JP2011006503A - Adhesive for ethylene-vinyl acetate copolymer and silicone resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive, with which joins an ethylene-vinyl acetate copolymer and a silicone resin, required when a mouth guard is produced by joining a surface layer material made from the silicone resin to inner and outer surfaces of a mouth guard substrate made from the ethylene-vinyl acetate copolymer.SOLUTION: This adhesive for the ethylene-vinyl acetate copolymer and the silicone resin includes: 100 pts.wt. of an organic solvent (a); and 0.1-20 pts.wt. of a siloxane-modified unsaturated ester polymer (b), preferably a siloxane-modified unsaturated ester polymer having a reactive functional group for a hydrosilylation reaction.

Description

  The present invention relates to an adhesive between an ethylene-vinyl acetate copolymer and a silicone resin. The present invention also relates to a method for producing a mouth guard by adhering a surface layer material made of a silicone resin to the inner and outer surfaces of a mouth guard base made of an ethylene-vinyl acetate copolymer using the adhesive.

  Conventionally, mouth guards (mouthpieces or mouth protectors) used in contact sports such as boxing as a sport protection device or oral protection device for preventing jaw tissue trauma during sports and protecting teeth and jaw bones Also known as).

  In general, the purpose of wearing a mouth guard for sports is to protect the teeth and periodontal tissues (especially the maxillary anterior teeth) from the external force directly applied to the face from the front and side, and by the teeth on the lips, tongue and cheeks by external force Prevents damage, protects teeth, periodontal tissue, prosthesis, etc. from impact due to contact with the upper jaw when external force is applied to the lower jaw, protects the temporomandibular joint (joint cavity, joint disc, etc.) from external force It is intended to protect or prevent damage to the brain such as concussion due to impact on the brain through the temporomandibular joint and dentition.

  By using an elastic material having excellent flexibility as a material, the mouth guard can exhibit effects such as prevention of trauma in the jaw and oral cavity and absorption / relaxation of shock to the brain as described above. That is, by mounting the mouth guard, the external force is diffused throughout the mouth guard, and the concentration of impact can be suppressed.

  Regarding the mouth guard, for example, in Patent Document 1, a mouth guard-shaped wax-up is performed on a model, buried with gypsum, casted, filled with polyvinyl alcohol gel, which is an elastic material, and cured by cooling or the like. A mouth guard manufactured by a method similar to a method for manufacturing a denture is disclosed.

  Further, in Patent Document 2 and Patent Document 3, one having a size suitable for the size of the user's dentition is selected from ready-made mouth guard bases (shells) prepared in a plurality of sizes, and the inner surface thereof is selected. A shell liner type mouth guard manufactured by lining a paste-like silicone resin as a gap layer, inserting it into a mouth guard user's oral dentition and curing it is disclosed.

  The mouth guard disclosed in the above-mentioned Patent Document 1 has a merit that the user's dentition model is prepared and a dentist or a dental technician is prepared by an indirect method, so that the fit with the mounted dentition is good. However, since it is manufactured by an expert, it cannot be manufactured by the user himself, it takes time and time to complete the manufacturing, and the manufactured mouth guard is relatively expensive. It was.

  On the other hand, the mouth guard disclosed in Patent Document 2 is generally called a shell liner mouth guard, and the inner surface (inner mouth) of a mouth guard base body (shell) having a size that fits the user's mouth. Lined with a room-temperature curable silicone resin as a liner, and then cured by mounting it in the oral cavity, so it can be made on-site without the need for technical operations. It is easy to manufacture a well-matched mouth guard and has the advantage of being inexpensive. Generally, an ethylene-vinyl acetate copolymer or a silicone resin is used as an elastic material for the shell of the shell liner type mouth guard, but the ethylene-vinyl acetate copolymer has an advantage that it is inexpensive and has good moldability. However, there was a problem of poor adhesion to the silicone resin.

  Therefore, in the mouth guard disclosed in the above-mentioned Patent Document 3, a hole is provided in the mouth guard base (shell), and the lined room temperature curable elastic material (liner) is leached out from the hole and hardened. Since the shell and the liner can be held with an appropriate fitting force, a shell liner type mouth guard can be produced even with a combination of an ethylene-vinyl acetate copolymer and a silicone resin having poor adhesion.

JP 2003-102478 A JP-A-61-13003 JP-A-8-206272

  The mouth guard disclosed in the above-mentioned Patent Document 3 holds the interface between the shell and the liner only with a mechanical fitting force, so that the durability is not sufficient, and the interface is not hygienic because it easily adheres to the interface. There is no problem. In order to solve this problem, it is required that the shell and the liner are closely adhered and fixed, and an adhesive that bonds the shell ethylene-vinyl acetate copolymer and the liner silicone resin is required.

  Further, when the mouth guard prepared by the above method is used for a long-term use or a use accompanied by strong biting, the ethylene-vinyl acetate copolymer may be frayed or have pores. In addition, due to changes in the oral tissue, there are cases where it becomes impossible to obtain an occlusion that can be tightly tightened when the mouth guard is worn, and the suitability (adhesion) of the mouth guard into the oral cavity may deteriorate. In order to improve such problems, there is no simple method for repairing or correcting directly in the oral cavity without using a model when repairing a deteriorated part, correction of occlusion, compatibility, etc. is desired. It is necessary to make a guard, and it is a problem that it takes time and cost. In order to solve this problem, a method of repairing the deteriorated portion or correcting the occlusal relationship using a silicone resin that can be cured in the oral cavity can be considered. An adhesive that bonds the polymer and the silicone resin is required. However, an adhesive between an ethylene-vinyl acetate copolymer and a silicone resin has not been known so far.

  Accordingly, an object of the present invention is to provide an adhesive that firmly bonds an ethylene-vinyl acetate copolymer and a silicone resin.

  Another object of the present invention is to provide a method for producing a mouth guard by bonding a surface layer material made of a silicone resin to the inner and outer surfaces of a mouth guard base made of an ethylene-vinyl acetate copolymer using such an adhesive. And

  The present inventors have intensively studied to solve the above problems. As a result, if an organic solution of a (meth) acrylic and / or vinyl ester-based polymer modified with siloxane is used as an adhesive for adhering an ethylene-vinyl acetate copolymer and a silicone resin, the above-described problems are caused. The inventors have found that this can be solved, and have completed the present invention.

  That is, according to the present invention, (a) 100 parts by weight of an organic solvent, and (b) an unsaturated ester polymer modified with siloxane (hereinafter also abbreviated as “siloxane-modified unsaturated ester polymer”) 0. There is provided an adhesive of ethylene-vinyl acetate copolymer and silicone resin comprising 1 to 20 parts by weight.

  If the adhesive of this invention is used, an ethylene-vinyl acetate copolymer and a silicone resin can be adhere | attached firmly. Therefore, in the mouth guard whose base is made of the ethylene-vinyl acetate copolymer, when a surface layer material made of a silicone resin is adhered to the inner and outer surfaces thereof, the mouth guard made of an ethylene-vinyl acetate copolymer is preferably used. In the case of manufacturing a shell liner type mouth guard by lining a silicone resin on the inner surface of the shell, both materials can be firmly bonded, and the reliability during use can be greatly enhanced.

<Adhesive composition>
The adhesive between the ethylene-vinyl acetate copolymer and the silicone resin of the present invention comprises an unsaturated ester polymer (b) modified with siloxane in an organic solvent (a). . This adhesive can extremely strongly bond the ethylene-vinyl acetate copolymer and the silicone resin.
[Ingredient (b):]
In the present invention, the siloxane-modified unsaturated ester polymer of component (b) constitutes a homopolymer or copolymer of a derivative of unsaturated ester (unsaturated ester monomer) as the main chain, A siloxane group is bonded.

  The unsaturated ester in the polymer is an unsaturated carboxylic acid saturated ester or a saturated carboxylic acid unsaturated ester, and typical examples of the former include methyl, ethyl, isopropyl, n-butyl, isobutyl, (meth) acrylic acid, An alkyl ester having 4 to 20 carbon atoms such as 2-ethylhexyl is preferable, and typical examples of the latter include vinyl acetate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl octoate and the like preferably 4 to 20 carbon atoms. And ester compounds such as vinyl esters of saturated fatty acids. Of these, methyl (meth) acrylate and vinyl acetate are particularly preferred.

  The siloxane group is a group having at least one silicon-oxygen bond, but is usually an organosiloxane group. These siloxane groups are preferably those having an average number of repeating units of siloxane units such as organomonosiloxane groups and organodisiloxane groups of 2 to 200, particularly 10 to 100, from the viewpoint of familiarity with silicone resins.

  From the viewpoint of enhancing the adhesion to the hydrosilylation reaction-curable silicone resin, the siloxane group is more preferably a siloxane group having a reactive functional group for hydrosilylation reaction. Examples of the reactive functional group for the hydrosilylation reaction include a polymerizable unsaturated hydrocarbon group or a Si—H group, and among them, a vinyl group, an allyl group, and a Si—H group are preferable. The -H group is preferred. From the viewpoint of reactivity, it is preferable that three or more reactive functional groups of the hydrosilylation reaction exist in one siloxane group.

  In the siloxane-modified unsaturated ester polymer of component (b), the siloxane group is 0.1 to 90 mol%, preferably 1 to 50 mol% of the unsaturated ester monomer unit constituting the unsaturated ester polymer. It is preferable that it exists in the range.

  Specific examples of the siloxane-modified unsaturated ester polymer include a structural unit (α) represented by the following formula (1), a structural unit (β) represented by the following formula (2) and / or (2 ′): And an unsaturated ester polymer containing a structural unit (γ) represented by the following formula (3).

In the above formulas (1), (2), (2 ′) and (3),
R ¹ , R ² and R ¹³ each represent a hydrogen atom, a methyl group or an ethyl group,
R ³ represents an alkyl group having 1 to 13 carbon atoms or an aryl group having 6 to 14 carbon atoms,
B represents an ester bond represented by COO or OCO;
A represents a C 2-20 divalent hydrocarbon group which may have an ether bond or an ester bond in the main chain;
R ¹⁴ represents an unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have an ether bond or an ester bond in the main chain;
X is the formula (4)

Or the formula (4 ')

A siloxane group represented by
R ^{4 to} R ¹² and R ^{15 to} R ²² in the formulas (4) and (4 ′) each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms,
n, c and d each represent the average number of repeating units, n is 1 to 100, c is 0 to 100, and d is an integer of 1 to 100.

In the structural units (α), (β) and (γ), R ¹ , R ² and R ¹³ in the formulas (1), (2), (2 ′) and (3) are each a hydrogen atom, It is selected from methyl group and ethyl group. Ease of raw material availability, ease of synthesis of copolymer, especially copolymerization reactivity of raw material monomer {unsaturated ester compound} To a hydrogen atom or a methyl group.

R ³ is an alkyl group having 1 to 13 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, or a tridecyl group, a phenyl group, a benzyl group, a naphthyl group, or the like. The number of carbons such as methyl, ethyl, n-propyl, etc. is selected from among the aryl groups having 6 to 14 carbon atoms, from the viewpoint of availability of raw materials and ease of synthesis of the copolymer. Is preferably a lower alkyl group of 3 or less.

  B is an ester bond represented by COO or OCO. In the case of COO, B is an unsaturated carboxylic acid saturated ester structural unit, and in the case of OCO, it is a saturated carboxylic unsaturated ester structural unit.

  A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may have an ether bond or an ester bond in the main chain, and may have an ether bond or an ester bond for ease of synthesis. A good divalent hydrocarbon group having 3 to 10 carbon atoms is preferred. Specifically, the following hydrocarbon groups are exemplified.

R ¹⁴ is a vinyl group, an allyl group, a 1-butenyl group, a 9-decenyl group, a 2- (2- (2- (2-propenyloxy) ethoxy) ethoxy) ethyl group, or 2- (3-butenoyloxy). It is a C2-C20 polymerizable unsaturated hydrocarbon group which may have an ether bond or an ester bond in the main chain, such as an ethyl group and an oleyl group.

In the structural unit (β), X in the general formulas (2) and (2 ′) is a siloxane group represented by the formula (4) and / or the formula (4 ′). R ^{4 to} R ¹² and R ^{15 to} R ²² in the general formula (4) and the formula (4 ′) each have 1 carbon atom such as a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an n-hexyl group. Is selected from alkyl groups of ˜6 and aryl groups of 6 to 14 carbon atoms such as phenyl group, benzyl group, naphthyl group, etc., and the synthesis and availability of (poly) siloxane which is a synthesis raw material, These groups are preferably a methyl group or a phenyl group because of the high reactivity of the resulting copolymer and the effect on the curability of the silicone resin to be bonded.

  In the general formulas (4) and (4 ′), n, c, and d (average number of repeating siloxane units in the structural unit) are 1 ≦ n ≦ 100, 0 ≦ c ≦ 100, 1 ≦ d ≦ 100. In the case of the formula (4), 10 ≦ (1 + c) n + d ≦ 100, 0 <d / (, from the properties of the copolymer obtained and ease of synthesis. 1 + c) n ≦ 10, in the case of formula (4 ′), 10 ≦ c + d ≦ 100, 0 <d / c ≦ 10 (provided that 1 ≦ d ≦ 100 when c = 0), n, c, d It is preferable to select

  In the case where n is 2 or more, in the units of formula (4) and formula (4 ′), there are a plurality of bonds that are bonded to the structural unit (β) as many as the number n. The structural unit (β) repeatedly contained in the unsaturated ester polymer is bonded differently. That is, one unit of (4) and formula (4 ′) having n bonds is bonded to n structural units (β) constituting the main chain of the unsaturated ester polymer. Become a form.

  The siloxane groups represented by the formulas (4) and (4 ′) can be used without limitation within the above ranges, and among them, the adhesiveness with the hydrosilylation reaction curable silicone resin is particularly high. In view of this, those having a Si—H group which is a reactive functional group of the hydrosilylation reaction are preferable. From the viewpoint of reactivity, it is more preferable to select n and c so that there are 3 or more Si—H groups on average in one unit of the structural unit (β).

The content ratio of the structural unit (α) in the siloxane-modified unsaturated ester polymer used as the component (b) is preferably in the range of 10 to 99.9 mol%, particularly 50 to 99 mol%. The content ratio of (β) is preferably in the range of 90 to 0.1 mol%, particularly 50 to 1 mol%, and the content ratio of the structural unit (γ) is 0 to 89.9 mol%, particularly 0 to 0 mol%. It is preferably in the range of 49 mol%. (The structural units (α), (β), and (γ) may each be composed of a plurality of units as well as a single unit as long as they are represented by the general formula).
The structural unit (γ) is a polymerizable unsaturated hydrocarbon of the structural unit (γ) with an unsaturated ester polymer comprising the structural unit (α) and the structural unit (γ) as a precursor. An unsaturated ester system modified with a siloxane represented by the above general formula by introducing an X group represented by the formula (4) and / or the formula (4 ′) into the group using a hydrosilation reaction When a polymer is produced, it is generally contained as an unreacted residual unit. Therefore, in the unsaturated ester polymer modified with siloxane containing the structural unit (γ), the structural unit (β) is represented by the formula (2) and / or (2 ′). Of the units, usually the former unit.

  When the content ratio of the structural unit (α) is less than the above range, or when the content ratio of other structural units (β) and (γ) is more than the above range, the organo (poly (poly) in the structural unit (β) ) Even if the molecular weight of the siloxane group is reduced, the proportion of the organo (poly) siloxane part in the copolymer is larger than that in the unsaturated ester polymer part. As a result, the adhesive and the ethylene-vinyl acetate copolymer The familiarity with a polymer will worsen and adhesive force will fall. In addition, when the content ratio of the structural unit (γ) is larger than the above range, an excessively unsaturated bond inhibits the room temperature curing reaction (hydrosilylation curing reaction) of the silicone resin as the adherend. , It will no longer work as an adhesive.

Furthermore, when the content ratio of the structural unit (β) is less than the above range, the ratio of the organo (poly) siloxane portion in the copolymer is decreased, and the compatibility with the silicone resin is deteriorated. Adhesive strength is not sufficient. (The organo (poly) siloxane portion refers to a SiO skeleton portion having an organic group. R ^{4 to} R ^{12 in} the general formula (2), R ¹⁵ to R ¹⁵ in the general formula (2 ′) It means a portion determined by R ²² , n, c, d, and the unsaturated ester polymer portion means, for example, a poly (meth) acrylate skeleton portion or a polyvinyl ester skeleton portion, and these Is a portion other than the organo (poly) siloxane portion in the copolymer, and is determined by the number of structural units (α), (β) and (γ) and the proportion of the unsaturated ester portion occupying the structural unit (β). )
The weight average molecular weight of the siloxane-modified unsaturated ester polymer used as the component (b) described above is familiar to the adherend ethylene-vinyl acetate copolymer (adhesion strength), soluble in a solvent, and swellable. From the point, it is preferably in the range of 5,000 to 1,000,000, more preferably in the range of 10,000 to 500,000, and in this range, X in the formula (2) and / or (2 ′) indicating the structural unit (β), That is, the values of n, c, d in the formula (4) and / or the formula (4 ′), the copolymerization ratios of the structural units (α), (β), and (γ), and the total number of these polymerizations are determined. The In addition, in such a copolymer, from the viewpoints of compatibility with ethylene-vinyl acetate copolymer and silicone resin part, reactivity, and ease of synthesis, the molecular weight of the unsaturated ester polymer part and organo ( It is preferable to select a combination in which the ratio of the poly) siloxane moiety to the molecular weight is 1: 0.1-2.

  In the present invention, typical examples of the siloxane-modified unsaturated ester polymer used as the component (b) are as follows in terms of the structure of the structural unit and the average number of repeating units. .

  In the following formulae, Ph represents a phenyl group. The order of description of the structural units (α), (β), and (γ) is not particularly significant, and does not indicate the arrangement of the units in the copolymerization.

の共重合体は、一般にワックス状から白色粉末状の固体である。

These copolymers are generally waxy to white powdery solids.

  Note that the order of bonding of the structural units and siloxane units in the copolymer and the copolymers used in the examples and comparative examples described later is completely arbitrary, and the number of repeating units shown in the structural formula is simply each structural unit. As well as the average total amount of each siloxane unit.

  In the copolymer, the structural unit (α) represented by the formula (1), the structural unit (β) represented by the formula (2) and / or (2 ′), and the formula (3) The combination of structural units (γ) is not limited at all. However, from the viewpoint of ease of obtaining a copolymer, when B in Formula (1) and Formula (3) is COO, B in Formula (2) is COO. Preferably, when B in Formula (1) and Formula (3) is OCO, B in Formula (2) is preferably OCO. In the case of Formula (2 ′), B in Formula (1) and Formula (3) may be either COO or OCO.

  The structural unit (α) represented by the formula (1), the structural unit (β) represented by the formula (2) and / or (2 ′), and the structural unit (γ represented by the formula (3) Siloxane-modified unsaturated ester-based polymers comprising, for example, Japanese Patent No. 3105733, Japanese Patent No. 3107702, JP-A-60-231704, and Makromol. Chem. Volume 186, P685-694 (1985).

  Further, a method of transesterifying with an unsaturated ester polymer using a siloxane compound represented by the following formula prepared by the method described in Macromolecules Vol. 24, P122-125 (1991), etc. It can also be produced by a method of dehydrating and condensing an ester polymer after hydrolysis.

[In the above two formulas,
R ^{4 to} R ¹² and R ^{15 to} R ²² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms,
A represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may have an ether bond or an ester bond in the main chain;
n, c, and d represent the average number of repeating units, respectively, n is 1 to 100, c is 0 to 100, and d is an integer of 1 to 100. However, when n is 2 or more, it is bonded to the number of structural units (β). ]
In the present invention, the siloxane-modified unsaturated ester polymer can be used as the component (b). Also, several kinds of siloxane-modified unsaturated ester polymers can be mixed and used. When mixed and used, the ratio is not particularly limited.

The compounding quantity of the siloxane modification unsaturated ester polymer of the (b) component in this invention is 0.1-20 weight part with respect to 100 weight part organic solvent (a). If the blending amount is less than 0.1 parts by weight, the bond between the polymer and the curable silicone resin is insufficient, so that a strong adhesive force cannot be obtained. On the other hand, if the blending amount exceeds 20 parts by weight, the adhesive layer is too thick and the adhesive strength is lowered. In order to impart an appropriate viscosity and obtain an operational feeling such as applicability, the amount is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight.
[Ingredient (a): ]
The organic solvent of component (a) used in the present invention is not particularly limited as long as it dissolves or swells each polymer of component (b) and the ethylene-vinyl acetate copolymer. Halogenated organic solvents such as perchloroethylene, trichlorethylene, methylene chloride, chloroform, etc., hydrocarbon compounds such as hexane, heptane, pentane; aromatic compounds such as benzene, toluene, xylene; ethanol, 1-propanol, 2-propanol, Alcohol compounds such as 1-butanol and 2-butanol; ether compounds such as diethyl ether, tetrahydrofuran and t-butyl methyl ether; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl formate, methyl acetate, ethyl acetate and acetic acid Propyl, isopropyl acetate Ester compounds and the like; may be used a non-halogenated organic solvents such as. Particularly, since the ethylene-vinyl acetate copolymer has good solubility and swelling properties and high adhesiveness, halogen-based organic solvents such as perchloroethylene, trichloroethylene, and methylene chloride; aromatic compounds such as toluene and benzene; tetrahydrofuran More preferred are ether compounds such as methylene chloride, toluene, and tetrahydrofuran.

The organic solvent of component (a) may be a single organic solvent or a mixture of several organic solvents.
[Other ingredients:]
The adhesive of the present invention may contain additives such as a colorant and a fragrance in addition to the components (a) to (b) described above as long as the effects of the present invention are not impaired.
[Preparation of adhesive]
The adhesive of the present invention can be easily prepared by dissolving or swelling the siloxane-modified unsaturated ester polymer (b) in the organic solvent (a).

<How to use the adhesive>
The use method of the adhesive of the present invention described above is not particularly limited as long as it is used as an adhesive between an ethylene-vinyl acetate copolymer and a silicone resin. A typical operation method is a method in which the adhesive is applied to an ethylene-vinyl acetate copolymer, the solvent is evaporated, and an uncured silicone resin paste is placed thereon and cured. At the same time as the silicone resin is cured, it adheres to the ethylene-vinyl acetate copolymer, and the adhesion is completed when the curing is completed.

  In addition, a well-known thing can be used without a restriction | limiting as an ethylene-vinyl acetate copolymer used as the object of use of this adhesive agent. The content ratio of the ethylene unit and the vinyl acetate unit in the ethylene-vinyl acetate copolymer is from 99.5 to 60 in terms of the solubility / swellability in a solvent and the properties (strength and flexibility) of the copolymer. It is preferable that the vinyl acetate unit is 0.5 to 40% by mass. Furthermore, it is more preferable that an ethylene unit is 95-70 mass% and a vinyl acetate unit is 5-30 mass%. Further, even if it contains polymerized units derived from other polymerizable monomers that can be copolymerized within a range that does not greatly affect the properties of the ethylene-vinyl acetate copolymer (usually within 10% by mass). good. Examples of other copolymerizable monomers that can be copolymerized include methyl (meth) acrylate, vinyl chloride, and styrene.

  Further, various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, a crystal nucleating agent, and a plasticizer may be added as long as the properties of the ethylene-vinyl acetate copolymer are not impaired. The content of these additives is usually in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer.

  In addition, blends of ethylene-vinyl acetate copolymer and other (co) polymers as long as the properties (hardness, flexibility) required for mouth guard and the adhesiveness of this adhesive are not impaired. May be used. Examples of other polymers to be blended include polyethylene, polyvinyl acetate, polyvinyl alcohol, polypropylene, polystyrene, polycaprolactone, poly (meth) acrylate methyl, and the content thereof is usually ethylene-vinyl acetate. It is within 80 parts by weight with respect to 100 parts by weight of the copolymer.

  In addition, the silicone resin to be used for this adhesive is made of a polymer of a compound having a siloxane bond as the main chain (organopolysiloxane) and usually has good flexibility after curing. Used. Known silicone resins having such flexibility can be used without limitation. Examples of the polymerization mode for curing include heat vulcanization type, condensation type, addition type, and ultraviolet curing type, but it can be cured directly in the patient's oral cavity and no by-product is generated. A room temperature addition polymerization type is preferred.

As such a room temperature addition polymerization type silicone resin-based curable composition,
(I) an organopolysiloxane having at least two organic groups having carbon-carbon unsaturated bonds at its ends in the molecule;
(Ii) an organohydrogenpolysiloxane having at least three SiH groups in the molecule;
(Iii) a hydrosilylation catalyst, and (iv) a silicone resin filler and / or a silica filler,
A curable composition comprising is preferred. The silicone resin-based curable composition further includes
(V) an organohydrogenpolysiloxane having one or two SiH groups in the molecule;
You may react by coexisting. When this component (v) is mix | blended, there exists a tendency for an elasticity modulus to become small, and it becomes easy to adjust the viscoelasticity of a hardening body.

  Details of each component used in these silicone resin-based curable compositions are known from JP-A-10-226613, JP-A-2001-79020, etc., and the same as those described in the present invention. Is used.

  Such a silicone resin-based curable composition is usually used by a so-called two-component mixing method. That is, the A material containing the curing catalyst and the B material not containing the curing catalyst (both materials are liquid or pasty) are separately adjusted and stored, and cured by kneading both immediately before use. Used.

  In addition, various fillers and various additives other than those described above may be added to the silicone resin-based curable composition as long as the physical properties of the cured product are not impaired.

According to the adhesive of the present invention, the silicone resin can be firmly adhered to the ethylene-vinyl acetate copolymer in a short time simultaneously with the curing of the silicone resin-based curable composition by the hydrosilation reaction.

(Use for repair and adjustment of mouth guard made of ethylene-vinyl acetate copolymer)
For mouth guards made of ethylene-vinyl acetate copolymer, if the mouth guard occlusal surface part is frayed or punctured due to tightening during use, etc., or if you want to correct the occlusal relationship and compatibility when wearing the mouth guard. The mouth guard can be easily repaired and adjusted by using the adhesive of the present invention and the silicone resin-based curable composition. A typical method is shown below, but is not limited thereto.

A mouth guard made of an ethylene-vinyl acetate copolymer is used as a mouth guard base, and a portion to be repaired or a portion to be adjusted is thoroughly washed and dried. Next, the adhesive is applied to the part to be repaired and adjusted, and the solvent is evaporated. After evaporating the solvent, an uncured paste of silicone resin is placed as a surface material on the adhesive application portion, and is placed on the user's dentition or the user's dentition model before curing. The mouth guard can be repaired or adjusted by curing the silicone resin while it is being worn.

(Use for manufacturing shell liner type mouth guard)
The adhesive of the present invention can be used effectively when manufacturing a mouth guard in which the base is made of the ethylene-vinyl acetate copolymer and the surface layer material made of silicone resin is bonded to the inner and outer surfaces thereof. Is done. As such a mouth guard, the shell liner type mouth guard is representative. That is, the shell liner type mouth guard refers to a mouth guard in a form in which a silicone resin is lined as a gap layer between the inner surface of the shell which is a mouth guard base and the oral cavity. The manufacture is a method as shown in the above-mentioned Patent Document 2, and by using the adhesive of the present invention in its implementation, a hygienic mouth guard that is durable and hardly adheres to the interface is manufactured. I can do things. Although the specific manufacturing method is shown below, it is not limited to this.

  That is, a mouth guard shell made of an ethylene-vinyl acetate copolymer is used as a mouth guard base, the adhesive is applied to the inner surface, and the solvent is evaporated. After evaporation of the solvent, an uncured paste of silicone resin that serves as a liner is lined on the inner surface to which the adhesive has been applied. Next, a mouth guard shell having an inner surface lined with an uncured paste of silicone resin is placed on the dentition of the mouth guard user to fit the shape. A shell liner type mouth guard can be manufactured by curing the uncured paste of the curable silicone resin in a state of being mounted on the dentition.

  Moreover, you may perform shaping | molding, such as cutting or shaving the excess part of a liner in the range which does not impair the function of a mouth guard. Moreover, what can identify a mouth guard user (owner), such as a name plate and a design sheet, may be inserted between the shell and the liner as long as the function of the mouth guard is not impaired.

  The mouth guard shell can be formed without any limitation as long as it is a known method. For example, a method of injecting a molten ethylene-vinyl acetate copolymer into a mouth guard shell mold or molding an ethylene-vinyl acetate copolymer softened by heating into a mold or model of a mouth guard shell. There is a method of forming by pressure welding.

  There are no restrictions on the shape of the mouth guard shell, but in order to produce a mouth guard that absorbs shock sufficiently and has a good fit, the mouth guard shell has a thickness of 0.5 mm to 3 mm, the inner surface of the mouth guard and the teeth. A shape having a gap of 0.5 mm to 3 mm (a gap layer in which the silicone resin is lined) between the rows is preferable.

  In addition, although there is no restriction on the preparation of the mouth guard shell, in order to manufacture a mouth guard that is easy and quick and has a good wearing feeling, ready-made mouth guard shells of several sizes such as S, M, and L are prepared. It is preferable to select one that matches the size of the user's dentition.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples. The materials used for the test are shown below.
Component (a) Organic solvent, methylene chloride (Wako Pure Chemicals, special grade)
・ Ethyl acetate (Wako Pure Chemicals, special grade)
・ Toluene (Wako Pure Chemicals, special grade)
・ Tetrahydrofuran (Wako Pure Chemicals, special grade)
Ingredient (b)
-Siloxane-modified (meth) acrylic polymer-Siloxane-modified vinyl ester polymer The following copolymers were used.

Copolymer (I)

Copolymer (b)

Copolymer (C)

Copolymer (d)

Copolymer (e)

共重合体（へ）

Copolymer (he)

Copolymer (g)

Copolymer (h)

Copolymer (R)

Copolymer (nu)

Copolymer (Le)

Copolymer (Wo)

Copolymer (wa)

Copolymer (f)

The above copolymer was synthesized by the following method.
Synthesis Method of Copolymer (I) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.26 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer (weight average molecular weight of 120,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50 to 1 (molar ratio) was obtained.

  In a flask, a hydrogen siloxane compound “DMS-M20H20” (Shin-Etsu Chemical)

27.7 g, toluene 300 ml, and platinum / divinylsiloxane complex solution 0.33 g adjusted to 1000 ppm platinum were added and heated to 80 ° C. and stirred while bubbling nitrogen. A solution prepared by dissolving 5 g of a copolymer (weight average molecular weight 120,000) of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized in the above method in 100 ml of toluene was added dropwise over 1 hour. Then, after completion of the dropwise addition, the mixture was further heated and stirred for 6 hours. After removing toluene under reduced pressure, the excess “DMS-M20H20” was washed with a methanol / ethanol mixed solvent, and then filtered and dried to obtain the copolymer (I). Obtained. The weight average molecular weight of the obtained polymer was 180,000 as a polystyrene standard.

Synthesis method of copolymer (b) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.40 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50 to 1 (molar ratio) (weight average molecular weight 80000) was obtained.

  Hydrogen siloxane compound "DMS-M10H10P10" of the following formula (Shin-Etsu Chemical)

And a copolymer having a copolymerization ratio of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above-described method (weight average molecular weight 80,000) and synthesized in the same manner as the synthesis of copolymer 1. Copolymer 2 was obtained. The weight average molecular weight of the obtained polymer was 120,000 based on polystyrene.

Synthesis method of copolymer (c) 25 g of methyl methacrylate, 1.30 g of methacrylic acid triethylene glycol monoallyl ether ester, 0.31 g of azobisisobutyronitrile and 30 ml of toluene were put into a flask, and nitrogen was bubbled. While stirring at 70 ° C., a copolymer (weight average molecular weight 100000) of methyl methacrylate and triethylene glycol monoallyl ether ester having a copolymerization ratio of 50: 1 (molar ratio) was obtained.

Copolymer (weight average) of 50: 1 (molar ratio) of the copolymerization ratio of hydrogen siloxane compound “DMS-M20H20” (Shin-Etsu Chemical Co., Ltd.) and methyl methacrylate and triethylene glycol monoallyl ether ester of methacrylic acid synthesized by the above method. Using a molecular weight of 100,000), the synthesis was performed in the same manner as the synthesis of the copolymer 1 to obtain a copolymer 3. The weight average molecular weight of the obtained polymer was 150,000 in terms of polystyrene.

Synthesis method of copolymer (d) 25 g of propyl methacrylate, 1.1 g of allyl methacrylate, 0.57 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer (weight average molecular weight 60,000) having a 57: 2 (molar ratio) copolymerization ratio of propyl methacrylate and allyl methacrylate was obtained.

Copolymer using hydrogensiloxane compound DMS-M20H20 (Shin-Etsu Chemical Co., Ltd.) and a copolymer (weight average molecular weight 60,000) of propyl methacrylate and allyl methacrylate synthesized by the above-mentioned method in a ratio of 57 to 2 (molar ratio). Synthesis was performed in the same manner as in Synthesis 1, and a copolymer 4 was obtained. The weight average molecular weight of the obtained polymer was 120,000 based on polystyrene.

Synthesis method of copolymer (e) Hydrogen siloxane compound "DHS-M20H20" (Shin-Etsu Chemical)

And a copolymer (weight average molecular weight 120,000) having a copolymerization ratio of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized with the copolymer (a). The same synthesis as in the method was performed to obtain a copolymer (e). The weight average molecular weight of the obtained polymer was 180,000 as a polystyrene standard.

25 g of methyl methacrylate in the synthesis flask of copolymer (he) , siloxane compound of the following formula

2.3 g, 0.26 g of azobisisobutyronitrile and 30 ml of toluene were heated and stirred at 80 ° C. for 5 hours while bubbling nitrogen to obtain a copolymer (f). The weight average molecular weight of the obtained polymer was 130,000 based on polystyrene.

Synthesis of Copolymer (G) Living Anion Polymerization of Cyclic Trimer of Dimethylsiloxane Using Butyllithium Catalyst, Dimethylvinylchlorosilane (CH ₂ ═CH—Si (CH ₃ ) ₂ Cl) Added to the Cup, Copolymerization with vinyl acetate was carried out under the following conditions using macromonomer A containing, on average, the following polysiloxane groups synthesized by ring reaction.

  [Macromonomer A]

For copolymerization, 10 g of the above macromonomer A, 90 g of vinyl acetate, 50 g of benzene and 0.75 g of azobisisobutyronitrile were put together in an ampule, sealed after nitrogen substitution, and polymerized at 60 ° C. for 1.5 hours. did. The ampoule is opened, the contents are poured into a large amount of petroleum ether, the precipitated polymer is further washed with petroleum ether to remove unreacted vinyl acetate and macromonomer A, and dried to obtain a copolymer (g). It was. The weight average molecular weight of the obtained polymer was 230000 as polystyrene standard.

Copolymerization was carried out under the same conditions as the copolymer (g) except that the macromonomer B having the following molecular structure was used as the synthesis average value of the copolymer (h) . The weight average molecular weight of the obtained polymer was 230000 as polystyrene standard.

  [Macromonomer B]

25 g of polyvinyl acetate (weight average molecular weight 100000) and 100 ml of 10% potassium carbonate / ethanol solution were placed in a copolymer (ri) synthesis flask and hydrolyzed with heating under reflux for 20 hours. It was filtered and dried to obtain a polymer in which a part of vinyl acetate was saponified with vinyl alcohol.

  Next, 10 g of the polymer, 400 ml of benzene, 5 g of a tin complex catalyst, and a siloxane compound of the following formula in a flask

10 g was added and heated under reflux for 6 hours to conduct a transesterification reaction. After allowing to cool, the organic layer was separated by diluting with water, washed with a saturated aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a copolymer (Li). The weight average molecular weight of the obtained polymer was 150,000 in terms of polystyrene.

Synthesis method of copolymer (nu) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 7.6 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer (weight average molecular weight 5000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50 to 1 (molar ratio) was obtained.

Using the hydrogen siloxane compound “DMS-M20H20” (Shin-Etsu Chemical) and a copolymer of 50 to 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above method (weight average molecular weight 5000). The same synthesis as that carried out with the copolymer (I) was carried out to obtain a copolymer (nu). The weight average molecular weight of the obtained polymer was 8,000 in terms of polystyrene.

Synthesis method of copolymer (l) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.12 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer (weight average molecular weight 250,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50: 1 (molar ratio) was obtained.

Using the hydrogen siloxane compound “DMS-M20H20” (Shin-Etsu Chemical) and a copolymer (weight average molecular weight 250,000) having a copolymerization ratio of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above-described method. The same synthesis as that carried out with the copolymer (I) was carried out to obtain a copolymer (L). The weight average molecular weight of the obtained polymer was 400000 as polystyrene standard.

Synthesis Method of Copolymer ( O ) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.056 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer (weight average molecular weight of 500,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50 to 1 (molar ratio) was obtained.

Using the hydrogen siloxane compound “DMS-M20H20” (Shin-Etsu Chemical) and a copolymer of 50 to 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above method (weight average molecular weight 500000) The same synthesis as that carried out with the copolymer (I) was carried out to obtain a copolymer (W). The weight average molecular weight of the obtained polymer was 800,000 as a polystyrene standard.

Synthesis method of copolymer (wa) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.027 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. Thus, a copolymer (weight average molecular weight 1000000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50: 1 (molar ratio) was obtained.

Copolymer using hydrogen siloxane compound DMS-M20H20 (Shin-Etsu Chemical Co., Ltd.) and a copolymer of methyl methacrylate and allyl methacrylate synthesized by the above-described method in a 50: 1 (molar ratio) copolymer (weight average molecular weight 1000000). Synthesis was performed in the same manner as in the synthesis of 1 to obtain a copolymer (wa). The weight average molecular weight of the obtained polymer was 1600000 as polystyrene standard.

Synthesis method of copolymer (f) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.26 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. As a result, a copolymer (f) (weight average molecular weight 120,000 based on polystyrene standard) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50: 1 (molar ratio) was obtained.

In the following Examples and Comparative Examples, the addition type silicone resin used for the measurement of the adhesive strength is obtained by kneading and curing the following A1, A2 paste and B1, B2 paste in the same amount.

A1 paste:
・ Polydivinyldimethylsiloxane "ME91" (Toshiba Silicone) 50 parts by weight

・ 50 parts by weight of polydivinyldimethylsiloxane “XC86-A9723” (Toshiba Silicone)

・ Platinum / vinylsiloxane complex solution (platinum 1000 ppm, Pt / V2) 0.3 part by weight ・ Polymethylsilsesquioxane fine particles (particle size 3 μm, obtained by hydrolyzing methyltrimethoxysilane) 40 parts by weight

A2 paste:
-Polydivinyldimethylsiloxane "ME91" (Toshiba Silicone) 50 parts by weight-Polydivinyldimethylsiloxane "XC86-A9723" (Toshiba Silicone) 50 parts by weight-Polyhydrogenmethylsiloxane
"DMS-M20H20" (Shin-Etsu Chemical) 2 parts by weight

    "TSL9586" (Toshiba Silicone) 7 parts by weight

The tensile strength of the cured silicone resin obtained by kneading these A1 and A2 pastes in equal amounts is about 2.0 MPa.

B1 paste:
-Polydivinyldimethylsiloxane "ME91" (Toshiba Silicone) 60 parts by weight-Polydivinyldimethylsiloxane "XC86-A9723" (Toshiba Silicone) 40 parts by weight-Platinum / vinylsiloxane complex solution (platinum 1000 ppm, Pt / V2) 0.3 Part by weight-Silica powder (primary particle size 0.01 μm, Leoroseal MT-10: Tokuyama) 10 parts by weight-Polypropylene glycol (molecular weight 3000, Wako Pure Chemical Industries) 0.1 part by weight B2 paste:
-Polydivinyldimethylsiloxane "ME91" (Toshiba Silicone) 40 parts by weight-Polydivinyldimethylsiloxane "XC86-A9723" (Toshiba Silicone) 60 parts by weight-Polyhydrogenmethylsiloxane "DMS-M20H20" (Shin-Etsu Chemical) 3 parts by weight・ Silica powder (“Leoroseal MT-10” (Tokuyama) 10 parts by weight ・ Polypropylene glycol (Wako Pure Chemicals) 0.1 part by weight Tensile strength of cured silicone resin obtained by kneading these B1 and B2 pastes in equal amounts The strength is about 2.0 MPa.

  The operations, measurement procedures, and evaluation criteria relating to the evaluation of adhesive strength, adhesion durability, and mouth guard hygiene are as follows.

(A) Evaluation of adhesive strength The prepared adhesive solution was applied to a sheet of ethylene-vinyl acetate copolymer having a length of 3 cm, a width of 3 cm, and a thickness of 1.5 mm, and both A1 and A2 pastes or both B1 and B2 pastes were applied. The same amount was taken, kneaded well, and placed on an ethylene-vinyl acetate copolymer sheet coated with an adhesive solution. Before curing the paste, the bottom surface of a 6 mm diameter, 2 cm high, cylindrical polymethylmethacrylate tensile test rod is primed with “Soft Primer Primer” (manufactured by Tokuyama Dental Co., Ltd.) before curing. The treated surface was placed on the paste and pressed. The excess paste that came out on the side of the rod was taken and left at 25 ° C. for 10 minutes to cure the paste. After curing, a tensile test was performed using an autograph (manufactured by Shimadzu Corporation).

  The test was conducted 5 times for each condition, and the average of 5 times was 500 kPa or more, ◯, 100 kPa or more, less than 500 kPa was rated as ○, and less than 100 kPa was evaluated as ×, and the adhesive strength was evaluated.

(B) Evaluation of adhesion durability Similar to the evaluation of adhesion strength, a specimen for a tensile test was produced.

  The test body produced by the above method was immersed in 37 ° C. water for 24 hours, and then a thermal cycle test at 4 ° C. and 60 ° C. was performed 5000 times using a thermal shock tester (Thomas Scientific Instruments Co., Ltd.). About the test body after a heat cycle test, the tensile test by an autograph was each performed similarly to evaluation of adhesive force.

  The test was conducted 5 times for each condition, and the evaluation of adhesion durability was evaluated as “A” when the average of 5 times was 500 kPa or more, “B” when 100 kPa or more and less than 500 kPa, and “B” when less than 100 kPa.

(C) Sanitary evaluation of mouth guard The prepared adhesive solution was applied to the inner surface of the mouth guard shell made of an ethylene-vinyl acetate copolymer, and the solvent was sufficiently dried. A1 and A2 pastes, or B1 and B2 pastes were taken in equal amounts, kneaded well, and placed on the surface to which the adhesive was applied. A mouth guard shell loaded with an uncured paste of silicone resin was placed on the dental model and matched in shape. The silicone resin uncured paste was cured to produce a shell liner type mouth guard.

The mouth guard prepared by the above method was immersed in an aqueous solution of 7.4 wt% coffee (Nescafe Excella, Nestlé Japan) and held at 60 ° C. for 5 hours with stirring. Then, it washed with water, dried, observed the coloring of the interface of an ethylene-vinyl acetate copolymer and a silicone resin, and evaluated in four steps from A to D according to the following determination.
A: No coloration B: Less than 10% of the interface is colored C: Less than 50% of the interface is colored D: 50% or more of the interface is colored All five times are A ◎ Five test results are A or B, C and D are not included ○ Five test results are A, B or C and D are not included The result was Δ, and the test result including D in the 5th test was evaluated as x.

Example 1
As shown in Table 1, 1.5 parts by weight of a siloxane-modified (meth) acrylic polymer [copolymer (I)] is added to and mixed with 100 parts by weight of methylene chloride (organic solvent). An adhesive of the present invention was prepared. Further, A1 and A2 pastes were used as the addition type silicone resin. When the adhesive strength, durability and hygiene were evaluated using the prepared adhesive, all were good as shown in Table 2.

Examples 2-22
An adhesive was prepared in the same manner as in Example 1 except that the composition shown in Table 1 was used, and the adhesive strength, durability, and hygiene were evaluated. The results are shown in Table 2. Even when any adhesive was used, it was good.

Examples 23-25
As shown in Table 1, adhesives were prepared in the same manner as in Example 1 except that B1 and B2 pastes were used as addition-type silicone resins, and the adhesive strength, durability, and hygiene were evaluated. The results are shown in Table 2. Even when any adhesive was used, it was good.

Comparative Example 1
As shown in Table 1, a sample was prepared by the same method as in Example 1 without using an adhesive, and the adhesive strength, durability, and hygiene were evaluated. The results are shown in Table 2. None of them adhered, and the durability and hygiene were poor.

Comparative Example 2
As shown in Table 1, adhesive strength, durability, and hygiene were evaluated in the same manner as in Example 1 using only the solvent (methylene chloride) without adding the siloxane-modified unsaturated ester polymer. The results are shown in Table 2. None of them adhered, and the durability and hygiene were poor.

Comparative Example 3
As shown in Table 1, in Example 1, instead of the siloxane-modified unsaturated ester polymer [copolymer (I)], as the unsaturated ester polymer not modified with siloxane, methyl methacrylate and allyl An adhesive was prepared in the same manner as in Example 1 using a polymer obtained by copolymerizing methacrylate at a ratio of 50: 1 (molar ratio) [copolymer (f)], and evaluation of adhesive strength, durability, and hygiene was performed. Went. The results are shown in Table 2. None of them adhered, and the durability and hygiene were poor.

Comparative Example 4
As shown in Table 1, in Example 1, instead of the siloxane-modified unsaturated ester polymer [copolymer (I)], “DMS-M20H20” which is a hydrogen siloxane compound was used. The adhesive was adjusted in the same manner as above, and the adhesive strength, durability, and hygiene were evaluated. The results are shown in Table 2. None of them adhered, and the durability and hygiene were poor.

Comparative Example 5
As shown in Table 1, the adhesive was adjusted in the same manner as in Example 1 using water as an insoluble solvent for the ethylene-vinyl acetate copolymer, and the adhesive strength, durability, and hygiene were evaluated. . The results are shown in Table 2. None of them adhered, and the durability and hygiene were poor.

Comparative Example 6
As shown in Table 1, using the copolymer (wa), the adhesive was adjusted in the same manner as in Example 1, and the adhesive strength, durability, and hygiene were evaluated. The results are shown in Table 2. Almost no adhesion, durability and hygiene were poor.

Claims (6)

  Adhesive of ethylene-vinyl acetate copolymer and silicone resin comprising (a) 100 parts by weight of organic solvent and (b) 0.1-20 parts by weight of unsaturated ester polymer modified with siloxane . (B) The ethylene-vinyl acetate copolymer according to claim 1, wherein the unsaturated ester polymer modified with siloxane is an unsaturated ester polymer modified with siloxane having a reactive functional group for hydrosilylation reaction. Adhesive between polymer and silicone resin. The unsaturated ester polymer modified with the siloxane of the component (b) has a structural unit (α) represented by the following formula (1) of 10 to 99.9 mol%, the following formula (2) and / or ( 2 ′) is contained in a proportion of 90 to 0.1 mol%, and the structural unit (γ) represented by the following formula (3) is contained in a proportion of 0 to 89.9 mol%. The adhesive according to claim 2, which is a copolymer having a weight average molecular weight of 1,000,000;

[In the above formulas (1), (2), (2 ′) and (3),
R ¹ , R ² and R ¹³ each represent a hydrogen atom, a methyl group or an ethyl group,
R ³ represents an alkyl group having 1 to 13 carbon atoms or an aryl group having 6 to 14 carbon atoms,
B represents an ester bond represented by COO or OCO;
A represents a C 2-20 divalent hydrocarbon group which may have an ether bond or an ester bond in the main chain;
R ¹⁴ represents a C 2-20 polymerizable unsaturated hydrocarbon group that may have an ether bond or an ester bond in the main chain;
X is the formula (4)

And / or formula (4 ′)

A siloxane group represented by
R ^{4 to} R ¹² and R ^{15 to} R ²² in the formulas (4) and (4 ′) each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms,
n, c and d each represent the average number of repeating units, n is 1 to 100, c is 0 to 100, and d is an integer of 1 to 100. ]   The adhesive according to any one of claims 1 to 3, wherein the ethylene-vinyl acetate copolymer is a mouth guard substrate, and the silicone resin is a surface layer material that adheres to the inner and outer surfaces of the mouth guard substrate.   The adhesive according to any one of claims 1 to 4, wherein the mouth guard substrate is a shell of a shell liner type mouth guard, and the surface layer material is a liner lining inside the shell.   After applying the adhesive according to any one of claims 1 to 3 to the inner surface of an ethylene-vinyl acetate copolymer mouth guard shell, a silicone resin uncured paste was lined, and then obtained. A method for producing a shell liner type mouth guard, characterized in that a mouth guard shell having a silicone resin uncured paste lined on the inner surface is fitted on a tooth row and the shape is adapted, and then the silicone resin uncured paste is cured. .