JP5213351B2 - Adhesive base material and silicone rubber adhesive using the same - Google Patents

Description

  The present invention relates to a base material made of metal, polymer resin, glass or ceramics modified so that silicone rubber can adhere to the surface, and an adhesive body of the base material and silicone rubber.

  In order to bond an adherend made of a hard material such as metal or ceramics to an adhesive member made of a soft material such as silicone rubber, physical bonding by intermolecular interaction at the bonding interface Alternatively, chemical bonding is performed by chemical bond formation at the bonding interface.

  As such a physical bonding method, a mechanical bonding method is known in which the surface of the member to be bonded is roughened to increase the contact area for bonding, and as a chemical bonding method, the bonding is performed. Adhesive method that presses an adhesive member after applying a heat-curable adhesive to the member, a surface to be bonded by chemically bonding to the surface molecules of the adhesive member after surface treatment of the member to be bonded and introduction of reactive groups Processing methods are known. In addition, a method of improving the reactivity between the vinyl group and silicone rubber by a treatment for attaching a vinyl compound to a metal surface as in Patent Document 1 is also known. Also, a method of applying a liquid silicone rubber composition comprising a vinyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a silane coupling agent such as a platinum catalyst to the surface of a metal plate that has been subjected to a degreasing and cleaning treatment, and curing and bonding the composition. Is also known.

  The bonded body by the mechanical bonding method is easily peeled off. Adhesives made by the adhesive method do not chemically bond them directly at the interface between the adherend and the adhesive member, so that the adhesive deteriorates when exposed to severe heat cycles or after a long period of time. As a result, the adhesive strength decreases. In addition, the bonded body by the surface treatment method generally has a relatively strong adhesive strength only by forming 2 to 4 chemical bonds per 10000 atoms on the surface of the non-adhesive substrate, and the ambient temperature or solvent during bonding. Adhesive strength is not governed by the environment such as the presence of the material, but it is difficult to reliably generate a chemical bond at the interface between the bonded member and the bonded member, and only a substrate made of a very limited material should be used. It is not possible and lacks versatility.

  In particular, when the adhesive member is made of silicone rubber, its strength is weak, and since the interaction and reactivity with the surface of the member to be bonded at the interface are poor, it is difficult to bond, and even when bonded, the strength is low. For this reason, there is only a method of bonding the silicone rubber and the adherend member surface with an adhesive that easily interacts with the silicone rubber, and a very strong bonding strength cannot be obtained.

  Moreover, since the adhesive layer is usually several μm to several 100 μm, it can disperse stress when it is pulled or bent, but the amount of the adhesive is too small to increase the adhesive strength so much. When the amount of the adhesive is increased and the adhesive layer is thickened, strain is concentrated due to stress, and the adhesive layer is easily peeled off. On the contrary, the adhesive strength is lowered. It is difficult to balance that.

  Furthermore, with the adhesive method, it is difficult to bond minute members to each other.

JP 2006-198797 A

  The present invention has been made in order to solve the above-mentioned problems, and a base material formed of metal, polymer resin, glass or ceramics, and silicone rubber is used more than before without a thick adhesive layer. An object of the present invention is to provide a simple adhesive base material for obtaining a silicone rubber bonded body which is bonded strongly and firmly and does not peel off or tear even if it is pulled or bent.

The adhesive substrate according to claim 1, which has been made to achieve the above object, comprises a hydrosilyl-containing silyl group, a vinyl-containing silyl group that reacts and bonds to a reactive group on the surface of the solid to be bonded. Dehydration of a hydroxyl group having at least one active silyl group selected from a group, an alkoxysilyl-containing silyl group, and a hydrolyzable group-containing silyl group on the surface of a substrate formed of metal, polymer resin, glass or ceramics Based on the silyl ether bond, an adhesive surface is formed ,
The active silyl group is
It is selected from a monohydrosilyl-containing silyl group and a dihydrosilyl-containing silyl group, and —SiH (R ¹ ) ₂ or —SiH ₂ (R ² ) (R ¹ and R ² are alkyl having 1 to 4 carbon atoms ) at the terminal of the group The hydrosilyl-containing silyl group having a group) or having a —SiH— group in the middle of the main chain of the group;
A vinyl silyl-containing silyl group, the terminal of the group has -Si-R ³ group a (R ³ is a vinyl containing group), or a middle -Si backbone of the group (R ⁴⁾ - group (R ⁴ is a vinyl-containing group) having the vinyl-containing silyl group;
It is selected from trialkoxysilyl terminal-containing silyl group and dialkoxysilyl terminal-containing silyl group, and at the terminal of the group, -Si (OR ⁵ ) ₂ R ⁶ group (R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms) Or an alkoxysilyl-containing silyl group having a —Si (OR ⁷ ) ₃ group (R ⁷ is an alkyl group having 1 to 4 carbon atoms);
The hydrolyzability selected from acyloxysilyl group, alkenyloxysilyl group, alkaneiminooxysilyl group, alkyloxysilyl group, alkylaminosilyl group, dialkylaminosilyl group, nitrogen-containing heterocyclic substituted silyl group, and arylaminosilyl group -Si (R ⁸ ) _a (R ⁹ ) _3-a group (R ⁸ is a hydrogen atom; a halogen atom; an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkyloxy group, A fluorine-substituted alkyl group; an aralkyl group; an aryl group, and R ⁹ is an acyloxy group having 1 to 12 carbon atoms, an alkenyloxy group, an alkaneiminooxy group, an alkyloxy group, an alkylamino group, a dialkylamino group; A cyclic group and an arylamino group, wherein a is a number of 0 to 3) and includes the hydrolyzable group having the hydrolyzable functional group. Silyl group
And
A catalyst comprising a platinum-containing catalyst or a rhodium-containing catalyst that bonds the solid by reacting and reacting with a reactive group on the surface of the solid on the adhesive surface is attached to the adhesive surface bonded with the silyl ether,
Further, a composition containing a silicone rubber component of polysiloxanes, vinyl silicones and / or silanol silicones, which is degassed under reduced pressure, is cured, and the surface is coated to adhere the silicone rubber. And
It is the base material for adhesion | attachment which adheres the said silicone rubber with the said composition degassed under reduced pressure .

The bonding substrate according to claim 2 is the bonding substrate according to claim 1, wherein the hydroxyl group is a hydroxyl group on the surface of the substrate, or corona discharge, atmospheric pressure plasma treatment and ultraviolet irradiation to the substrate. It is a hydroxyl group produced by any of the treatments described above, and is characterized in that the silyl ether bond is formed on the active silyl group derived from the alkoxysilyl group of the alkoxysilane compound.

  The adhesive base material according to claim 3 is the adhesive base material according to claim 2, wherein the solid surface is oxidized to have the hydroxyl group, and the active silyl group derived from an alkoxysilyl group includes the active silyl group. It is characterized by silyl ether bonding.

  According to a fourth aspect of the present invention, there is provided the adhesive substrate according to the third aspect, wherein a monomolecular film is formed by the silyl ether bond with the alkoxysilane compound.

The bonding substrate according to claim 5 is the bonding substrate according to claim 2 , wherein the treatment is continued until a surface tension of at least 55 kJ / m is obtained on the surface of the substrate. Features.

The adhesive substrate according to claim 6 is the adhesive substrate according to claim 1 , wherein the silyl ether bond has the following chemical formula [1]
Sub.-O-SiR ²⁰ ... [1]
(In the formula [1], Sub. Is the substrate that is the adherend substrate and is a group that forms this silyl ether bond, and -SiR ²⁰ is the hydrosilyl-containing silyl group that is a polysiloxy group ). It is characterized by being expressed .

The bonding substrate according to claim 7 is the bonding substrate according to claim 1 , wherein the silyl ether bond has the following chemical formula [2]
Sub.-O-SiR ²¹ ... [2]
(Wherein [2], Sub. Is a group which forms a silyl ether linkage A wherein the substrate is a adherend substrate, -SiR ²⁰ in the vinylsilyl-containing silyl group chromatic 1 to 30 vinyl groups It is characterized by being expressed .

An adhesive base material according to an eighth aspect is the one according to the first aspect , wherein the silyl ether bond has the following chemical formula [3]
Sub.-O-SiR ²² ... [3]
(In the formula [3], Sub. Is a substrate that forms the silyl ether bond and is the substrate that is the adherend substrate, and —SiR ²² is — (C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,-(C ₂ H ₅ O) CH ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,-(C ₂ H ₅ O) ₂ SiCH = CHSi (OC ₂ H ₅ ) ₃ ,-(CH ₃ O) ₂ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ ,-(CH ₃ O) ₂ SiCH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,-(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₃ Si (OCH ₃ ) ₃ ,-(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₄ Si (OCH ₃ ) ₃ ,-(CH ₃ O) CH ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ ,-(C ₂ H ₅ O) CH ₃ SiOSi (OC ₂ H ₅ ) ₂ CH ₃ ,-(C ₂ H ₅ O) Si (OC ₂ H ₅ ) ₂
Any one of the above-mentioned alkoxysilyl terminal-containing silyl groups . ) .

The bonding substrate according to claim 9 is the bonding substrate according to claim 1 , wherein the silyl ether bond has the following chemical formula [4]:
Sub.-O-Si (R ⁸ ) _a (R ⁹ ) _3-a ... [4]
(In the formula [4], Sub. Is a substrate that forms the silyl ether bond and is the substrate that is the adherend substrate, and —Si (R ⁸ ) _a (R ⁹ ) _3-a is R ⁸ _{but, H-, F-, CH 3 -} , C 2 H 5 -, CH 2 = CH-, nC 3 H 7 -, iC 3 H 7 -, CH 2 = CHCH 2 -, C 4 H 9 -, C _{6 H 13 -, C 8 H} 17 -, C 6 H 5 -, CH 3 C 6 H 4 -, C 6 H 5 CH 2 -, CF 3 CF 2 CH 2 CH 2 -, CF 3 CF 2 CF 2 CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , CH ₃ O-, or C ₂ H ₅ O-, R ⁹ is CH ₃ COO-, CH ₂ = C (CH ₃ ) O-, C ₂ H ₅ (CH ₃ ) C = NO-, CH ₃ O-, (CH ₃ ) ₂ N-, (C ₂ H ₅ ) ₂ N-, (iC ₃ H _{7) 2 N-, O (CH} 2 CH 2) 2 N -, (CH 3) 3 CNH-, with C ₆ H ₁₀ NH-, or C ₆ H ₅ NH- in which the hydrolyzable group-containing silyl group It is characterized by being expressed by

  The adhesive substrate according to claim 10 is the adhesive substrate according to claim 1, wherein the reactive group is hydrosilyl, vinylsilyl, hydroxysilyl, alkyloxysilyl, alkenyloxysilyl, acyloxysilyl, iminooxysilyl, alkyl. It is at least one selected from aminosilyl.

Adhesive base material according to claim 11 has been described in claim 1, wherein the active silyl group is the vinyl-containing silyl group, wherein the platinum-containing catalyst or the said adhesive surface to expose it A rhodium-containing catalyst is attached, and the reactive group is hydrosilyl.

  The adhesive base material according to claim 12 is the adhesive base material according to claim 11, wherein the platinum-containing catalyst is a platinum complex, and the rhodium-containing catalyst is a rhodium complex.

  The adhesive substrate according to claim 13 is the adhesive substrate according to claim 11, wherein the platinum-containing catalyst or rhodium-containing catalyst is applied by application or immersion in a solution or suspension containing the catalyst. It is characterized by.

  The adhesive substrate according to claim 14 is the adhesive substrate according to claim 11, wherein the platinum atom or rhodium atom of the platinum-containing catalyst or rhodium-containing catalyst is coordinated to the plurality of vinyl-containing silyl groups. It is characterized by being.

The adhesive substrate according to claim 15 is the adhesive substrate according to claim 11, wherein the vinyl-containing silyl group has (CH ₂ = CH-) (CH ₃ O-) ₂ Si-O-[(CH ₂ = CH-) (CH ₃ O-) Si-O] _b1 -Si (-OCH ₃ ) ₂ (-CH = CH ₂ ) (b1 is a number from 0 to 100),
(CH ₂ = CH-) (C ₂ H ₅ O-) ₂ Si-O-[(CH ₂ = CH-) (C ₂ H ₅ O-) Si-O] _b2 -Si (-OC ₂ H ₅ ) ₂ (number of b2 is _{0~100) (-CH = CH 2)} ,
(CH ₂ = CH-) (C ₃ H ₇ O-) ₂ Si-O-[(CH ₂ = CH-) (C ₃ H ₇ O-) Si-O] _b3 -Si (-OC ₃ H ₇ ) ₂ (number of b3 is _{0~100) (-CH = CH 2)} ,
It is derived from a vinyl-containing silyl compound selected from:

  The adhesive substrate according to a sixteenth aspect is the one according to the first aspect, wherein the solid is a silicone rubber or a silicone resin.

A silicone rubber adhesive according to claim 17 is formed of polysiloxanes, vinyl silicones and / or silanol silicones on the surface of the substrate of the bonding base material according to any one of claims 1 to 16 . subjected to a composition and degassed under reduced pressure includes a silicone rubber component, is cured silicone rubber to be formed, characterized in that it is bonded is coated.

  The silicone rubber adhesive body according to claim 18 is the adhesive body according to claim 17, wherein the plurality of adhesive base materials are interposed in the form of granular, cloth-like, thin-film-like, film-like or plate-like silicone rubber. And being bonded.

The silicone rubber adhesive according to claim 19 is the adhesive according to claim 17, wherein the polysiloxane is H (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _c [Si (R ¹¹ ). R ¹² O] _d Si (CH ₃ ) ₂ H (R ¹¹ and R ¹² are each an alkyl group, alkenyl group, alkyloxy group, fluorine-substituted alkyl group having 1 to 12 carbon atoms; aralkyl group; aryl group; HSi (CH ₃ ) ₂ O-, c is a number from 1 to 80, d is a number from 0 to 80), and the vinyl silicone is CH ₂ = CH (CH ₃ ) ₂ SiO [SiCH = CH ₂ (CH ₃ ) O] _e [Si (R ¹³ ) R ¹⁴ O] _f Si (CH ₃ ) ₂ CH═CH ₂ (R ¹³ and R ¹⁴ are each an alkyl group, alkenyl group, alkyloxy group having 1 to 12 carbon atoms. Group, fluorine-substituted alkyl group; aralkyl group; aryl group, e is a number of 1 to 80, f is a number of 0 to 80), and the silanol silicone is A- (CH ₃ ) ₂ SiO [Si (CH ₃ ) ₂ O] _g [Si (R ¹⁵ ) R ¹⁶ O] _h Si (CH ₃ ) ₂ -A (R ¹⁵ and R ¹⁶ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkyloxy group, a fluorine-substituted alkyl group; an aralkyl group; an aryl group, and A is a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkenyloxy group. , An aryloxy group, an acyloxy group, an iminooxy group, and an amino group, and g is a number of 1 to 80, and h is a number of 0 to 80).

A method for producing a silicone rubber bonded body according to claim 20 is obtained by forming polysiloxanes, vinyl silicones and / or silanols on the surface of the substrate of the bonding base material according to any one of claims 1 to 16. given the unrealized vacuum degassed composition of the silicone rubber component of silicones, and cured under room temperature or under heating, to coat the surface, characterized in that bonding the silicone rubber.

  The method for producing a silicone rubber bonded body according to claim 21 is the method according to claim 20, wherein the composition contains a crosslinking agent and / or a crosslinking catalyst.

  The bonding substrate of the present invention introduces a hydroxyl group into the surface of a substrate formed of metal, polymer resin or ceramics, and chemically combines the hydroxyl group and an active silyl group derived from an alkoxysilane compound. By making silyl ether bond, it becomes easy to cross-link and adhere to silicone rubber.

  Due to the bonding of the silyl group, a very thin monomolecular film of silyl ether is formed. This film is chemically stable and has been modified so that the surface of the substrate is sufficiently adhered to the silicone rubber even if it is thin. Furthermore, this film is stable for a long period of time and cross-links or interacts with the silicone rubber to form a strong and difficult-to-peel silicone rubber adhesive.

  In particular, when the base material for adhesion is a silyl ether bond with a vinyl-containing silyl group that is an active silyl group to form an adhesion surface, and a platinum-containing catalyst or a rhodium-containing catalyst is attached thereto, a hydrosilyl-containing silicone rubber, An extremely strongly bonded silicone rubber adhesive is formed.

  According to this method for producing a silicone rubber bonded body, a silicone rubber bonded body can be obtained easily and in large quantities regardless of the size.

Preferred form for carrying out the invention

  Hereinafter, preferred embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

  A bonding substrate to which the present invention is applied, for example, a silicone rubber bonding substrate is manufactured as follows.

  The substrate surface of the metal adherend substrate is subjected to corona discharge treatment to generate hydroxyl groups derived from metal oxide molecules on the substrate surface to form a silicone rubber crosslinking reactive substrate surface. If impurities such as organic substances are attached to the surface of the substrate, it is oxidized by corona discharge treatment to generate carboxyl groups derived from organic substances on the surface of the substrate. It becomes the substrate surface.

On the other hand, a functional alkoxysilyl compound such as HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ that reacts with the hydroxyl group to form a silyl ether and a solvent The solution is applied to the surface of the substrate to be bonded on which hydroxyl groups are generated, dried, and then heated. The triethoxysilyl group of this functional alkoxysilyl compound reacts with a hydroxyl group on the surface of the substrate to become the active silyl group, and forms a chemically strong silyl ether bond together with the dehydrogenated residue of the hydroxyl group. With this alkoxysilyl compound, a silicone rubber adhesive base material coated with a monomolecular film of silyl ether in which a silyl group such as a hydrosilyl-containing silyl group is ether-bonded can be obtained.

  Such a monomolecular film consists of molecular chains that do not exceed the basic unit of the silyl compound used first.

  When a composition containing a silicone rubber component is applied to this silicone rubber bonding substrate and cured, the silicone rubber adhesive is bonded to the surface by crosslinking the silicone rubber to the monomolecular film of silyl ether on the substrate. Is obtained. The silyl ether molecule and the silicone rubber on the substrate surface are chemically cross-linked with the silyl ether molecule and the silicone rubber component to form a covalent bond, or are attracted and interacted with each other by silyl groups. It is cross-linked electrochemically and is firmly bonded. Therefore, it is assumed that the silicone rubber adhesive has a strong adhesive strength and is difficult to peel off.

  Examples of silicone rubber adhesive substrates bonded with a silyl group such as a hydrosilyl-containing silyl group are shown, but vinyl-containing silyl groups exemplified by vinylsilyl-containing silyl groups, alkoxysilyl terminal-containing silyl groups, hydrolyzable It may be a silyl ether bond with an active silyl group such as a group-containing silyl group.

  Such active silyl groups are all formed by the reaction of the alkoxysilyl group of the functional alkoxysilyl compound with the hydroxyl group on the surface of the adherend substrate.

The silyl ether bond formed on such a substrate (Sub .: Substrate) with such a hydrosilyl-containing silyl group has the following chemical formula [1]:
Sub.-O-SiR ²⁰ ... [1]
It is represented by Hydrosilyl-containing silyl group —SiR ²⁰ has R ²⁰ having —SiH (R ¹ ) ₂ or —SiH ₂ (R ² ) (R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms) at the end, Alternatively, it has a —SiH— group in the middle of its main chain and may be a polysiloxy group.

More specifically, -SiR ²⁰ is
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H,
-(CH ₃ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H,
-(iC ₃ H ₇ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) H ₂ ,
-(nC ₃ H ₇ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H,
-(nC ₄ H ₉ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(tC ₄ H ₉ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(C ₂ H ₅ O) CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(CH ₃ O) CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H,
-(CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(nC ₃ H ₇ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(iC ₃ H ₇ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(nC ₄ H ₉ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-(tC ₄ H ₉ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
-[(-O) (-) SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H] _k1
-[(-O) (-) SiCH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H] _k2 ,
-[(-O) (-) SiCH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H] _k3 ,
-[(-O) (-) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H] _k4 ,
-[(-O) (-) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H] _k5 ,
-(CH ₃ O) ₂ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
-(CH ₃ O) CH ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
-(CH ₃ ) ₂ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
-[(-O) (-) SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H] _k6 ,
-[(-O) (-) SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ OC ₆ H ₄ Si (CH ₃ ) ₂ H] _k7 ,
-[(-O) (-) SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₂ H ₄ Si (CH ₃ ) ₂ H] _k8 ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _m1 Si (CH ₃ ) ₂ H,
-(C ₂ H ₅ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _m2 Si (C ₂ H ₅ ) ₂ H,
-(C ₂ H ₅ O) CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _m3 Si (CH ₃ ) ₂ H,
(CH ₃ ) ₃ SiO [-Si (CH ₃ )] O [SiH (CH ₃ ) O] _m4 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (CH ₃ ) CH ₂ CH ₂ CH ₂ ) (-) SiCH ₃ ] O [SiH (CH ₃ ) O] _m5 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (OCH ₃ ) CH ₂ CH ₂ CH ₂ ) (-) SiCH ₃ ] O [SiH (CH ₃ ) O] _m6 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (CH ₃ ) CH ₂ CH ₂ CH ₂ ) (-) SiCH ₃ ] O [SiH (CH ₃ ) O] _m7 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _m8 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (CH ₃ ) O [SiH (CH ₃ ) O] _m9 [Si (CH ₃ ) ₂ O] _n1 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) (-) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _m10 [Si (CH ₃ ) ₂ O] _n2 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (OCH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) (-) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _m11 [Si (CH ₃ ) ₂ O] _n3 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [( _-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _m12 [Si (CH ₃ ) ₂ O] _n4 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (OCH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) (-) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _m13 [Si (CH ₃ ) ₂ O] _n5 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [-Si (C ₂ H ₅ ) O] [SiH (C ₂ H ₅ ) O] _m14 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (C ₂ H ₅ )] O [SiH (C ₂ H ₅ ) O] _m15 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(-Si (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) (-) Si (C ₂ H ₅ )] O [SiH (C ₂ H ₅ ) O] _m16 Si (CH ₃ ) ₃ ,
-Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _m17 Si (CH ₃ ) ₂ H,
-Si (OCH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _m18 Si (CH ₃ ) ₂ H,
-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _m19 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m20 Si (CH ₃ ) ₂ H,
_{H (CH 3) 2 SiO [} (- Si (CH 3) 2 CH 2 CH 2 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m21 Si (CH 3) 2 H,
H (CH ₃ ) ₂ SiO [(-Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m22 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m23 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m24 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m25 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m26 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m27 Si (CH ₃ ) ₂ H,
_{H (CH 3) 2 SiO [} (- Si (OCH 3) 2 C 6 H 4 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m28 Si (CH 3) 2 H,
_{H (CH 3) 2 SiO [} (- Si (OCH 3) 2 CH 2 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m29 Si (CH 3) 2 H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m30 Si (CH ₃ ) ₂ H,
_{H (CH 3) 2 SiO [} (- Si (OCH 3) 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m31 Si (CH 3) 2 H,
_{H (CH 3) 2 SiO [} (- Si (OCH 3) 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m32 Si (CH 3 ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m33 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m34 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m35 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m36 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (OCH ₃ ) ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m37 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m38 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m39 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m40 Si (CH ₃ ) ₂ H,
_{H (CH 3) 2 SiO [} (- Si (O-) C 6 H 4 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m41 Si (CH 3) 2 H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m42 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m43 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m44 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m45 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m46 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m47 Si (CH ₃ ) ₂ H,
_{H (CH 3) 2 SiO [} (- Si (O-) CH 2 C 6 H 4 CH 2 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m48 Si (CH 3) 2 H,
H (CH ₃ ) ₂ SiO [(-Si (O-) CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _m49 Si (CH ₃ ) ₂ H,
_{H (CH 3) 2 SiO [} (- Si (O-) C 6 H 4 CH 2 CH 2) Si (CH 3) O] [HSiCH 3 O] m50 Si (CH 3) 2 H,
H (CH ₃ ) ₂ SiO [(-) Si (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _m51 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _n6 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-) Si (OCH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _m52 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _n7 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-) Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _m53 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _n8 Si (CH ₃ ) ₂ H,
-(CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _m54 [SiCH ₃ (C ₆ H ₅ ) O] _n9 Si (CH ₃ ) ₂ H,
-Si (OC ₂ H ₅ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _m55 [SiCH ₃ (C ₆ H ₅ ) O] _n10 Si ( CH ₃ ) ₂ H,
-Si (O-) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _m56 [SiCH ₃ (C ₆ H ₅ ) O] _n11 Si (CH ₃ ) ₂ H,
-Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _m57 [SiCH ₃ (C ₆ H ₅ ) O] _n12 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO (-) Si (CH ₃ ) O [SiH (CH ₃ ) O] _m58 [SiCH ₃ (C ₆ H ₅ ) O] _n13 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-) Si (OC ₂ H ₅ ) ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ )] O [SiH (CH ₃ ) O] _m59 [SiCH ₃ (C ₆ H ₅ ) O] _n14 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-) Si (O-) CH ₂ CH ₂ CH ₂ Si (CH ₃ )] O [SiH (CH ₃ ) O] _m60 [SiCH ₃ (C ₆ H ₅ ) O] _n15 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(-) Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ )] O [SiH (CH ₃ ) O] _m61 [SiCH ₃ (C ₆ H ₅ ) O] _n16 Si (CH ₃ ) ₂ H
Is mentioned. In these groups, k1 to k8, m1 to m61, and n1 to n16 are numbers from 1 to 100. One group preferably has 1 to 99 hydrosilyl groups (SiH groups).

Examples of functional alkoxysilyl compounds that form such hydrosilyl-containing silyl groups include:
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H,
(iC ₃ H ₇ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) H ₂ ,
(nC ₃ H ₇ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H,
(nC ₄ H ₉ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(tC ₄ H ₉ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H,
CH ₃ O (CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(nC ₃ H ₇ ) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(iC ₃ H ₇ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(nC ₄ H ₉ ) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(tC ₄ H ₉ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(CH ₃ O) ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
(CH ₃ O) ₂ CH ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
CH ₃ O (CH ₃ ) ₂ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ OC ₆ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₂ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _p1 Si (CH ₃ ) ₂ H,
C ₂ H ₅ O (CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _p2 Si (C ₂ H ₅ ) ₂ H,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _p3 Si (CH ₃ ) ₂ H,
(CH ₃ ) ₃ SiOSiH (CH ₃ ) O [SiH (CH ₃ ) O] _p4 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p5 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSiOCH ₃ CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p6 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p7 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(Si (OC ₂ H ₅ ) ₂ CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p8 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ O [SiH (CH ₃ ) O] _p9 [Si (CH ₃ ) ₂ O] _q1 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ Osi (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _p10 [Si (CH ₃ ) ₂ O] _q2 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _p11 [Si (CH ₃ ) ₂ O] _q3 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ O [SiH (C ₂ H ₅ ) O] _p12 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(Si (OC ₂ H ₅ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (C ₂ H ₅ )] O [SiH (C ₂ H ₅ ) O] _p13 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (C ₂ H ₅ )] O [SiH (C ₂ H ₅ ) O] _p14 Si (CH ₃ ) ₃ ,
C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p15 Si (CH ₃ ) ₂ H,
Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p16 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p17 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p18 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p19 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p20 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p21 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p22 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p23 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p24 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p25 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p26 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p27 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p28 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p29 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p30 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p31 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p32 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p33 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p34 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p35 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(CH ₃ O) Si (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p36 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _q4 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [Si (OCH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p37 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _q5 Si (CH ₃ ) ₂ H,
C ₂ H ₅ O (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _p38 [SiCH ₃ (C ₆ H ₅ ) O] _q6 Si (CH ₃ ) ₂ H,
Si (OC ₂ H ₅ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _p39 [SiCH ₃ (C ₆ H ₅ ) O] _q7 Si (CH ₃ ) ₂ H,
C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _p40 [SiCH ₃ (C ₆ H ₅ ) O] _q8 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO (C ₂ H ₅ O) Si (CH ₃ ) O [SiH (CH ₃ ) O] _p41 [SiCH ₃ (C ₆ H ₅ ) O] _q9 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [Si (OC ₂ H ₅ ) ₃ CH ₂ CH ₂ CH ₂ Si (CH ₃ )] O [SiH (CH ₃ ) O] _p42 [SiCH ₃ (C ₆ H ₅ ) O] _q10 Si (CH ₃ ) ₂ H
Is mentioned. In these groups, p1 to p42 and q1 to q10 are numbers from 1 to 100. One molecule preferably has 1 to 99 hydrosilyl groups.

The silyl ether bond formed on the adherend substrate (Sub.) With a vinylsilyl-containing silyl group has the following chemical formula [2]
Sub.-O-SiR ²¹ ... [2]
It is represented by In the vinylsilyl-containing silyl group —SiR ²¹ , R ²¹ has a —Si—R ³ group (R ³ is a vinyl-containing group), or —Si (R ⁴ ) — group (R ⁴ ) in the middle of the main chain of the group. Has a vinyl-containing group).

-SiR ²¹ is more specifically
-(C ₂ H ₅ O) ₂ SiCH ₂ -CH = CH ₂ ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ -CH = CH ₂ ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ CH ₂ -CH = CH ₂ ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -CH = CH ₂ ,
-C ₂ H ₅ OSi (CH = CH ₂ ) OSi (OC ₂ H ₅ ) -CH = CH ₂ ,
-(CH ₃ O) ₂ SiCH ₂ CH ₂ C ₆ H ₄ -CH = CH ₂ ,
-(CH ₃ O) Si (CH = CH ₂ ) O [SiOCH ₃ (CH = CH ₂ ) O] _r1 Si (OCH ₃ ) ₂ -CH = CH ₂ ,
-(C ₂ H ₅ O) Si (CH = CH ₂ ) O [SiOC ₂ H ₅ (CH = CH ₂ ) O] _r2 Si (OC ₂ H ₅ ) ₂ -CH = CH ₂ ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _r3 -CH = CH ₂ ,
-(CH ₃ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _r4 -CH = CH ₂ ,
-(CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _r5 -CH = CH ₂ ,
-(C ₂ H ₅ O) CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _r6 -CH = CH ₂ ,
-(-O) SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _r7 -CH = CH ₂ ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ (Si (CH ₃ ) ₃ O) Si (CH ₃ ) O [SiCH ₃ ( -) O] _s1 Si (CH ₃ ) ₃ ,
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ (Si (CH ₃ ) ₃ O) Si (CH ₃ ) O [SiCH ₃ ( -) O] _s2 [Si (CH ₃ ) ₂ O] _r8 Si (CH ₃ ) ₃ ,
-C ₂ H ₅ OSi (CH = CH ₂ ) O [SiCH ₃ (-) O] _s3 Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
-C ₂ H ₅ OSi (CH = CH ₂ ) O [SiCH ₃ (-) O] _s4 Si (CH = CH ₂ ) OC ₂ H ₅ -CH = CH ₂ ,
-(-O) Si (CH = CH ₂ ) O [SiCH ₃ (-) O] _s5 Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
-(-O) Si (CH = CH ₂ ) O [SiCH ₃ (-) O] _s6 Si (CH = CH ₂ ) (O-)-CH = CH ₂ ,
-(-O) Si (CH = CH ₂ ) O [SiCH ₃ (-) (O-)] _s7 Si (CH = CH ₂ ) (O-)-CH = CH ₂ ,
-Si (CH = CH ₂ ) O [Si (-) OC ₂ H ₅ ] _s8 [Si (O-) CH = CH ₂ ] ₂ ,
-Si (CH = CH ₂ ) O [Si (O-)] _r9 [Si (-) OC ₂ H ₅ ] _s9 [Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ] ₂ ,
-Si (CH = CH ₂ ) O [Si (-) (O-)] _s10 [Si (O-) CH = CH ₂ ] ₂
Is mentioned. In these groups, r1 to r9 and s1 to s10 are numbers from 1 to 30. One group preferably has 1 to 30 vinyl groups (CH═CH ₂ groups).

Examples of functional alkoxysilyl compounds that form vinylsilyl-containing silyl groups include:
(C ₂ H ₅ O) ₃ SiCH ₂ CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ (CH ₂ ) ₇ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) OSi (OC ₂ H ₅ ) CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ H ₄ CH = CH ₂ ,
(CH ₃ O) ₂ Si (CH = CH ₂ ) O [SiOCH ₃ (CH = CH ₂ ) O] _t1 Si (OCH ₃ ) ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [SiOC ₂ H ₅ (CH = CH ₂ ) O] _t2 Si (OC ₂ H ₅ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t3 CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t4 CH = CH ₂ ,
CH ₃ O (CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t5 CH = CH ₂ ,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t6 CH = CH,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t7 CH = CH,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ (Si (CH ₃ ) ₃ O) Si (CH ₃ ) O [SiCH ₃ (- ) O] _u1 Si (CH ₃ ) ₃ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ (Si (CH ₃ ) ₃ O) Si (CH ₃ ) O [SiCH ₃ (- ) O] _u2 [Si (CH ₃ ) ₂ O] _t8 Si (CH ₃ ) ₃ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [SiCH ₃ (OC ₂ H ₅ ) O] _u3 Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [Si (OC ₂ H ₅ ) ₂ O] _u4 Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [Si (OC ₂ H ₅ ) ₂ O] _u5 Si (OC ₂ H ₅ ) ₂ CH = CH ₂
Is mentioned. In these groups, t1 to t8 and u1 to u5 are numbers from 1 to 30. One molecule preferably has 1 to 30 vinyl groups.

Further, the silyl ether bond formed on the adherend substrate (Sub.) With the alkoxysilyl terminal-containing silyl group has the following chemical formula [3]:
Sub.-O-SiR ²² ... [3]
It is represented by In the alkoxysilyl terminal-containing silyl group —SiR ²² , R ²² is —Si (OR ⁵ ) ₂ R ⁶ group (R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms), or —Si (OR ⁷ ) ₃ group. (R ⁷ is an alkyl group having 1 to 4 carbon atoms). -SiR ²² is more specifically
-(C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
-(C ₂ H ₅ O) CH ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
-(C ₂ H ₅ O) ₂ SiCH = CHSi (OC ₂ H ₅ ) _3,
-(CH ₃ O) ₂ SiCH ₂ CH ₂ Si (OCH ₃ ) _3,
-(CH ₃ O) ₂ SiCH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
-(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₃ Si (OCH ₃ ) ₃ ,
-(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₄ Si (OCH ₃ ) _3,
-(CH ₃ O) CH ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ ,
-(C ₂ H ₅ O) CH ₃ SiOSi (OC ₂ H ₅ ) ₂ CH ₃ ,
-(C ₂ H ₅ O) Si (OC ₂ H ₅ ) ₂
Is mentioned.

Examples of functional alkoxysilyl compounds that form alkoxysilyl terminal-containing silyl groups include:
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH = CHSi (OC ₂ H ₅ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ (CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si [CH ₂ CH ₂ ] ₃ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₄ Si (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₂ Si (OC ₂ H ₅ ) ₂ ,
(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ ,
(C ₂ H ₅ O) ₂ CH ₃ SiOSi (OC ₂ H ₅ ) ₂ CH ₃ ,
(CH ₃ O) ₃ SiO [Si (OCH ₃ ) ₂ O] _v1 Si (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiO [Si (OC ₂ H ₅ ) ₂ O] _v2 Si (OC ₂ H ₅ ) ₃ ,
(C ₃ H ₇ O) ₃ SiO [Si (OC ₃ H ₇ ) ₂ O] _v3 Si (OC ₃ H ₇ ) ₃
Is mentioned. In these groups, v1 to v3 are numbers from 0 to 30.

In addition, the silyl ether bond formed on the adherend substrate (Sub.) With a hydrolyzable group-containing silyl group has the following chemical formula [4]:
Sub.-O-Si (R ⁸ ) _a (R ⁹ ) _3-a ... [4]
(R ⁸ is a hydrogen atom; a halogen atom; an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkyloxy group, a fluorine-substituted alkyl group; an aralkyl group; an aryl group, and R ⁹ is an alkyl group having 1 to 12 carbon atoms. An acyloxy group, an alkenyloxy group, an alkaneiminooxy group, an alkyloxy group, an alkylamino group, a dialkylamino group; a nitrogen-containing heterocyclic group, and an arylamino group, where a is a number from 0 to 3. More specifically, in the hydrolyzable group-containing silyl group -Si (R ⁸ ) _a (R ⁹ ) _3-a , R ⁸ is H-, F-, CH _3- , C ₂ H _5- , CH _{2 = CH-, nC 3 H 7} -, iC 3 H 7 -, CH 2 = CHCH 2 -, C 4 H 9 -, C 6 H 13 -, C 8 H 17 -, C 6 H 5 -, CH 3 _{C 6 H 4 -, C 6} H 5 CH 2 -, CF 3 CF 2 CH 2 CH 2 -, CF 3 CF 2 CF 2 CH 2 CH 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH ₂ CH _2- , CH ₃ O-, C ₂ H ₅ O-, and R ⁹ is CH ₃ COO-, CH ₂ = C (CH ₃ ) O-, C ₂ H ₅ (CH ₃ ) C = NO-, CH ₃ O-, (CH ₃ ) ₂ N-, (C ₂ H ₅ ) ₂ N-, (iC ₃ H ₇ ) ₂ N-, O (CH ₂ CH ₂ ) ₂ N-, (CH ₃ ) ₃ CNH-, C ₆ H ₁₀ NH-, C ₆ H ₅ NH-.

As an example of a functional alkoxysilyl compound that forms a hydrolyzable group-containing silyl group,
CH ₃ Si (OCOCH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCOCH ₃ ) ₂ , nC ₃ H ₇ Si (OCOCH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OCOCH ₃ ) ₃ , C ₆ H ₅ Si ( OCOCH ₃ ) ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si (OCOCH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OCOCH ₃ ) ₃ , CH ₃ OSi (OCOCH ₃ ) ₃ , C ₂ H ₅ OSi (OCOCH ₃ ) ₃ , CH ₃ Si (OCOC ₃ H ₇ ) ₃ , CH ₃ Si [OC (CH ₃ ) = CH ₂ ] ₃ , (CH ₃ ) ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , nC ₃ H ₇ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₂ = CHCH ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , C ₆ H ₅ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₂ = CHCH ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₃ OSi [OC (CH ₃ ) = CH ₂ ] ₃ , C ₂ H ₅ OSi [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₃ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , (CH ₃ ) ₂ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₂ , nC ₃ H ₇ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₂ = CHCH ₂ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , C ₆ H ₅ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₂ = CHCH ₂ Si [ ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₃ OSi [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , C ₂ H ₅ OSi [ON = C (CH ₃ ) C ₂ H ₅ ] ] ₃ , CH ₃ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₃ Si [ N (CH ₃ )] ₃ , (CH ₃ ) ₂ Si [N (CH ₃ )] ₂ , nC ₃ H ₇ Si [N (CH ₃ )] ₃ , CH ₂ = CHCH ₂ Si [N (CH ₃ )] ₃ , C ₆ H ₅ Si [N (CH ₃ )] ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si [N (CH ₃ )] ₃ , CH ₂ = CHCH ₂ Si [N (CH ₃ )] ₃ , CH ₃ OSi [N (CH ₃ )] ₃ , C ₂ H ₅ OSi [N (CH ₃ )] ₃ , and CH ₃ Si [N (CH ₃ )] ₃ are examples of hydrolyzable organosilanes.

  These functional alkoxysilyl compounds include water, methanol, ethanol, isopropanol, ethylene glycol and other alcohols; acetone, methyl ethyl ketone and other ketones; ethyl acetate and other esters; methylene chloride and other halides, butane, hexane, etc. These olefins are used by dissolving in ethers such as tetrahydrofuran and butyl ether, aromatics such as benzene and toluene, amides such as dimethylformamide and methylpyrrolidone, and mixed solvents thereof.

  The amount of the functional alkoxysilyl compound added is generally in the range of 0.001 to 5 g with respect to 100 g of the solvent. If it is 0.001 g or less, the adhesive effect is not sufficient, and if it is 5 g or more, a multilayer thin film is formed even if the conditions are controlled.

  Although the example of the metal adherend base material was shown, you may use the polymer resin, glass, or the ceramic adherend substrate.

  The hydroxyl group thereof may be a hydroxyl group derived from a general metal oxide, a polymer having a hydroxyl group, or a hydroxyl group possessed by ceramics.

  Examples of such metals include Mg, Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd, In, Ta, Co, Ni, Sn, Sb, Bi, Pb, Cu, and Ag. , Pt, Pd, and Au, such as binary alloys, ternary alloys, and multi-component alloys of these metal materials. Examples of such alloys include Mg alloy, Al alloy, Fe—Cr—Ni alloy, Ni alloy, Co alloy, Cu—Zn alloy, Cu—Sn alloy, Cu—Ni alloy, and Ag alloy. Any metal or alloy adherend substrate is one in which an oxide film is formed so that a hydroxyl group can be introduced to the surface.

  Examples of polymer resins include cellulose, hydroxyethyl cellulose, starch, cellulose derivatives such as cellulose diacetate, surface saponified vinyl acetate resin, low density polyethylene, high density polyethylene, i-polypropylene, petroleum resin, polystyrene, s-polystyrene, Chroman indene resin, terpene resin, styrene-divinylbenzene copolymer, acrylonitrile-butadiene-styrene resin (ABS resin), polyacrylate, polyacrylate, polyacrylonitrile, methyl methacrylate, ethyl methacrylate, poly Cyanoacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ethylene copolymer, poly Vinylidene fluoride, vinylidene fluoride / ethylene copolymer, vinylidene fluoride / propylene copolymer, 1,4-transpolybutadiene, polyoxymethylene, polyethylene glycol, polypropylene glycol, phenol / formalin resin, cresol / formalin resin, Resorcin resin, melamine resin, xylene resin, toluene resin, glyphal resin, modified glyphal resin, polyethylene terephthalate, polybutene terephthalate, unsaturated polyester resin, allyl ester resin, polycarbonate, 6-nylon (Nylon is a registered trademark), 6 ' 6-nylon, 6'10-nylon, polyimide, polyamide, polybenzimidazole, polyamideimide, silicon resin, silicone rubber, silicone resin, furan resin, polyurethane resin, epoxy Resin, polyphenylene oxide, polydimethylphenylene oxide, polyxylene, polyphenylene sulfide (PPS), polysulfone (PSF), polyethersulfone (PES), polyetheretherketone (PEEK), polyimide (PPI, Kapton), liquid crystal resin , Kevlar fibers, blends of carbon fibers and these materials, polymer materials such as polytetrafluoroethylene (PTFE), or natural rubber, 1,4-cisbutadiene rubber, isoprene rubber, polychloroprene, styrene-butadiene copolymer Polymerized rubber, hydrogenated styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, hydrogenated acrylonitrile / butadiene copolymer rubber, polybutene, polyisobutylene, ethylene / propylene rubber, ethylene / propylene / terpolymer, chlorine Polyethylene, chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, chloroprene rubber, chlorinated acrylic rubber, brominated acrylic rubber, fluoro rubber, epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber Rubber materials such as A mixture thereof or a cross-linked product thereof may be used.

  Metal materials such as Mg, Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd, In, Ta, Co, Ni, Sn, Sb, Bi, Pb, Cu, and Ag as ceramics Sintered bodies of these alloys, sintered bodies of oxides of binary alloys of these metal materials, sintered bodies of oxides of ternary alloys, and sintered bodies of oxides of multicomponent alloys.

  The substrate to be adhered may be any material made of these metals, polymer resins, glass or ceramics, and may be particles, such as a film, plate, or cloth having a shape such as a rectangle, square, or polygon. It may be a product shape such as a cylinder, an air thread, a hose, or a net, or may be a shape such as a sphere or an elliptical sphere.

  Although an example in which a corona discharge is applied to an adherend substrate to introduce a hydroxyl group is shown, atmospheric pressure plasma treatment or ultraviolet irradiation may be performed.

  Corona discharge is performed according to the method described in “Corona Treatment”, Journal of the Adhesion Society of Japan, Vol. 36, No. 3, 126 (2000). Atmospheric pressure plasma treatment is performed using “plasma treatment”, Journal of the Adhesion Society of Japan, Vol. In accordance with 41, No. 1, 4 (2005), ultraviolet irradiation involves exposure to ultraviolet rays and treatment. By these treatments, as described in LJ Gerenser: J. Adhesion Sci. Technol. 7, 1019 (1997), a hydroxyl group on the substrate surface of a metal, polymer resin, glass or ceramic adherend substrate, A carboxyl group, a carbonyl group, or the like is generated or appears on the surface.

  The polymer resin may or may not have a hydroxyl group from the beginning, but the surface of the substrate to be bonded made of the polymer resin may be treated with corona discharge, atmospheric pressure plasma treatment, or ultraviolet irradiation without having a hydroxyl group. By applying, hydroxyl groups are efficiently generated there.

  These optimum processing conditions vary depending on the material type and history of the adherend substrate surface, but it is important to continue the treatment until a surface tension of 55 kJ / m or more is obtained on the surface. Thereby, sufficient adhesive strength is obtained.

  Specifically, the corona discharge treatment of the surface of the resin and the resin compound is performed using a corona surface reformer (for example, a corona master manufactured by Shinko Electric Measurement Co., Ltd.), power source: AC100V, output voltage: 0 to 20 kV, oscillation frequency: 0 to 40 kHz, 0.1 second to 60 seconds, temperature 0 to 60 ° C.

  In addition, the atmospheric pressure plasma treatment of the surface of the resin and the resin blend is performed using an atmospheric pressure plasma generator (for example, Matsushita Electric Works Co., Ltd .: trade name Aiplasuma), plasma treatment speed of 10 to 100 mm / s, power source: 200 or 220 V AC (30 A), compressed air: 0.5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, irradiation time: 0.1 second to 60 seconds.

In addition, ultraviolet irradiation of the surface of the resin and the resin compound is performed using an ultraviolet-light emitting diode (UV-LED) irradiation device (for example, UV-LED irradiation device manufactured by OMRON Corporation: trade name ZUV-C30H). , Wavelength: 200 to 400 nm, power source: 100 V AC, light source peak illuminance: 400 to 3000 mW / cm ² , irradiation time: 1 to 60 seconds.

  You may make the surface of the to-be-adhered base material which has produced | generated the hydroxyl group on the surface by pretreatments, such as corona discharge, contact the solution of the functional alkoxysilyl compound which is a molecular adhesive by immersion or spraying. There is no limitation on the dipping and spraying time, and it is important that the surface of the adherend substrate is uniformly moistened.

  The substrate to be bonded with the functional alkoxysilyl compound is dried while being heated by placing it in an oven, blowing warm air with a dryer, or irradiating high frequency. Heating and drying are performed at a temperature range of 50 ° C to 250 ° C for 1 to 60 minutes. Below 50 ° C., the reaction time of the hydroxyl group generated on the surface of the adherend substrate and the functional alkoxysilyl compound takes too long, resulting in a decrease in productivity and an increase in cost. Further, at 250 ° C. or higher, the surface of the adherend substrate is deformed or decomposed even if the heat drying time is short. Since heat transfer is insufficient in heat drying for 1 minute or less, the bonding between the hydroxyl group on the adherend substrate surface and the functional alkoxysilyl compound becomes insufficient. Moreover, productivity will fall in 60 minutes or more.

  When the reaction between the hydroxyl group on the surface of the adherend substrate and the functional alkoxysilyl compound is insufficient, the above immersion and drying may be repeated about 1 to 5 times. As a result, it is possible to sufficiently advance the reaction by shortening the time of dipping and drying per time and increasing the number of reactions.

  Furthermore, by using a combination of the functional alkoxysilyl compound and the silane compound, a silyl ether having silicone rubber crosslinking reactivity can be formed on the surface of the adherend substrate.

For example, after reacting the hydroxyl group of the adherend substrate surface with the above functional alkoxysilyl compound, a silane compound, for example
HSi (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
HSi (CH ₃ ) ₂ C ₆ H ₄ OC ₆ H ₄ Si (CH ₃ ) ₂ H,
CH ₃ Si (H) ₂ C ₂ H ₄ Si (H) ₂ CH ₃ ,
HSi (CH ₃ ) ₂ C ₂ H ₄ Si (CH ₃ ) ₂ H,
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
HSi (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _x1 Si (CH ₃ ) ₂ H (where x1 = 1 to 840),
(CH ₃ ) ₃ SiO [SiH (R ¹⁷ ) O] _x2 [Si (CH ₃ ) ₂ O] _y1 Si (CH ₃ ) ₃ (where R ¹⁷ = CH _3- , C ₂ H _5- , C ₆ H ₅ -; Y1 = 1-50; x2 = 0-50)
HSi (CH ₃ ) ₂ O [SiC ₆ H ₅ (OSi (CH ₃ ) ₂ H)] _x3 Si (CH ₃ ) ₂ H (x3 = 1-5),
HSi (CH ₃ ) ₂ O [SiCH ₃ (H) O] _x4 [SiCH ₃ (C ₆ H ₅ ) O] _y2 Si (CH ₃ ) ₂ H (x4 = 1-10, y2 = 1-10)
Is mentioned. By immersing in a 0.01-5% alcohol solution of these silane compounds and heating to 0-200 ° C. for 1-60 minutes, a silicone rubber bonding substrate is obtained. If it is 0.01% or less, it takes too much reaction time, and if it is 5% or more, cleaning and recovery costs are required. The reactivity is low below 0 ° C, and the productivity is inferior above 200 ° C. The reaction is not completed in 1 minute or less, and the productivity is inferior in 60 minutes or more.

Similarly, the following unsaturated alkoxysilane compounds, such as
CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) ₃ ,
CH ₂ = CHCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₂ = CHSi (OC ₂ H ₅ ) ₂ OSi (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
CH ₂ = CHC ₆ H ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₂ = CHSi (OCH ₃ ) ₂ O [SiOCH ₃ (CH = CH ₂ ) O] _x5 Si (OCH ₃ ) ₂ CH = CH ₂ (however, x5 = 1-30),
CH ₂ = CHSi (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _y3 [Si (R ¹⁸ ) ₂ O] _x6 Si (CH ₃ ) ₂ CH = CH ₂ (However, R ¹⁸ = CH ₃ −, C ₂ H ₅ −, C ₆ H ₅ −, or CF ₃ CH ₂ CH ₃ −, x6 = 0 to 2100, y3 = 0 to 2100),
(CH ₃ ) ₃ SiO [Si (CH ₃ ) ₂ O] _y4 [SiCH ₃ (CH = CH ₂ ) O] _x7 Si (CH ₃ ) ₃ (where x7 = 0 to 2100, y4 = 0 to 2100),
(CH ₃ ) ₃ SiO [Si (CH ₃ ) ₂ O] _y5 [SiCH ₃ (CH = CH ₂ ) O] _x8 [SiCH ₃ (R ¹⁹ ) O] _z1 Si (CH ₃ ) ₃ (R ¹⁹ = CH ₃ −, C ₂ H ₅ −, C ₆ H ₅ −, or CF ₃ CH ₂ CH ₃ −, x8 = 0 to 2100, y5 = 0 to 2100, z1 = 0 to 2100)
Is mentioned. After reacting with the hydroxyl group on the surface of the substrate to be bonded with these unsaturated alkoxysilane compounds, a suspension of a mixture of 0.01 to 5% of the silane compound and 10 to 1000 ppm of the platinum catalyst is used. Even if immersed for 1 to 60 minutes at ° C., a silicone rubber bonding substrate can be obtained.

  At this time, if the silane compound concentration is 0.01% or less, it takes too much reaction time, and if it is 5% or more, cleaning and recovery costs are required. If the platinum catalyst concentration is 10 ppm, the reaction rate is too slow, and if it is 1000 ppm or more, the cost becomes a problem. Below 0 ° C, the reactivity is low, so the productivity is low. Above 200 ° C, the SiH group is oxidized and the performance decreases. The reaction may not be completed in 1 minute or less, and the productivity is inferior in 60 minutes or more.

Also, silanol terminated siloxanes such as HOSi (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] ₂ Si (CH ₃ ) ₂ OH after reacting with functional polyalkoxysilane with hydroxyl group When immersed in a 0.01% to 5% methanol solution at 0 to 200 ° C. for 1 to 60 minutes, a silicone rubber bonding substrate containing silanol groups on the surface is obtained.

  If the silanol-terminated siloxane concentration is 0.01% or less, the reaction time is too long, and if it is 5% or more, cleaning and recovery costs are required. Below 0 ° C., the reactivity is low and the productivity is inferior. Above 200 ° C., a multimolecular film may be formed, which is not preferable. The reaction may not be completed in 1 minute or less, and the productivity is inferior in 60 minutes or more.

  The silicone rubber bonding substrate into which a crosslinking reactive group such as a hydrosilyl (SiH) group, an unsaturated group, and a silanol (SiOH) group obtained as described above is introduced is a silicone rubber as described below. It is brought into contact with the component composition, and then left or heated to cause cross-linking adhesion.

A silicone rubber adhesive is obtained when the silicone rubber adhesive substrate is brought into contact with the silicone rubber component composition and treated at 0 to 200 ° C. for 1 to 240 minutes under a pressure of from atmospheric pressure to 100 kg / cm ² .

At this time, the crosslinking rate is low at 0 ° C. or lower and the productivity is inferior, but at 200 ° C. or higher, the polymer resin to be used is not preferable because it has a limit of thermal stability. If it is less than 1 minute, the crosslinking reaction is not sufficient and often does not adhere. Usually, the strength of the silicone rubber adhesive is low at atmospheric pressure or below except for producing a foam, and even if it is 100 kg / cm ² or more, there is no particular advantage, so this is not preferable.

The silicone rubber component has the following chemical formula [5]
H (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _c [Si (R ¹¹ ) R ¹² O] _d Si (CH ₃ ) ₂ H ・ ・ ・ [5]
(Wherein, R ¹¹ and R ^12, more specifically _{CH 3 -, C 2 H 5} -, CH 2 CH = CH 2 -, nC 3 H 7 -, iC 3 H 7 -, nC 6 H 13 −, NC ₈ H ₁₇ −, C ₆ H ₅ −, C ₆ H ₅ CH ₂ −, C ₆ H ₅ CH ₂ CH ₂ −, C ₁₀ H ₇ −, CF ₃ CH ₂ CH ₂ −, CF ₃ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , A group represented by HSi (CH ₃ ) ₂ O—, c is a number from 1 to 80, and d is a number from 0 to 80),
The following chemical formula [6]
CH ₂ = CH (CH ₃ ) ₂ SiO [SiCH = CH ₂ (CH ₃ ) O] _e [Si (R ¹³ ) R ¹⁴ O] _f Si (CH ₃ ) ₂ CH = CH ₂ ... [6]
(Wherein, R ¹³ and R ^14, more _{specifically, CH 3 -, C 2 H} 5 -, CH 2 = CH-, CH 2 = CHCH 2 -, nC 3 H 7 -, iC 3 H 7 −, NC ₆ H ₁₃ −, nC ₈ H ₁₇ −, C ₆ H ₅ −, CH ₂ = CHC ₆ H ₄ −, CH ₂ = CHC ₆ H ₄ CH ₂ −, C ₆ H ₅ CH ₂ CH ₂ −, C ₁₀ H ₇ −, CF ₃ CH ₂ CH ₂ −, CF ₃ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —, a group exemplified by HSi (CH ₃ ) ₂ O—, e is a number from 1 to 80, and f is a number from 0 to 80)
Vinyl silicones selected from
Or the following chemical formula [7]
A- (CH ₃ ) ₂ SiO [Si (CH ₃ ) ₂ O] _g [Si (R ¹⁵ ) R ¹⁶ O] _h Si (CH ₃ ) ₂ -A ・ ・ ・ [7]
(Wherein R ¹⁵ and R ¹⁶ are CH ₃ −, C ₂ H ₅ −, CH ₂ = CH−, CH ₂ = CHCH ₂ −, nC ₃ H ₇ −, iC ₃ H ₇ −, nC ₆ H ₁₃ − , nC ₈ H ₁₇ −, C ₆ H ₅ −, CH ₂ = CHC ₆ H ₄ −, CH ₂ = CHC ₆ H ₄ CH ₂ −, C ₆ H ₅ CH ₂ CH ₂ −, C ₁₀ H ₇ −, CF ₃ CH ₂ CH ₂ −, CF ₃ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- group, A is HO-, CH ₃ O-, C ₂ H ₅ O-, nC ₃ H ₇ O-, iC ₃ H ₇ O-, C ₆ H ₅ O−, CH ₃ COO−, CH ₂ = C (CH ₃ ) O−, C ₂ H ₅ (CH ₃ ) C = NO−, (CH ₃ ) ₂ N−, (C ₂ H ₅ ) ₂ N− And silanol silicone derivatives selected from the group exemplified by the formula: g is a number from 1 to 80, and h is a number from 0 to 80.

  The silicone rubber component composition contains at least one of these silicone rubber components. Addition type silicone rubber composition comprising a mixture of chemical formula [5] and chemical formula [6], peroxide type silicone rubber composition comprising only chemical formula [6], and chemical formula [7] or a mixture of chemical formula [5] and chemical formula [7] The condensation type silicone rubber composition which consists of may be sufficient.

  In addition to the silicone rubber component, the silicone rubber component composition may contain a filler, a crosslinking agent, and a catalyst.

  Examples of the filler include wet silica, dry silica, talc, nipsil, carbon black, and metal oxide, and are added in the range of 10 to 100 parts. If it is 10 parts or less, the reinforcing effect is not sufficient, and if it is 100 parts or more, filling becomes difficult.

  Silicone rubber is formed by a crosslinking system such as a peroxide crosslinking system, an addition crosslinking system, and a condensation crosslinking system. Thereby, the crosslinked adhesive material of the base material for silicone rubber adhesion and silicone rubber is obtained.

  Peroxide type silicone rubber composition includes benzoyl peroxide, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2 0.5 to 5 parts of a peroxide such as 1,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di (t-butylperoxyisopropyl) benzene is added. If it is 0.5 parts or less, crosslinking is insufficient, and if it is 5 parts or more, crosslinking may occur during molding.

  The bonded body crosslinked with the surface of the base material for bonding silicone rubber and the peroxide type silicone rubber composition can be obtained by heating in the temperature range of 80 to 200 ° C. for 1 to 60 minutes. Adhesives are difficult to obtain at 80 ° C or lower, and silicone rubber may turn yellow at 200 ° C or higher. In less than 1 minute, crosslinking is insufficient, and in more than 60 minutes, productivity is low and cost is high.

  For addition type silicone rubber composition, chloroplatinic acid, platinum carbonylcyclovinylmethylsiloxane complex, platinum divinyltetramethyldisiloxane complex, platinum cyclovinylmethylsiloxane complex, platinum octanal / octanol complex as catalyst used for addition type crosslinking , Tris (dibutyl sulfide) rhodium trichloride and the like are added within the range of 1 to 100 ppm. If this is 1 ppm or less, crosslinking is insufficient, and if it is 100 ppm or more, the cost increases, which is not preferable.

  The above catalyst is used by adding to the silicone rubber component composition of any of the addition type silicone rubber compositions of the chemical formula [5], the silicone rubber of the chemical formula [6], and mixtures thereof.

  In the case of a normal industrial product having a rubber molded product thickness of 10 mm or less, the silicone rubber component composition can be crosslinked at a temperature range of 0 to 150 ° C. with a crosslinking time of 1 to 240 minutes. Adhesives are difficult to obtain at temperatures below 0 ° C, and there are no particular problems at temperatures above 150 ° C. In less than 1 minute, crosslinking is insufficient, and in more than 240 minutes, productivity is low and cost is high. When the thickness of the rubber molded product exceeds 10 mm, the thermal conductivity is deteriorated and the internal cross-linking is slowed down, so that the cross-linking may be performed for a long time at a low mold temperature. In that case, it is also possible to change the crosslinking temperature stepwise. In the case of a molded product made of a relatively thin rubber, it may be crosslinked at room temperature, for example, over a whole day and night. In that case, thermal expansion at the crosslinking temperature and shrinkage when used at room temperature do not occur, and a molded product with very good dimensional accuracy becomes possible.

The mixing ratio of the silicone rubber represented by the chemical formula [5] and the silicone rubber represented by the chemical formula [6] is based on a SiH group / CH = CH ₂ ratio of 1 (stoichiometry). 4.5 / 1. The hardness is lower than 1.3 / 1 or less, and the same result is often obtained at 4.5 / 1 or more. The optimum SiH group / CH = CH ₂ ratio is affected by the additives such as fillers, and is therefore selected as appropriate.

In particular, when the concentration of the crosslinking reactive group SiH group on the substrate surface is high, the adhesive strength is increased even if the SiH group / CH = CH ₂ ratio is high. However, when the SiH group concentration is low, if the SiH group / CH = CH ₂ ratio is high, the adhesive strength is low. Further, when the concentration of the crosslinkable group CH═CH ₂ group on the substrate surface is high, the adhesive strength cannot be increased unless the SiH group / CH═CH ₂ ratio is increased.

In the condensation type silicone rubber composition, as a condensation type crosslinking agent, CH ₃ Si (OCOCH ₃ ) ₃ , C ₂ H ₅ OSi (OCOCH ₃ ) ₃ , CH ₃ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₃ Si [ON = C (CH ₃ ) C ₂ H ₅ ]] ₃ , CH ₃ OSi [ON = C (CH ₃ ) C ₂ H ₅ ]] ₃ , CH ₃ Si [N (CH ₃ )] ₃ etc. 0.5 to 10 parts, and as the catalyst, organic tin compounds such as bis (ethylhexyl) tin, bis (neodecanate) tin, dibutylralauryltin, metal salts such as zinc octylate and iron octylate, titanates, titanium 0.5-10 parts of chelate compounds, amines and the like are added.

  In the condensation type silicone rubber composition, the condensation type crosslinking agent is added to the silanol silicone rubber of the chemical formula [7], and the catalyst is either the H silicone polymer of the chemical formula [5] or the silanol silicone rubber of the chemical formula [7]. Or added to a mixture thereof.

  The bonding substrate and the silicone rubber bonded body using the bonding substrate may be in another mode as described below.

A substrate cleaned with a metal such as aluminum as a substrate is subjected to a surface treatment such as corona discharge treatment to generate hydroxyl groups on the substrate, and (CH ₂ = CH-) (CH ₃ O-) ₂ Si- O-[(CH ₂ = CH-) (CH ₃ O-) Si-O] _b1 -Si (-OCH ₃ ) ₂ (-CH = CH ₂ ) Immersion in a solution of a vinyl-containing silyl compound and heat treatment Then, the vinyl-containing silyl compound reacts with the hydroxyl group on the substrate. When it is immersed in a platinum-containing catalyst, for example, a hexane solution of a platinum complex such as a platinum-tetramethyldivinyldisiloxane complex, and dried, a base material for adhesion having a platinum-containing catalyst on the substrate is obtained. . Although the chemical structure is not necessarily clear, it is presumed that the platinum atom of the platinum complex is coordinated to a plurality of vinyl-containing silyl groups generated on the surface of the bonding substrate.

  A hydrosilyl group-containing polysiloxane, or a vinyl group-containing polysiloxane and, if necessary, a composition containing a platinum-containing catalyst are applied to the base material for adhesion and cured. As a result, the hydrosilyl group of the hydrosilyl group-containing polysiloxane undergoes a hydrosilylation reaction to the double bond of the vinyl-containing silyl group preferentially over the cross-linking polymerization of the vinyl-containing silyl groups of the adhesive substrate, thereby increasing the molecular weight. Thus, a silicone rubber adhesive body obtained by coating and adhering a silicone rubber formed of polysiloxanes onto the surface of the substrate of the adhesive base material is obtained.

  As a platinum-containing catalyst, for example, SIP6829.2 (trade name manufactured by Gelest), which is a hexane solution of a platinum-tetramethyldivinyldisiloxane complex, a vinylmethyl cyclic siloxane solution of a platinum carbonylcyclovinylmethylsiloxane complex of 1.85 to 2.1%, SIP6830.3 (trade name, manufactured by Gelest) which is a vinyl polydimethylsiloxane solution at both ends of 3 to 3.5% platinum-divinyltetramethyldisiloxane complex, xylene of 2.1 to 2.4% platinum-divinyltetramethyldisiloxane complex SIP6831.2LC (trade name, manufactured by Gelest) which is a solution, SIP6831.2LC (trade name, manufactured by Gelest) which is a low coloring type of xylene solution of platinum-divinyltetramethyldisiloxane complex of 2.1 to 2.4%, 2 SIP6832.2 (trade name made by Gelest), which is a cyclic methylvinylsiloxane solution of ~ 2.5% platinum-cyclovinylmethylsiloxane complex, 2 ~ 2.5% platinum- Platinum complexes such as octanol solution of Kutanaru / octanol complex SIP6833.2 (Gelest Inc. of trade name) and the like. In place of the platinum-containing catalyst, a rhodium-containing catalyst such as a rhodium complex such as INRH078 (trade name manufactured by Gelest), which is a toluene solution of 3 to 3.5% tris (dibutyl sulfide) rhodium trichloride, may be used. .

  Although an example in which silicone rubber is bonded to a single bonding substrate has been shown, a plurality of, for example, two bonding substrates are faced to each other on the surfaces where silyl ether bonds are formed by active silyl groups, and silicone rubber is interposed therebetween. Even if a plurality of adhesive substrates are bonded by applying a composition or by interposing a granular, cloth-like, thin-film-like, film-like or plate-like silicone rubber, if necessary, it is heated. Good. The substrates of the plurality of adhesive substrates may be the same or different.

  Examples of the prototype of the silicone rubber bonding substrate and silicone rubber bonded body of the present invention will be described in detail below.

(Example 1) H-terminal dimethylsiloxane (HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H, bp: 70 ° C) and unsaturated silane (CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) _3, bp: 176 ° C) reaction:
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H 0.5 mol (67 g), CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) ₃ 0.1 mol (20.4 g), room temperature reaction type platinum catalyst solution (Gelest SIP6830 .3) 0.2 ml was placed in a 200 ml Erlenmeyer flask and stirred at 50 ° C. for 24 hours under a nitrogen stream. When the reaction mixture is distilled after completion of the reaction, unreacted HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H is distilled off, and crude HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ 33.8 g of Si (OC ₂ H ₅ ) ₃ was obtained. This was produced by distillation under reduced pressure of 82-3 ° C./10 mmHg.
Elemental analysis Found (Calcud): C; 46.0% (46.10%), H; 8.9% (8.93%)

(Example 2) SiH substrate surface preparation method A:
HSi (CH ₃ ) ₂ OSi after corona discharge treatment (corona master) on the surface of base materials such as polyethylene terephthalate (PET) resin plate (30mm × 50mm), Al plate (30mm × 50mm) and glass plate (30mm × 50mm) (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ soaked in a methanol-water mixed solution (95/5, 0.5wt%) for 2 minutes, dried at room temperature, and then at 150 ° C for 10 minutes An HSi group-containing substrate surface is obtained.

As a result of measuring the surface of the obtained HSi group-containing base material by XPS (ESCA-5600 manufactured by PHI, Al output: 350 W, take-in angle: 45 degrees), all were C1s: 184 eV, Si1s for HSi; ev, Si1s for From the fact that SiCH ₃ ; was observed, it was found that the surface of the HSi group-containing base material was formed on any substrate made of PET resin, Al plate, and glass.

(Example 3) Production method B of SiH substrate surface:
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ after corona discharge treatment (corona master) of substrate surface such as PET resin plate (30mm × 50mm), Al plate (30mm × 50mm) and glass plate (30mm × 50mm) When immersed in a methanol solution (0.2 wt%) of CH ₂ CH ₂ Si (OCH ₃ ) ₃ for 2 minutes, dried at room temperature and then 10 minutes at 150 ° C., a CH ₂ = CH group-containing substrate surface is obtained. When this is dipped in 100 ml of HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H10 g and platinum catalyst solution (Gelest SIP6830.3) 0.2 ml isopropanol solution at 70 ° C. for 10 minutes, the surface of the substrate containing HSi group is obtained. It was. As a result of measuring the surface of the obtained HSi group-containing base material with an X-ray induced photoelectron spectroscopy (XPS) analyzer (ESCA-5600 manufactured by PHI, Al output: 350 W, take-in angle: 45 degrees), all C1s: 184 eV , Si1s for HSi; ev, Si1s for SiCH ₃ ; was found to indicate that the surface of the HSi group-containing base material was formed on any of the PET resin, Al plate, and glass substrates.

(Example 4) Preparation method of CH ₂ = CH-group-containing substrate surface C:
CH ₂ = CHSi (OCH ₃ ) ₂ O [after corona discharge treatment (corona master) of substrate surface such as PET resin plate (30mm × 50mm), Al plate (30mm × 50mm) and glass plate (30mm × 50mm) SiOCH ₃ (CH = CH ₂ ) O] ₂ Si (OCH ₃ ) ₂ CH = CH ₂ is immersed in a methanol-water mixed solution (95/5, 0.1 wt%) for 2 minutes, dried at room temperature, and then treated at 170 ° C for 5 minutes. If it is made for a minute, a CH ₂ ═CH group-containing substrate surface is obtained.
As a result of measuring the obtained CH ₂ = CH group-containing substrate surface by XPS (PCA ESCA-5600, Al output: 350 W, take-in angle: 45 degrees), all were C1s for CH ₂ = CH: 184 eV; From this, it was found that the surface of the CH ₂ ═CH group-containing base material was formed on any substrate made of PET resin, Al plate, and glass.

(Example 5) Preparation method D of alkoxysilyl group-containing substrate surface:
After corona discharge treatment (corona master) on the substrate surface such as PET resin plate (30mm × 50mm), Al plate (30mm × 50mm) and glass plate (30mm × 50mm), (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Substrate surface containing C ₂ H ₅ OSi group after being immersed in ethanol-water mixed solution of Si (OC ₂ H ₅ ) ₃ (95/5, 0.1wt%) for 2 minutes, dried at room temperature and then at 120 ° C for 60 minutes Is obtained.

As a result of measuring the obtained C ₂ H ₅ OSi group-containing substrate surface by XPS (ESCA-5600, manufactured by PHI, Al output: 350 W, take-in angle: 45 degrees), all were C1s for C ₂ H ₅ OSi: 184 eV; O1s for C ₂ H ₅ OSi: 184 eV; Si1s for C ₂ H ₅ OSi: 184 eV; therefore, the surface of the C ₂ H ₅ OSi group-containing substrate was made of PET resin, Al plate, or glass It was found that it was also generated on the substrate.

(Example 6) Adhesive of base material surface and silicone rubber:
A mixture of 100 parts of terminal vinyl type silicone (Chisso Corporation, DMS-V31, molecular weight; 28000) and 30 parts of hexamethylsilazane-treated silica, 3 parts of methyl H siloxane copolymer and 2 ml of platinum catalyst (200 ppm, SIP6830 from Chisso Corporation) ) To obtain a silicone rubber compound. Each substrate surface prepared by the above-mentioned substrate surface preparation methods A, B and C was put in a mold, and a silicone rubber compound was poured to a thickness of 2 cm, and an adhesive was obtained when left at 40 ° C. . As a result of measuring the peel strength at a tensile rate of 5 mm / min by putting a 1 width fillet into the adhesive, no adhesive was obtained in the comparative example in which the substrate surface of the present invention was not used, and the peel strength was Is 0 kN / m, but all the adhesives obtained using the surface of the base material into which unsaturated groups or SiH groups were introduced showed a value of 4 kN / m or more, and the fracture surface was silicone rubber layer failure. It was. This result shows that the surface of the base material into which the unsaturated group or SiH group is introduced easily adheres to the addition type silicone rubber.

(Example 7) Adhesive of base material surface and silicone rubber:
Silanol silicone (mixed by Chisso Corporation, DMS-S33, molecular weight 43500) 100 parts, 50 parts of hexamethylsilazane-treated silica, 4 g of CH ₃ Si (OCOCH ₃ ) ₃ and 0.1 g of dibutyltin malate are mixed to form a silicone rubber A formulation is prepared. The surface of the alkoxysilyl group-containing substrate was placed in a mold, and the silicone rubber compound was placed in the mold and heated at 140 ° C. for 20 minutes to obtain an adhesive. As a result of measuring the peel strength at a tensile speed of 5 mm / min by putting a 1-width fillet on the adhesive, no adhesive was obtained in the comparative example, and the peel strength was 0 kN / m, but unsaturated. All of the adhesives obtained using the surface of the base material into which a group or SiH group was introduced showed a value of 5 kN / m or more, and the fracture surface was a silicone rubber layer fracture. This result shows that the surface of the base material into which the alkoxysilyl group is introduced easily adheres to the condensed silanol silicone rubber.

(Example 8) Adhesive of base material surface and silicone rubber:
A mixture of 100 parts of terminal vinyl type silicone (VDF-131, manufactured by Chisso Corporation) and 40 parts of hexamethylsilazane-treated silica is mixed with 4 parts of dicumyl peroxide to obtain a silicone rubber compound. Each surface of the CH ₂ ═CH group-containing substrate was placed in a mold, and a silicone rubber compound was placed on the surface and heated at 150 ° C. for 20 minutes to obtain an adhesive. As a result of measuring the peel strength at a tensile speed of 5 mm / min by putting a 1-width fillet on the adhesive, no adhesive was obtained in the comparative example, and the peel strength was 0 kN / m, but unsaturated. All of the adhesives obtained using the surface of the base material into which a group or SiH group was introduced showed a value of 6 kN / m or more, and the fracture surface was a silicone rubber layer fracture. This result shows that the surface of the CH ₂ ═CH group-containing substrate is easily bonded by the peroxide crosslinking system.

(Example 9) Another adhesive substrate and silicone rubber adhesive
(Preparation of Adhesive Substrate) An Al plate as a substrate was cleaned by irradiating ultrasonically in acetone for 30 minutes, and then subjected to cleaning treatment by irradiating twice for 10 minutes in ion-exchanged water. The surface of the substrate was subjected to corona discharge treatment in an air atmosphere, and the surface was oxidized to generate hydroxyl groups on the surface. Each of the six substrates is (CH ₂ = CH-) (CH ₃ O-) ₂ Si-O-[(CH ₂ = CH-) (CH ₃ O-) Si-O] _b1 -Si (-OCH ₃ ) ₂ (—CH═CH ₂ ) (wherein b1 is 3.78 and average molecular weight is 635.6) 0.1 g / L, 0.5 g / L, 1.0 g / L of vinylmethoxysiloxane (VMS) , 2.0 g / L, 3.0 g / L, 5.0 g / L and 10 g / L of ethanol aqueous solution (ethanol: water volume ratio 95: 5) was immersed for 5 minutes. The substrate was pulled up and heat-treated at 150 ° C. for 10 minutes. Unreacted vinylmethoxysiloxane (VMS) was washed with ethanol and dried to obtain a bonding substrate (VMS-Al). The surface analysis by X-ray photoelectron spectroscopy (XPS measurement) was performed on the cleaned Al substrate and the obtained base material for adhesion. The result is shown in FIG. Table 1 shows the ratio of elements on the surface of the cleaned Al substrate and the obtained base material for adhesion.

  As is clear from FIG. 1 and Table 1, vinyl methoxysiloxane (VMS) was introduced on the surface of the Al plate.

  (Preparation of Silicone Rubber Adhesive) Next, poly (methylvinylsiloxane) and poly (methylsiloxane), trade name KE-1935-A / B manufactured by Shin-Etsu Chemical Co., Ltd., and a platinum-containing catalyst were mixed at the time of use. After that, the pressure was reduced to a vacuum and deaerated to prepare a liquid silicone rubber forming composition. This composition is applied to a bonding substrate (VMS-Al), heated to 50 ° C. and cured, and reacted with a vinyl group derived from vinyl methoxysiloxane (VMS) on the bonding substrate to crosslink silicone. When rubber was used, six types of silicone rubber adhesives were obtained for each concentration of vinyl methoxysiloxane (VMS) ethanol solution. For control, a control silicone rubber adhesive was obtained in the same manner except that an ethanol solution of vinyl methoxysiloxane (VMS) was not used. About these silicone rubber adhesive bodies, the 90 degree peel test which peels a silicone rubber according to the test method of JISK6256-2: 2005 was performed, and peeling strength was measured. The correlation between the concentration of vinyl methoxysiloxane (VMS) in ethanol and the peel strength is shown in FIG.

  As is clear from FIG. 2, the peel strength of the silicone rubber adhesive was stronger as the concentration of the ethanol solution of vinyl methoxysiloxane (VMS) was 0.1 to 1.0 g / L, but when it exceeded 1.0 g / L It became almost constant at about 1.0 kN / m. In any case, the ethanol strength of vinyl methoxysiloxane (VMS) was not used, and the strength was stronger than the peel strength of 0.4 kN / m of the control silicone rubber adhesive when the concentration was 0 g / L.

(Example 10) Another base material for adhesion and silicone rubber adhesive
(Preparation of adhesive substrate) In the same manner as in Example 9 (Preparation of adhesive substrate), a 1.0 g / L aqueous ethanol solution of vinylmethoxysiloxane (VMS) was used, and the adhesive substrate (VMS-Al ) Seven of these were dipped in a hexane solution of 100 ppm platinum-tetramethyldivinyldisiloxane complex for 1, 2, 3, 4, 5, 7, and 10 minutes, respectively, and then removed and dried. Thus, a base material for adhesion (Pt-VMS-Al) having a platinum-containing catalyst on the surface was obtained.

  (Preparation of Silicone Rubber Adhesive) Next, poly (methyl vinyl siloxane), poly (methyl siloxane) and a platinum-containing catalyst were mixed at the time of use in the same manner as in Example 9, and then degassed by reducing the pressure to a vacuum. A silicone rubber forming composition was prepared. This composition is applied to an adhesive substrate (Pt-VMS-Al), cured by heating to 50 ° C., and reacted with vinyl groups derived from vinyl methoxysiloxane (VMS) on the adhesive substrate to crosslink. When the silicone rubber was used, seven types of silicone rubber adhesives were obtained for each immersion time of the hexane solution of the platinum-tetramethyldivinyldisiloxane complex. For comparison, a control silicone rubber adhesive was obtained in the same manner except that a hexane solution of a platinum-tetramethyldivinyldisiloxane complex was not used. About these silicone rubber adhesive bodies, it carried out similarly to Example 9, the 90 degree peel test which peels a silicone rubber was performed, and peel strength was measured. FIG. 3 shows the correlation between the immersion time of the platinum-tetramethyldivinyldisiloxane complex in a hexane solution and the peel strength.

  As is clear from FIG. 3, the peel strength of the silicone rubber adhesive was stronger as it was dipped longer when the immersion time of the hexane solution of the platinum-tetramethyldivinyldisiloxane complex was 1 to 2 minutes, but exceeded 2 minutes. It became almost constant at about 4.0kN / m. In either case, the peel strength of the control silicone rubber adhesive was about 1.0 kN / m, which was a case where the immersion time was 0 minutes without using a hexane solution of the platinum-tetramethyldivinyldisiloxane complex.

Example 11 Another Adhesive Base Material and Silicone Rubber Adhesive
(Preparation of adhesive substrate) In the same manner as in Example 9 (Preparation of adhesive substrate), a 1.0 g / L aqueous ethanol solution of vinylmethoxysiloxane (VMS) was used, and the adhesive substrate (VMS-Al ) Four of these were immersed in hexane solutions of 20 ppm, 60 ppm, 100 ppm and 200 ppm of platinum-tetramethyldivinyldisiloxane complex for 3 minutes, then taken out and dried, and the surface was attached with a platinum-containing catalyst. A substrate (Pt-VMS-Al) was obtained.

  (Preparation of Silicone Rubber Adhesive) Next, poly (methyl vinyl siloxane), poly (methyl siloxane) and a platinum-containing catalyst were mixed at the time of use in the same manner as in Example 9, and then degassed by reducing the pressure to a vacuum. A silicone rubber forming composition was prepared. This composition is applied to an adhesive substrate (Pt-VMS-Al), cured by heating to 50 ° C., and reacted with vinyl groups derived from vinyl methoxysiloxane (VMS) on the adhesive substrate to crosslink. When the silicone rubber was made, four types of silicone rubber adhesives were obtained for each concentration of the hexane solution of the platinum-tetramethyldivinyldisiloxane complex. For comparison, a control silicone rubber adhesive was obtained in the same manner except that a hexane solution of a platinum-tetramethyldivinyldisiloxane complex was not used. About these silicone rubber adhesive bodies, it carried out similarly to Example 9, the 90 degree peel test which peels a silicone rubber was performed, and peel strength was measured. FIG. 4 shows the correlation between the concentration of the hexane solution of the platinum-tetramethyldivinyldisiloxane complex and the peel strength.

  As can be seen from FIG. 4, the peel strength of the silicone rubber adhesive was substantially constant at a concentration of about 4.0 kN / m when the concentration of the platinum-tetramethyldivinyldisiloxane complex in the hexane solution was 200 ppm or more. In either case, the peel strength of the control silicone rubber adhesive was about 1.0 kN / m, which was a case where the hexane solution of platinum-tetramethyldivinyldisiloxane complex was not used and the concentration was 0 g / L.

(Example 12) Another adhesive base material and silicone rubber bonded body A glass plate was used in place of the Al plate in Example 9, and a 1.0 g / L aqueous ethanol solution of vinyl methoxysiloxane (VMS) was used. In the same manner as in Example 9, an adhesive base material (VMS-Glass) was obtained instead of VMS-Al. After being immersed in a hexane solution of 100 ppm platinum-tetramethyldivinyldisiloxane complex for 3 minutes, it was taken out and dried to obtain an adhesive substrate (Pt-VMS-Glass) having a platinum-containing catalyst on the surface. . Next, poly (methyl vinyl siloxane), poly (methyl siloxane) and a platinum-containing catalyst were mixed at the time of use in the same manner as in Example 9 and then degassed under reduced pressure to prepare a liquid silicone rubber-forming composition. did. This composition is applied to an adhesive substrate (Pt-VMS-Glass), heated to 150 ° C. to cure, and reacted with vinyl groups derived from vinyl methoxysiloxane (VMS) on the adhesive substrate to crosslink. When the silicone rubber was made, a silicone rubber adhesive was obtained. The silicone rubber adhesive was subjected to a 90 ° peel test for peeling the silicone rubber in the same manner as in Example 9, and the peel strength was measured. The result was 3.7 kN / m.

(Examples 13 to 15) Another adhesive base material and silicone rubber adhesive body An epoxy resin (EpoxyResin) plate, a polypropylene (PP) plate, and a polyethylene (PE) plate were used instead of the glass plate in Example 12 Except for the above, in the same manner as in Example 12, the bonding substrate (Pt-VMS-EpoxyResin), the bonding substrate (Pt-VMS-PP), the bonding substrate (Pt-VMS-PE) and their silicones A rubber adhesive was obtained. Similarly, a 90 ° peel test was conducted to peel the silicone rubber, and the peel strength was measured. The silicone rubber adhesive obtained from the adhesive base material (Pt-VMS-EpoxyResin) was 3.8 kN / m. The silicone rubber adhesive obtained from (Pt-VMS-PP) was 3.2 kN / m, and the silicone rubber adhesive obtained from the base material for adhesion (Pt-VMS-PE) was 3.3 kN / m.

  As is clear from these examples, the silicone rubber bonded body prepared using the bonding base material to which the present invention is applied has high adhesive strength. In particular, when the adhesive surface is bonded to a base material for adhesion with a vinyl-containing silyl group and a platinum-containing catalyst attached to a solid such as silicone rubber having hydrosilyl as a reactive group, the silicone rubber will break. A silicone rubber adhesive was obtained.

  The adhesive base material of the present invention is used to protect a base material or impart elasticity by coating the base material made of metal, polymer resin, glass or ceramic with silicone rubber. .

Silicone rubber adhesives obtained by bonding silicone rubber to a base material are used for home appliances, stationery, and the like that require elasticity on the surface. Moreover, since the silicone rubber adhesive body which adhere | attached this several base material through the silicone rubber is joined via a chemical bond, it is used for the product which requires strong joint strength.

It is a figure which shows the result of the surface analysis by the X-ray photoelectron spectroscopy measurement of the base material for adhesion | attachment to which this invention is applied. It is a figure which shows the correlation of the density | concentration of the vinyl methoxysiloxane which immerses the base material for adhesion when producing the silicone rubber adhesive body to which this invention is applied, and the peeling strength of the obtained silicone rubber adhesive body. It is a figure which shows the correlation with the immersion time of the platinum containing catalyst which immerses the base material for adhesion when producing the silicone rubber adhesive body which applies this invention, and the peeling strength of the obtained silicone rubber adhesive body. It is a figure which shows the correlation of the density | concentration of the platinum containing catalyst which immerses the base material for adhesion | attachment when producing the silicone rubber adhesive body to which this invention is applied, and the peeling strength of the obtained silicone rubber adhesive body.

Claims (21)

At least one active silyl group selected from a hydrosilyl-containing silyl group, a vinyl-containing silyl group, an alkoxysilyl-containing silyl group, and a hydrolyzable group-containing silyl group that reacts and bonds to a reactive group on the surface of the solid to be bonded. A bonded surface is formed by silyl ether bonding to the dehydrogenated group of the hydroxyl group on the surface of the substrate formed of metal, polymer resin, glass or ceramics ,
The active silyl group is
It is selected from a monohydrosilyl-containing silyl group and a dihydrosilyl-containing silyl group, and —SiH (R ¹ ) ₂ or —SiH ₂ (R ² ) (R ¹ and R ² are alkyl having 1 to 4 carbon atoms ) at the terminal of the group The hydrosilyl-containing silyl group having a group) or having a —SiH— group in the middle of the main chain of the group;
A vinyl silyl-containing silyl group, the terminal of the group has -Si-R ³ group a (R ³ is a vinyl containing group), or a middle -Si backbone of the group (R ⁴⁾ - group (R ⁴ is a vinyl-containing group) having the vinyl-containing silyl group;
It is selected from trialkoxysilyl terminal-containing silyl group and dialkoxysilyl terminal-containing silyl group, and at the terminal of the group, -Si (OR ⁵ ) ₂ R ⁶ group (R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms) Or an alkoxysilyl-containing silyl group having a —Si (OR ⁷ ) ₃ group (R ⁷ is an alkyl group having 1 to 4 carbon atoms);
The hydrolyzability selected from acyloxysilyl group, alkenyloxysilyl group, alkaneiminooxysilyl group, alkyloxysilyl group, alkylaminosilyl group, dialkylaminosilyl group, nitrogen-containing heterocyclic substituted silyl group, and arylaminosilyl group -Si (R ⁸ ) _a (R ⁹ ) _3-a group (R ⁸ is a hydrogen atom; a halogen atom; an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkyloxy group, A fluorine-substituted alkyl group; an aralkyl group; an aryl group, and R ⁹ is an acyloxy group having 1 to 12 carbon atoms, an alkenyloxy group, an alkaneiminooxy group, an alkyloxy group, an alkylamino group, a dialkylamino group; A cyclic group and an arylamino group, wherein a is a number of 0 to 3) and includes the hydrolyzable group having the hydrolyzable functional group. Silyl group
And
A catalyst comprising a platinum-containing catalyst or a rhodium-containing catalyst that bonds the solid by reacting and reacting with a reactive group on the surface of the solid on the adhesive surface is attached to the adhesive surface bonded with the silyl ether,
Further, a composition containing a silicone rubber component of polysiloxanes, vinyl silicones and / or silanol silicones, which is degassed under reduced pressure, is cured, and the surface is coated to adhere the silicone rubber. And
An adhesive base material for adhering the silicone rubber with the composition degassed under reduced pressure . The hydroxyl group is a hydroxyl group on the surface of the substrate, or a hydroxyl group generated by any one of corona discharge, atmospheric pressure plasma treatment and ultraviolet irradiation to the substrate, and is derived from the alkoxysilyl group of the alkoxysilane compound. The base material for adhesion according to claim 1, wherein the silyl ether bond is bonded to an active silyl group.   The adhesive base according to claim 2, wherein the solid surface is oxidized to have the hydroxyl group, and the silyl ether bond is formed to the active silyl group derived from an alkoxysilyl group.   The adhesion base material according to claim 3, wherein a monomolecular film is formed by the silyl ether bond with the alkoxysilane compound. The adhesive substrate according to claim 2 , wherein the treatment is continued until the surface of the substrate has a surface tension of at least 55 kJ / m . The silyl ether bond has the following chemical formula [1]
Sub.-O-SiR ²⁰ ... [1]
(In the formula [1], Sub. Is the substrate that is the adherend substrate and is a group that forms this silyl ether bond, and -SiR ²⁰ is the hydrosilyl-containing silyl group that is a polysiloxy group ). adhesive base material according to claim 1, characterized in that represented. The silyl ether bond is represented by the following chemical formula [2]
Sub.-O-SiR ²¹ ... [2]
(Wherein [2], Sub. Is a group which forms a silyl ether linkage A wherein the substrate is a adherend substrate, -SiR ²⁰ in the vinylsilyl-containing silyl group chromatic 1 to 30 vinyl groups The adhesive base material according to claim 1 , which is represented by: The silyl ether bond has the following chemical formula [3]
Sub.-O-SiR ²² ... [3]
(In the formula [3], Sub. Is a substrate that forms the silyl ether bond and is the substrate that is the adherend substrate, and —SiR ²² is — (C ₂ H ₅ O) ₂ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,-(C ₂ H ₅ O) CH ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,-(C ₂ H ₅ O) ₂ SiCH = CHSi (OC ₂ H ₅ ) ₃ ,-(CH ₃ O) ₂ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ ,-(CH ₃ O) ₂ SiCH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,-(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₃ Si (OCH ₃ ) ₃ ,-(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₄ Si (OCH ₃ ) ₃ ,-(CH ₃ O) CH ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ ,-(C ₂ H ₅ O) CH ₃ SiOSi (OC ₂ H ₅ ) ₂ CH ₃ ,-(C ₂ H ₅ O) Si (OC ₂ H ₅ ) ₂
Any one of the above-mentioned alkoxysilyl terminal-containing silyl groups . The adhesive base material according to claim 1 , which is represented by: The silyl ether bond has the following chemical formula [4]
Sub.-O-Si (R ⁸ ) _a (R ⁹ ) _3-a ... [4]
(In the formula [4], Sub. Is a substrate that forms the silyl ether bond and is the substrate that is the adherend substrate, and —Si (R ⁸ ) _a (R ⁹ ) _3-a is R ⁸ _{but, H-, F-, CH 3 -} , C 2 H 5 -, CH 2 = CH-, nC 3 H 7 -, iC 3 H 7 -, CH 2 = CHCH 2 -, C 4 H 9 -, C _{6 H 13 -, C 8 H} 17 -, C 6 H 5 -, CH 3 C 6 H 4 -, C 6 H 5 CH 2 -, CF 3 CF 2 CH 2 CH 2 -, CF 3 CF 2 CF 2 CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , CH ₃ O-, or C ₂ H ₅ O-, R ⁹ is CH ₃ COO-, CH ₂ = C (CH ₃ ) O-, C ₂ H ₅ (CH ₃ ) C = NO-, CH ₃ O-, (CH ₃ ) ₂ N-, (C ₂ H ₅ ) ₂ N-, (iC ₃ H _{7) 2 N-, O (CH} 2 CH 2) 2 N -, (CH 3) 3 CNH-, with C ₆ H ₁₀ NH-, or C ₆ H ₅ NH- in which the hydrolyzable group-containing silyl group The adhesive base material according to claim 1 , which is represented by:   The adhesive according to claim 1, wherein the reactive group is at least one selected from hydrosilyl, vinylsilyl, hydroxysilyl, alkyloxysilyl, alkenyloxysilyl, acyloxysilyl, iminooxysilyl, and alkylaminosilyl. Substrate for use. The active silyl group is the vinyl-containing silyl group, it said platinum-containing catalyst or the rhodium-containing catalyst has been subjected to the adhesion surface to expose the, claims, characterized in that the reactive group and hydrosilyl Item 2. The bonding substrate according to Item 1.   The adhesive substrate according to claim 11, wherein the platinum-containing catalyst is a platinum complex, and the rhodium-containing catalyst is a rhodium complex.   The bonding substrate according to claim 11, wherein the platinum-containing catalyst or the rhodium-containing catalyst is applied or dipped in a solution or suspension containing the catalyst.   The bonding substrate according to claim 11, wherein platinum atoms or rhodium atoms of the platinum-containing catalyst or the rhodium-containing catalyst are coordinated to a plurality of the vinyl-containing silyl groups. The vinyl-containing silyl group is represented by (CH ₂ = CH-) (CH ₃ O-) ₂ Si-O-[(CH ₂ = CH-) (CH ₃ O-) Si-O] _b1 -Si (-OCH ₃ ) ₂ (-CH = CH ₂ ) (b1 is a number from 0 to 100),
(CH ₂ = CH-) (C ₂ H ₅ O-) ₂ Si-O-[(CH ₂ = CH-) (C ₂ H ₅ O-) Si-O] _b2 -Si (-OC ₂ H ₅ ) ₂ (number of b2 is _{0~100) (-CH = CH 2)} ,
(CH ₂ = CH-) (C ₃ H ₇ O-) ₂ Si-O-[(CH ₂ = CH-) (C ₃ H ₇ O-) Si-O] _b3 -Si (-OC ₃ H ₇ ) ₂ (number of b3 is _{0~100) (-CH = CH 2)} ,
The base material for adhesion according to claim 11, wherein the base material is derived from a vinyl-containing silyl compound selected from:   The base material for adhesion according to claim 1, wherein the solid is silicone rubber or silicone resin. A composition degassed under reduced pressure containing a silicone rubber component of polysiloxanes, vinyl silicones and / or silanol silicones on the surface of the substrate of the adhesive substrate according to any one of claims 1 to 16. A silicone rubber adhesive , wherein the silicone rubber formed by being attached and cured is coated and adhered.   18. The bonded silicone rubber body according to claim 17, wherein the plurality of bonding base materials are bonded together via the granular, cloth-like, thin-film-like, film-like, or plate-like silicone rubber. . The polysiloxane is H (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _c [Si (R ¹¹ ) R ¹² O] _d Si (CH ₃ ) ₂ H (R ¹¹ and R ¹² are carbon atoms 1 to 12 alkyl groups, alkenyl groups, alkyloxy groups, fluorine-substituted alkyl groups; aralkyl groups; aryl groups; HSi (CH ₃ ) ₂ O—, c is a number from 1 to 80, d is 0 to 80 Number)
The vinyl silicone is CH ₂ ═CH (CH ₃ ) ₂ SiO [SiCH═CH ₂ (CH ₃ ) O] _e [Si (R ¹³ ) R ¹⁴ O] _f Si (CH ₃ ) ₂ CH═CH ₂ ( R ¹³ and R ¹⁴ are an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkyloxy group, a fluorine-substituted alkyl group; an aralkyl group; an aryl group, e is a number from 1 to 80, and f is a number from 0 to 80. Number)
The silanol silicones are A- (CH ₃ ) ₂ SiO [Si (CH ₃ ) ₂ O] _g [Si (R ¹⁵ ) R ¹⁶ O] _h Si (CH ₃ ) ₂ -A (R ¹⁵ and R ¹⁶ are , An alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkyloxy group, a fluorine-substituted alkyl group; an aralkyl group; an aryl group, and A is a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkenyloxy group, an aryl group. 18. The silicone rubber adhesive according to claim 17, which is an oxy group, an acyloxy group, an iminooxy group, or an amino group, wherein g is a number from 1 to 80, and h is a number from 0 to 80. Over the surface of the substrate of the bonding substrate according to any one of claims 1 to 16, polysiloxanes, vinyl silicones and / or silanol silicones composition the silicone rubber components were unrealized vacuum degassing And is cured at room temperature or under heating to cover the surface and adhere silicone rubber.   The method for producing a silicone rubber adhesive according to claim 20, wherein the composition contains a crosslinking agent and / or a crosslinking catalyst.

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