and can form a thin coating layer on the surface of a silicone-based soft lining material. The present inventors have found that the coating layer firmly adheres to the silicone-based soft lining material and can impart lubricity to the surface of the roughened silicone-based soft lining material without impairing its durability. Was.

That is, the present invention relates to (A) 100 parts by weight of an organopolysiloxane having at least two organic groups having a terminal unsaturated bond in a molecule, and (B) a hydrogen atom bonded to a silicon atom in the molecule. And (C) a platinum catalyst in terms of platinum atoms in terms of the amount of the component (A) in which the number of hydrogen atoms is 0.5 or more per one unsaturated bond in the component (A). A) and 0.1 to 1000 ppm by weight based on the total amount of the component (B), and (D) 0 to 1000 parts by weight of a volatile solvent,
A coating material for a silicone-based soft lining material, which has a viscosity of 1 to 100 poise.

The component (A) used in the present invention comprises an organopolysiloxane having at least two organic groups having a terminal unsaturated bond in a molecule (hereinafter abbreviated as an unsaturated bond-containing silicone). It is a main component that becomes a rubber elastic coating layer by being crosslinked with an organohydrogenpolysiloxane (hereinafter abbreviated as SiH siloxane).

The unsaturated bond-containing silicone of the component (A) is not limited in the structure of other organic groups as long as it is an organopolysiloxane having at least two organic groups having terminal unsaturated bonds in one molecule. It may be linear or branched, and may be a mixture thereof.

Examples of the organic group having a terminal unsaturated bond include a vinyl group, an allyl group, a 1-butenyl group and the like, and a vinyl group bonded to a silicon atom is preferred due to ease of synthesis and reactivity. Most advantageous. These organic groups having a terminal unsaturated bond may be present at the terminal or in the middle of the molecular chain of the organosiloxane, or may be present at both of them, but have excellent reactivity and rubber elasticity after curing. In order to have chemical and physical properties such as mechanical strength of the coating layer, it is preferable that at least one of the coating layers exists at the terminal.

The organic group bonded to the silicon atom other than the organic group having a terminal unsaturated bond includes a methyl group, an ethyl group,
Propyl group, butyl group, alkyl group such as octyl group, aryl group such as phenyl group, chloromethyl group, 3,
Examples thereof include a substituted alkyl group such as a 3,3-trifluoropropyl group. Of these, the rubber elastic coating layer which is easy to synthesize and has a good chemical strength such as sufficient mechanical strength and coloring resistance after curing is obtained. A methyl group is the most preferable in terms of maintaining the physical and physical properties.

[0013] Typical examples of the unsaturated bond-containing silicone used in the present invention are as follows.

[0014]

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(Where Ph represents a phenyl group) and the like. In addition, the bonding order of each repeating structural unit in the compounds used in the compounds and Examples and Comparative Examples described later is completely arbitrary, and the number of repeating structural units shown in the structural formula is simply the total amount of each structural unit. It only shows the average value.

The SiH siloxane of the component (B) in the present invention is a component having a function of crosslinking the above-mentioned unsaturated bond-containing silicone to form a rubber elastic coating layer. In order to react with the unsaturated bond-containing silicone to form a crosslinked structure, at least three hydrogen atoms bonded to the silicon atom are required in the molecule. If the number is less than 3, a crosslinked structure is not obtained and a rubber elastic coating layer cannot be obtained.

Examples of the organic group bonded to a silicon atom other than a hydrogen atom include those similar to the organic group having a terminal unsaturated bond and the organic group having no terminal unsaturated bond in the aforementioned component (A). However, a methyl group is most preferred because it is easy to synthesize and maintains good chemical and physical properties such as sufficient mechanical strength and coloring resistance after curing. Such SiH siloxane may be linear, branched, or cyclic, and may be a mixture thereof.

A typical example of the SiH siloxane used in the present invention is as follows.

[0019]

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(However, Ph represents a phenyl group). In the SiH siloxane used in Examples and Comparative Examples described above and below, the bonding order of each repeating structural unit in the molecule is completely arbitrary similarly to the unsaturated bond-containing silicone, and the repeating structural unit represented by the structural formula Is merely an average value of the total amount of each constituent unit. .

In the present invention, the unsaturated bond-containing silicone and S
Although the amount of each iH siloxane varies greatly depending on its molecular weight, usually, one or more unsaturated bonds in the unsaturated bond-containing silicone have at least 0.5 hydrogen atoms bonded to silicon atoms in the SiH siloxane, Preferably, they may be blended in a ratio of 1 to 10. If the proportion is too small, the curability becomes insufficient, and if the proportion is too large, the obtained rubber elastic coating layer becomes brittle or an excess of hydrogen atoms bonded to silicon atoms remains, so that the stability over time of the rubber elastic coating layer becomes poor. It tends to decrease.

In addition, a hydrogen atom bonded to a silicon atom by an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to a silicon atom in a molecule is bonded to one unsaturated bond in the unsaturated bond-containing silicone. If it is 0.5 or more, an organohydrogenpolysiloxane containing only two or one hydrogen atom bonded to a silicon atom in the molecule may be further added.

As the component (C) platinum catalyst used in the present invention, any platinum catalyst can be used as long as it is used in a usual hydrosilylation reaction. 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 unsaturated bond-containing silicone and the SiH siloxane. When the amount is less than 0.1 ppm, the crosslinking reaction between the unsaturated bond-containing silicone and the SiH siloxane does not proceed sufficiently, and when the amount is more than 1000 ppm, when the rubber elastic coating layer is yellow or severe due to precipitation of platinum black. Problems such as black coloring and difficulty in controlling the crosslinking reaction occur.

The volatile solvent of the component (D) used in the present invention is a volatile solvent capable of simultaneously dissolving the components (A), (B) and (C). It is used to adjust the viscosity to 1 to 100 poise. Examples of the volatile solvent include methylene chloride, toluene, tetrahydrofuran and the like,
Of these, methylene chloride is most preferred because of its high volatility. The amount of the volatile solvent may be selected so that the viscosity of the composition of the present invention before curing is 1 to 100 poise, and the viscosity of the components (A) and (B) substantially depends on the viscosity. The amount is determined. Usually, component (A) 1
It is used in an amount of 1000 parts by weight or less based on 00 parts by weight. However, when the viscosity of the mixture containing the components (A), (B) and (C) as a basic component is already in the range of 1 to 100 poise. There is no need to use volatile solvents.

The viscosity of the composition of the present invention needs to be adjusted to be 1 to 100 poise. When the viscosity is less than 1 poise, that is, when the viscosity of the component (A) unsaturated bond-containing silicone, that is, the molecular chain is short, the viscosity is low and the overall viscosity is less than 1 poise, it is sufficient for the cured rubber elastic coating layer Component (A), the unsaturated bond-containing silicone has a sufficient viscosity, that is, a molecular chain length, but the total viscosity of the component (D) is less than 1 poise by adding a volatile solvent. When it is small, a sufficient thickness of the rubber elastic coating layer cannot be secured, so that sufficient surface lubricity cannot be obtained. On the other hand, when the viscosity is more than 100 poise, there are problems such as poor operability, an increased thickness of the rubber elastic coating layer after curing, and insufficient mechanical strength. In addition, the viscosity prescribed | regulated in this invention means the viscosity before hardening of the curable composition which consists of an essential component as mentioned above.

Further, if necessary, other additives may be added to the coating material of the present invention as far as the physical properties are not significantly reduced and the viscosity is maintained. Examples of such additives include silica-based powders such as crushed quartz, fused silica, wet silica, and dry silica, silicone resin powders such as polymethylsilsesquioxane particles, and fluorocarbon resin powders such as polytetrafluoroethylene and polyvinylidene fluoride. Fillers such as carbon black, glass fiber, pulverized polymer, powdered polymer, composite filler (pulverized composite of inorganic oxide and polymer), non-reactive silicone, reaction inhibitor, ultraviolet absorber, plasticizer, Pigments,
Examples include antioxidants, antibacterial agents and the like.

The coating material for a silicone-based soft backing material of the present invention is generally composed of an unsaturated bond-containing silicone, a platinum catalyst and, if necessary, an upper containing a volatile solvent and other additives; Is usually prepared as a two-pack type consisting of an unsaturated bond-containing silicone, a volatile solvent and other additives containing other additives, and the two are generally mixed and used immediately before use.

The method of preparation includes unsaturated bond-containing silicone,
By weighing the necessary components from SiH siloxane, platinum catalyst, volatile solvent and additives in appropriate amounts and mixing in a mixing vessel or kneading until uniform using a general kneader such as a kneader or planetary. A viscous liquid or paste-like composition can be obtained. At this time, when a volatile solvent is contained, it must be mixed in a closed container.

In the method of using the coating material of the present invention, two kinds of liquids or pastes are properly measured and kneaded immediately before use, applied to the coated portion of the silicone-based soft lining material, and sufficiently cured as it is. Hold until done.

The silicone-based soft lining material coating material of the present invention has at least two vinyl groups in the molecule as an organic group having a terminal unsaturated bond and has a methyl group as an organic group other than the organic group. Unsaturated bond-containing silicone, SiH siloxane having at least three hydrogen atoms bonded to a silicon atom in the molecule and having a methyl group as an organic group bonded to the silicon atom is used as an unsaturated bond in the unsaturated bond-containing silicone. The platinum / vinylsiloxane complex is converted into an unsaturated bond-containing silicone and SiH in an amount of 1 to 10 hydrogen atoms per bond.
0.1 to 1000 ppm based on the total amount of siloxane, and if necessary, a volatile solvent is contained, and the viscosity is 1 to 1.
100-poise silicone-based soft lining material coating material can be obtained from raw materials, ease of synthesis, polymerization reactivity, operability, mechanical hardness of rubber elastic coating layer after curing, chemical resistance such as coloring resistance, etc. This is a preferred embodiment because it is particularly excellent in physical properties.

[0032]

The coating material for a silicone-based soft lining material obtained according to the present invention has a strong adhesion to the silicone-based soft lining material after curing, and has sufficient mechanical strength and a smooth surface. Can be formed. As a result, the surface of the silicone-based soft lining material roughened by cutting can be lubricated, and the tactile sensation by the tongue can be improved, and the danger of plaque formation due to the adhesion of food residues can be avoided. Was.

[0033]

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 the unsaturated bond-containing silicones used in the following Examples and Comparative Examples, and Table 2 shows the SiH siloxanes.
Shown in

[0035]

[Table 1]

[0036]

[Table 2]

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

(1) Test Materials The following two types of pastes A and B were prepared as silicone-based soft lining materials. These were kneaded and hardened in equal amounts to obtain a cured silicone rubber. The surface of the cured body is polished with a paper cone (paper cone, rough light company) using a dental engine to roughen the surface. On this surface, take the required amount of liquid or paste for each of Party A and Party B, apply after kneading, leave at 37 ° C in air for 10 minutes,
Let it cure. The operability at that time, the change in gloss before and after curing, and the strength of the coating layer were measured by the following methods.

A paste: 100 parts by weight of compound 100 parts by weight of polymethylsilsesquioxane fine particles (particle size: 2 μm) 1 part by weight of a platinum / vinylsiloxane complex solution (1000 ppm of platinum) B paste: 97 parts by weight of compound 3 parts by weight of compound Methylsilsesquioxane fine particles (particle size: 2 μm) 100 parts by weight The cured silicone rubber prepared here has a tensile strength of about 20 kgf / cm ² .

(2) Operability Take the required amount of liquid or paste for each of Party A and Party B,
The mixture is kneaded with a small brush and applied to the surface of the cured silicone rubber cured product. The operability at that time was evaluated. The evaluation points were evaluated in three stages of A, B and C according to the following criteria.

A: good B: generally good C: bad (how bad the condition is recorded in the table) (3) Glossiness Before and after coating with the silicone-based soft backing coating material of the present invention Gloss meter (Tokyo Denshoku Co., Ltd .: TC-108D, incident angle 4)
5)). The glossiness of the roughened surface before coating was 1.5%, and the glossiness of the lubricated surface cured by pressing the pp sheet was 62.0%.

(4) Strength of Coating Layer The surface of the cured silicone rubber coated with the coating material for a silicone-based soft backing material of the present invention was scratched with a stainless steel spatula, and the state of the destruction was evaluated by observation. The evaluation points are A, B, according to the following criteria.
C was evaluated in three stages. In this case, the strength of the coating layer indicates an overall strength including the mechanical strength of the coating layer itself and the adhesive strength to the silicone-based soft lining material.

A: Not destroyed B: Partially destroyed C: Destruction Example 1 100 parts by weight of the compounds shown in Table 1 were mixed with platinum vinylsiloxane complex in an amount such that platinum was 50 ppm based on the total amount of the compounds. The mixture was placed in a flask and agitated to give an instep.

100 parts by weight of the compounds shown in Table 1 and 40 parts by weight of the compounds shown in Table 2 were placed in a flask and stirred to obtain a second preparation.

The instep preparation and the second preparation were stirred and mixed in an amount of 1: 1 to prepare a coating material, which was evaluated according to the above-mentioned evaluation method. Table 4 shows the results.

Examples 2 to 11 and Comparative Examples 1 to 5 In the same manner as in Example 1, materials having the respective compositions shown in Table 3 were stirred in a flask without powder components, and mixed with powder components. Was kneaded with planetary to prepare liquids or pastes (instep and supple). The same platinum catalyst as that used in Example 1 was used.

[0047]

[Table 3]

[0048]

[Table 4]

The coating materials were prepared by stirring and mixing the instep preparations and the preparations of Examples and Comparative Examples in the amounts shown in Table 3 and tested according to the evaluation method described above. Table 4 shows the results.

[0050]

[Table 5]

From the results shown in Table 4, the silicone-based soft lining material coating material of the present invention (Examples 1 to 11) has good operability, imparts a glossy surface, and has a sufficient coating layer. It turns out that it has strength. On the other hand, in Comparative Example, when the number of hydrogen atoms bonded to silicon atoms in the component (B) is less than 3 (Comparative Example 1), the composition does not cure, and the viscosity at the time of mixing before curing is 1 Below poise (Comparative Examples 2 and 3), sufficient surface gloss and sufficient coating layer strength could not be obtained, and when the viscosity before mixing was 100 poise or more before curing (Comparative Example 4), the operability was poor and the components ( The number of hydrogen atoms bonded to silicon atoms in B) is the number of components (A)
If the number of unsaturated bonds is less than 0.5 (Comparative Example 5), the paste is not sufficiently cured. Thus, it can be seen that in all of the comparative examples, good properties were not exhibited as the coating material for the silicone-based soft lining material.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI C09D 183/07 C09D 183/07 (58) Field surveyed (Int.Cl. ⁷ , DB name) A61C 13/23 A61K 6/093

Claims (1)

(57) [Claims] (A) An organopolysiloxane having at least two organic groups having a terminal unsaturated bond in a molecule.
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule, wherein the hydrogen atom is contained in an amount of 0.1% to one unsaturated bond in the component (A). 5 or more, (C) 0.1 to 1000 ppm of platinum catalyst based on the total amount of component (A) and component (B) in terms of platinum atom, and (D) volatile solvent 0
A coating material for a silicone-based soft lining material, wherein the coating material has a viscosity of 1 to 100 poise.