JP5191192B2 - Molecular adhesive, cross-linking reactive solid surface, and method for producing the cross-linking reactive solid surface - Google Patents

Description

  The present invention relates to a crosslinking reactive solid surface excellent in adhesiveness to rubber, particularly sulfur crosslinking rubber, and a method for producing the crosslinking reactive solid surface. Furthermore, the present invention relates to a method for producing a solid material-rubber cross-linked adhesive obtained from a solid material having a cross-linking reactive solid surface and rubber.

  Conventionally, there have been many demands for rubber composite materials composed of rubber and solid materials such as crosslinked rubber, resin, fiber, metal and ceramics, but there are many problems with the bonding method between different materials of solid material and rubber. there were.

  As a conventional bonding method, for example, there is known a method in which a solid surface such as a resin is subjected to a pretreatment such as a degreasing process or a blasting process, a primer or an adhesive is applied, and then an uncrosslinked rubber is brought into contact and subjected to thermocompression bonding. It has been. However, since such a method goes through a very complicated process, it has been difficult to produce a uniform product. Furthermore, it is necessary to select an appropriate adhesive depending on the surface of the solid such as crosslinked rubber, resin, fiber, metal and ceramics, and the type of rubber material, thereby further complicating the bonding technique.

  In addition, the method of using an adhesive requires facilities and equipment for using the adhesive and equipment that can reduce the concentration of the adhesive component diffused in the air. There are many problems.

  In addition, a method is known in which a silane coupling agent is added to rubber instead of an adhesive to adhere the rubber and the dissimilar material. A thick interface layer with a good elastic modulus was required. However, it is difficult in principle to obtain an intermediate elastic modulus between rubber and a different material without using an adhesive, and it is practically impossible to bond such a different interface without an adhesive. there were.

As a method for adhering rubber and a different material such as resin and rubber, a method using a molecular adhesive composed of an alkoxysilane-containing triazine thiol metal salt is known (see, for example, Patent Documents 1 and 2). In Patent Documents 1 and 2, cross-linking reactivity can be imparted to the solid surface by reacting the alkoxysilyl group of the molecular adhesive with the OH group-containing solid surface, and as a result, the surface and the rubber material. It is described that can be bonded. However, the adhesion method using the alkoxysilyl group-containing triazine thiol compound described in these patent documents has sufficient adhesive strength in the cross-linking adhesion between a sulfur-crosslinked rubber-containing uncrosslinked rubber and metal, resin, etc. Could not be obtained.
JP 2006-213677 A JP 2007-119752 A

  An object of the present invention is to provide a cross-linking reactive solid surface excellent in adhesiveness to rubber, particularly sulfur cross-linking rubber, and a method for producing the cross-linking reactive solid surface. Furthermore, an object of the present invention is to provide a method for producing a solid material-rubber crosslinked adhesive having high adhesive strength between rubber, particularly sulfur-crosslinked rubber and solid material.

  As a result of various studies on the above problems, the present inventors have found a cross-linking reactive solid surface excellent in adhesiveness to rubber, particularly sulfur cross-linking rubber, and a method for producing the cross-linking reactive solid surface. I was able to. In addition, the present inventors have found a method for producing a solid material-rubber crosslinked adhesive having high adhesive strength by contacting and thermocompression bonding a solid material having a crosslinking reactive solid surface and a rubber crosslinked compound.

That is, the present invention is as follows.
Item 1. General formula (1):
[X _a (YO) _{3 -a} SiR ¹ ] _b Z (1)
(In the formula, X and Y may be the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms; R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms; The alkylene group may include —NH—, —CO—, —O—, —S—, —COO—, —C ₆ H ₄ —, wherein Z is —SH, —SCSN (CH ₃ ). ₂ , -SSSCN (CH ₃ ) ₂ , -SCSN (C ₂ H ₅ ) ₂ , -SCSN (C ₄ H ₉ ) ₂ , -SCSN (C ₈ H ₁₇ ) ₂ , -SS-, -SSS-, -SSSS −,

It is. a is 0, 1 or 2, and b is 1 or 2. )
A molecular adhesive characterized by exhibiting crosslinking reactivity comprising a compound represented by the formula:
Item 2. Item 1. Molecular adhesive and general formula (2):

(Wherein R ² is —OR ³ (R ³ is an alkyl group having 1 to 4 carbon atoms), —NR ⁴ R ⁵ (R ⁴ and R ⁵ may be the same or different, and R ⁴ and R ⁵ may be bonded to each other, and each represents H, an alkyl group having 1 to 4 carbon atoms, an alkylene group, an alkenyl group, or a phenylene group, and the alkylene group includes —NH—, —CO—, -O-, -S-, -COO-) or -SM ¹ (M ¹ is an alkali metal or H), and M ² and M ³ are the same or different. It may be an alkali metal or H.)
The molecular-adhesive composition containing the triazine compound represented by these.
Item 3. General formula (3):

(In the formula, X is an alkyl group or alkenyl group having 1 to 4 carbon atoms, R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms, and the alkylene group includes —NH— and —CO—. , —O—, —S—, —COO—, —C ₆ H ₄ —, wherein Z is —SH, —SCSN (CH ₃ ) ₂ , —SSCSN (CH ₃ ) ₂ , —SCSN. _{(C 2 H 5) 2,} -SCSN (C 4 H 9) 2, -SCSN (C 8 H 17) 2, -SS -, - SSS -, - SSSS-,

It is. a is 0, 1 or 2, and b is 1 or 2. )
A crosslinkable reactive solid surface having a crosslinkable reactive group represented by the formula:
Item 4. General formula (4):

(In the formula, X is an alkyl group or alkenyl group having 1 to 4 carbon atoms, R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms, and the alkylene group includes —NH— and —CO—. , —O—, —S—, —COO—, —C ₆ H ₄ —, wherein R ² is —OR ³ (R ³ is an alkyl group having 1 to 4 carbon atoms), —NR ⁴ R ⁵ (R ⁴ and R ⁵ may be the same or different, and R ⁴ and R ⁵ may be bonded to each other, and each of H, an alkyl group having 1 to 4 carbon atoms, an alkylene group, An alkenyl group or a phenylene group, and the alkylene group may contain —NH—, —CO—, —O—, —S—, —COO—, or —SM ¹ (M ¹ is an alkali metal) Or M ³ is an alkali metal or H, and Q is -S-, -SS-, -SSS-, -SSSS -, - CH (OH) CH 2 -)
A crosslinkable reactive solid surface having a crosslinkable reactive group represented by the formula:
Item 5. Item 5. The crosslinking reactive solid surface according to Item 3 or 4, wherein the solid surface is a solid surface of metal, ceramics or polymer.
Item 6. General formula (1):
[X _a (YO) _{3 -a} SiR ¹ ] _b Z (1)
(In the formula, X and Y may be the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms; R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms; The alkylene group may include —NH—, —CO—, —O—, —S—, —COO—, —C ₆ H ₄ —, wherein Z is —SH, —SCSN (CH ₃ ). ₂ , -SSSCN (CH ₃ ) ₂ , -SCSN (C ₂ H ₅ ) ₂ , -SCSN (C ₄ H ₉ ) ₂ , -SCSN (C ₈ H ₁₇ ) ₂ , -SS-, -SSS-, -SSSS −,

It is. a is 0, 1 or 2, and b is 1 or 2. )
A step of bringing a solution containing a molecular adhesive characterized by having a crosslinking reactivity into contact with a solid surface having an OH group on the surface, and heating the solid surface in contact with the solution containing the molecular adhesive Item 5. The method for producing a crosslinking reactive solid surface according to Item 3 or 4, comprising a step.
Item 7. In addition to the solution containing the molecular adhesive, the general formula (2):

(Wherein R ² is —OR ³ (R ³ is an alkyl group having 1 to 4 carbon atoms), —NR ⁴ R ⁵ (R ⁴ and R ⁵ may be the same or different, and R ⁴ and R ⁵ may be bonded to each other, H, an alkyl group having 1 to 4 carbon atoms, an alkylene group, an alkenyl group, or a phenylene group, and the alkylene group includes —NH—, —CO—, —O -, - S -, - a COO- or may contain) -SM ¹ (M ¹ is an alkali metal or H), be different even M ^2, M ³ are respectively the same Well, it is alkali metal or H.)
Item 7. A method for producing a cross-linking reactive solid surface according to Item 6, comprising a triazine compound represented by the formula:
Item 8. General formula (5):
X _a (YO) _3-a SiR ¹ Z ′ (5)
(In the formula, X and Y may be the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms; R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms; The alkylene group may contain —NH—, —CO—, —O—, —S—, —COO—, —C ₆ H ₄ —, wherein Z ′ is —Cl, —Br. a is 0, 1 or 2.)
A reactive solid surface obtained by heating a solid surface in contact with a solution containing a silane coupling agent by bringing the solution containing the silane coupling agent represented by ,
General formula (6):
M ⁴ _p Z (6)
(In the formula, M ⁴ is H, Li, Na, K or Cs , and Z is —SH, —SCSN (CH ₃ ) ₂ , —SSCSN (CH ₃ ) ₂ , —SCSN (C ₂ H ₅ ) _{2. , -SCSN (C 4 H 9)} 2, -SCSN (C 8 H 17) 2, -SS -, - SSS -, - SSSS-,

It is. p is 1 or 2. )
Item 5. The method for producing a cross-linking reactive solid surface according to Item 3 or 4, further comprising a step of contacting a solution containing a sulfur compound represented by the formula:
Item 9. The resulting cross-linking reactive solid surface;
General formula (2):

(Wherein R ² is —OR ³ (R ³ is an alkyl group having 1 to 4 carbon atoms), —NR ⁴ R ⁵ (R ⁴ and R ⁵ may be the same or different, and R ⁴ and R ⁵ may be bonded to each other, H, an alkyl group having 1 to 4 carbon atoms, an alkylene group, an alkenyl group, or a phenylene group, and the alkylene group includes —NH—, —CO—, —O -, - S -, - a COO- or may contain) -SM ¹ (M ¹ is an alkali metal or H), be different even M ^2, M ³ are respectively the same Well, it is alkali metal or H.)
Item 9. The method for producing a cross-linking reactive solid surface according to Item 6 or 8, comprising a step of contacting a solution containing a triazine compound represented by the formula: and a step of heating a solid surface in contact with the solution containing a triazine compound.
Item 10. Item 10. The method for producing a crosslinking reactive solid surface according to any one of Items 6 to 9, wherein the solid surface is a solid surface of metal, ceramics or polymer.
Item 11. Item 5. A method for producing a solid material-rubber crosslinked adhesive, comprising a step of contacting and thermocompression bonding a crosslinking reactive solid surface of a solid material having a crosslinking reactive solid surface according to Item 3 or 4 and a rubber crosslinked compound.
Item 12. Item 12. The method for producing a solid material-rubber crosslinked adhesive according to Item 11, wherein the rubber crosslinking compound is a compound comprising a rubber material, a filler, a crosslinking agent, a crosslinking accelerator and a metal activator.

The present invention is described in detail below.
1. Molecular Adhesive The present invention relates to a general formula (1):
[X _a (YO) _{3 -a} SiR ¹ ] _b Z (1)
(In the formula, X and Y may be the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms; R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms; The alkylene group may include —NH—, —CO—, —O—, —S—, —COO—, —C ₆ H ₄ —, wherein Z is —SH, —SCSN (CH ₃ ). ₂ , -SSSCN (CH ₃ ) ₂ , -SCSN (C ₂ H ₅ ) ₂ , -SCSN (C ₄ H ₉ ) ₂ , -SCSN (C ₈ H ₁₇ ) ₂ , -SS-, -SSS-, -SSSS −,

It is. a is 0, 1 or 2, and b is 1 or 2. )
The present invention relates to a molecular adhesive characterized by exhibiting crosslinking reactivity comprising a compound represented by the formula:

  Here, the molecular adhesive includes both a group capable of chemically bonding to the surface of a solid material having an OH group (alkoxysilyl group) and a group capable of crosslinking reaction with a rubber molecular chain (crosslinking reactive group). In addition, by chemically bonding the molecular adhesive to the surface of the solid material, crosslinking reactivity can be imparted to the surface of the solid material.

X and Y in the general formula (1) may be the same or different and are alkyl groups or alkenyl groups having 1 to 4 carbon atoms, and are not particularly limited. _{, CH 3 -, C 2 H} 5 -, n-C 3 H 7 -, i-C 3 H 7 -, CH 2 = CHCH 2 -, n-C 4 H 9 -, t-C 4 H 9 - the Among these, CH ₃ — is preferable.

The _{Y, CH 3 -, C 2} H 5 -, n-C 3 H 7 -, i-C 3 H 7 -, n-C 4 H 9 -, i-C 4 H 9 -, t-C 4 H _9- can be mentioned, and among these, CH ₃ -and C ₂ H ₅ -are preferred.

R ¹ is a C 1-18 alkylene group which may contain a phenylene group, —NH—, —CO—, —O—, —S—, —COO—, or —C ₆ H ₄ —. _{Specifically, -CH 2 -, - CH 2} (CH 2) n-2 CH 2 - (n is 2 to 18 _{integer), - C 6 H 4 -} , - CH 2 C 6 H 4 -, - CH ₂ C ₆ H ₄ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ NHCH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —, — (CH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ NHCOOCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ NHCONHCH ₂ CH ₂ CH ₂ — and the like can be mentioned, among them —CH ₂ ( _{CH 2) n-2 CH 2} - are preferred, -CH ₂ CH ₂ CH ₂ - is more preferable.

Z _{is, -SH, -SCSN (CH 3)} 2, -SSCSN (CH 3) 2, -SCSN (C 2 H 5) 2, -SCSN (C 4 H 9) 2, -SCSN (C 8 H 17) ₂ , -SS-, -SSS-, -SSSS-,

Of these, -SH, -SS-, -SSS-, and -SSSS- are preferred from the viewpoint of crosslinkability with rubber.

  a is 0, 1 or 2, but is preferably 0 or 1 and more preferably 0 from the viewpoint of reactivity with the solid surface.

Among the molecular adhesives of the present invention represented by the general formula (1), in the general formula (1), X is CH ₃ —, Y is CH ₃ —, C ₂ H ₅ —, and R ¹ is — CH ₂ CH ₂ CH ₂ —, Z is preferably —SH, —SS—, —SSS—, —SSSS—, and a is preferably 0 or 1.

  Specific examples of the molecular adhesive of the present invention represented by the general formula (1) include bis (triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like. be able to.

  As the molecular adhesive, the compound represented by the general formula (1) may be used alone or in combination of two or more.

The molecular adhesive of the present invention represented by the general formula (1) can be chemically bonded to an OH group on a solid surface by an alkoxysilyl group represented by X _a (YO) _{3 -a} Si-, and is represented by -Z. The crosslinkable reactive group can cause a cross-linking reaction with the rubber, and as a result, enables adhesion between different materials of the solid surface and the rubber.

2. Molecular adhesive composition When the solid surface and rubber are bonded, the molecular adhesive and the general formula (2):

It is preferable to use it as a molecular adhesive composition containing a triazine compound represented by the following from the viewpoint of the adhesive strength between a solid surface and rubber.

R ² in the general formula (2) is —OR ³ , —NR ⁴ R ^5, or —SM ¹ .

R ³ is an alkyl group having 1 to 4 carbon atoms, and specific examples include the same groups as those described above for Y in the general formula (1).

R ⁴ and R ⁵ may be the same or different from each other, and R ⁴ and R ⁵ may be bonded to each other, and each represents H, an alkyl group having 1 to 4 carbon atoms, or an alkylene group. , An alkenyl group, or a phenylene group. The alkylene group may contain —NH—, —CO—, —O—, —S—, and —COO—. As a C1-C4 alkyl group and an alkenyl group, the thing similar to what was mentioned by X of the above-mentioned general formula (1) can be mentioned.
The alkylene group having 1 to 4 carbon _{atoms, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 - and the like.

Specific examples of —NR ⁴ R ^{5 in} the case where R ⁴ and R ⁵ are bonded include

Etc.

M ^{1 to} M ³ may be the same or different, and are an alkali metal or H. Examples of the alkali metal include Li, Na, K, and Cs .

  Specific examples of the triazine compound represented by the general formula (2) include 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2-dibutylamino-4,6. -Dithiol, 1,3,5-triazine-2-diallylamino-4,6-dithithiol and the like can be mentioned.

  The blending ratio of the molecular adhesive represented by the general formula (1) and the triazine compound represented by the general formula (2) is preferably molecular adhesive: triazine compound = 1: 10 to 10: 1 (molar ratio). 1 to 5: 1 (molar ratio) is more preferable. It is preferable for the blending ratio to be in the above-mentioned range since higher adhesive strength can be expressed in the adhesion between the solid surface and the rubber.

3. Crosslinking reactive solid surface As the crosslinking reactive solid surface of the present invention,
General formula (2):
^{_{-O- [X a (-O) 2}} -a SiR 1] b Z (2)
A solid surface having a crosslinking reactive group represented by:
General formula (4):

It is the solid surface which has a crosslinking reactive group represented by these.

Examples of X, Y, R ¹ , Z, a, and b in the general formula (2) are the same as those described above.

Examples of X, R ¹ , R ² and M ³ in the general formula (4) are the same as those described above.

The Q in the general formula (4), -S -, - SS -, - SSS -, - SSSS -, - CH (OH) CH 2 - is.

  The solid surface is not particularly limited, and examples thereof include solid surfaces such as metals, ceramics, and polymers.

  Although it does not specifically limit as a metal, For example, Mg, Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd, In, Ta, Co, Ni, Sn, Sb Bi, Pb, Cu, Ag, Pt, Pd, Au and their binary, ternary and multi-component alloys. Examples of the alloy 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. The formation of an oxide film on these surfaces is a condition for the metal that can be used in the present invention.

  Among these, aluminum and stainless steel are preferable.

  The ceramic is not particularly limited. For example, Mg, Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd, In, Ta, Co, Ni, Sn, Sb, Examples thereof include metal materials such as Bi, Pb, Cu, Ag, and Si, and sintered bodies of oxides, carbides, nitrides, and borides of these binary, ternary, and multicomponent alloys.

  The polymer is not particularly limited, and examples thereof include cellulose and derivatives thereof, hydroxyethyl cellulose, starch, cellulose diacetate, surface saponified vinyl acetate resin, low density polyethylene, high density polyethylene, i-polypropylene, petroleum resin, polystyrene, s-styrene, chroman indene resin, terpene resin, styrene divinylbenzene copolymer, ABS resin, polymethyl acrylate, polyethyl acrylate, polyacrylonitrile, methyl methacrylate, ethyl methacrylate, polycyanoacrylate, poly Vinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ethylene copolymer, polyvinylidene fluoride, vinylidene fluoride, Tylene 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, polybutylene terephthalate, unsaturated polyester resin, allyl ester resin, polycarbonate, 6-nylon, 6,6-nylon, 6,10-nylon, polyimide, polyamide, polybenz Imidazole, polyamideimide, silicon resin, silicon 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 fiber, carbon fiber and more Polymer materials other than polytetrafluoroethylene such as blends of materials, natural rubber, 1,4-cisbutadiene rubber, isoprene rubber, polychloroprene, styrene / butadiene copolymer rubber, hydrogenated styrene / butadiene copolymer rubber, acrylonitrile・ Butadiene copolymer rubber, hydrogenated acrylonitrile / butadiene copolymer rubber, polybutene, polyisobutylene, ethylene / propylene rubber, ethylene / propylene terpolymer, chlorinated polyethylene, chlorosulfonated polyethylene Cross-linked products of rubber materials such as alkylated chlorosulfonated polyethylene, chloroprene rubber, chlorinated acrylic rubber, brominated acrylic rubber, fluorine rubber, epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber Etc. Among these, an epoxy resin is preferable.

  The shape of the solid material is not particularly limited. For example, particles, films, plates, rectangles, squares, polygons, various product shapes, cloths, cylinders, air threads, hoses, nets, spheres, ellipsoids, etc. Can be mentioned.

4). Method for producing crosslinking reactive solid surface The method for producing the crosslinking reactive solid surface is not particularly limited, and examples thereof include the following methods.

As the first manufacturing method,
General formula (1):
[X _a (YO) _{3 -a} SiR ¹ ] _b Z (1)
(Wherein, X and Y are the same as R ¹ , Z, a and b as described above.)
The manufacturing method including the process of making the solution containing the molecular adhesive characterized by showing by these and the OH group containing solid surface contact, and heating may be mentioned.

  Examples of the solid surface include the same as described above.

  In order to cause a chemical reaction between the molecular adhesive represented by the general formula (1) and the solid surface, it is necessary to have —OH groups on the solid surface. When a solid material having no —OH group on the surface is used, it is necessary to introduce an —OH group by a pretreatment, and even a solid having an —OH group is a molecular adhesion represented by the general formula (1). A pretreatment may be performed in order to improve the reactivity with the agent.

  Examples of the pretreatment method include corona discharge treatment, atmospheric pressure plasma treatment, and UV irradiation treatment.

  As these treatment methods, known methods can be used. For example, in the case of corona discharge treatment, “Corona treatment”, Journal of the Adhesion Society of Japan, Vol. 36, no. 3, 126 (2000), if it is atmospheric pressure plasma treatment, “plasma treatment”, Journal of the Adhesion Society of Japan, Vol. 41, no. 1, 4 (2005) can be suitably used. By these treatments, a large number of —OH groups, —COOH groups, —C═O groups and the like are generated on the solid surface or appear on the surface (LJ Gerenser: J. Adhesion Sci. Technol. 7, 1019). (1997)).

  In general, the solid surface is contaminated by absorbing dirt components in the atmosphere, but by performing the pretreatment as described above, -OH groups can be generated on the surface simultaneously with cleaning.

  The corona discharge treatment is performed using a corona surface reformer (for example, a corona master manufactured by Shinko Electric Measurement Co., Ltd.), power supply: AC 100 V, output voltage: 0 to 20 kV, oscillation frequency: 0.1 to 40 kHz. It can be performed under conditions of 60 seconds and a temperature of 0 to 60 ° C.

  The atmospheric pressure plasma treatment is performed using an atmospheric pressure plasma generator (for example, Aiplasma manufactured by Matsushita Electric Works Co., Ltd.), a plasma treatment speed of 10 to 100 mm / s, a power source: 200 or 220 V AC (30 A), and compressed air: 0.00. It can be performed under the conditions of 5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, and irradiation time: 0.1 to 60 seconds.

UV irradiation uses a UV-LED irradiation device (for example, UV-LED irradiation device ZUV-C30H manufactured by OMRON Corporation), wavelength: 200 to 400 nm, power source: 100 V AC, light source peak illuminance: 400 to 3000 mW / It can be performed under conditions of cm ² and irradiation time: 1 to 60 seconds.

  The concentration of the solution containing the molecular adhesive represented by the general formula (1) is not particularly limited and can be appropriately selected. For example, 0.01 to 100 mmol / L is preferable, and 0.1 More preferably, it is -10 mmol / L. By setting the concentration within the above range, the adhesive strength is increased, which is preferable.

  Further, the solvent is not particularly limited. For example, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and methylene chloride. List halides, olefins such as butane and hexane, ethers such as tetrahydrofuran and butyl ether, aromatics such as benzene and toluene, amides such as dimethylformamide and methylpyrrolidone, water, and a mixed solvent thereof. Can do.

  Further, the solution containing the molecular adhesive represented by the general formula (1) is further added to the general formula (2):

(In the formula, R ² , M ² and M ³ are the same as above.)
It is preferable that the triazine compound represented by the formula (1) is contained because higher adhesion strength can be expressed in the adhesion between the cross-linking reactive solid surface of the present invention and the rubber.

  The blending ratio of the triazine compound is preferably the same ratio as the blending ratio in the molecular adhesive composition.

  The method for contacting the solution containing the molecular adhesive represented by the general formula (1) with the OH group-containing solid surface is not particularly limited, and a known method can be used. Examples of the contact method include dipping, coating, spraying, and the like, but a dipping method is preferred because it can be uniformly contacted with the solution.

  The immersion treatment conditions are not particularly limited. For example, the immersion treatment is preferably performed at a solution temperature of 0 to 100 ° C. for 1 second to 60 minutes. Immersion conditions are governed by the temperature, time, and concentration of the solution and cannot be uniquely determined. However, at a constant concentration, the time tends to be long when the temperature is low, and the time is short when the temperature is high. .

The heating conditions, preferably carried out for 1 second to 600 minutes at 40-250 ° C., more preferably between 1-6 0 minutes at 50 to 200 ° C., more preferably from 1 to 30 minutes. When the heating condition is within this range, productivity is high and economically preferable.

  The heating method is not particularly limited and a known method can be used, and examples thereof include a method using an oven, a dryer, high-frequency heating, or the like.

  If the reaction between the solution containing the molecular adhesive and the OH group-containing solid surface is insufficient, the above contact and heating can be repeated about 1 to 10 times. That is, it may be more effective to shorten the time of contact and heating and increase the number of reactions.

  Moreover, you may wash | clean the solid surface using the above-mentioned solvent, and it can carry out by a well-known method as a washing | cleaning method. By washing, unreacted molecular adhesive on the solid surface can be removed, which is preferable.

Next, as the second production method of the cross-linking reactive solid surface,
General formula (5):
X _a (YO) _3-a SiR ¹ Z ′ (5)
(In the formula, X, Y, R ¹ and a are the same as above, and Z ′ is —Cl and —Br.)
A solution containing a silane coupling agent represented by the above and an OH group-containing solid surface are brought into contact with each other and heated to a reactive solid surface.
General formula (6):
M ⁴ _p Z (6)
(In the formula, M ⁴ is H, Li, Na, K, or Cs , and Z is the same as described above. P is 1 or 2.)
It is the method including the process of contacting the solution containing the sulfur compound represented by these.

  Z 'in the general formula (5) is -Cl or -Br.

By bringing the OH group-containing solid surface into contact with a solution containing the silane coupling agent represented by the general formula (5), the general formula (7):
—O—X _a (—O) _2-a SiR ¹ Z ′ (7)
A reactive solid surface having a group represented by Such a reactive solid surface is effective for adhesion to a halogen-containing rubber as it is, but is further immersed in a solution containing a sulfur compound represented by the general formula (6) to react with the general formula. A crosslinking reactive solid surface having a crosslinking reactive group represented by the general formula (2) can be obtained by a nucleophilic substitution reaction with a sulfur compound represented by (6).

  The concentration of the solution containing the silane coupling agent represented by the general formula (5) is not particularly limited and may be appropriately selected. For example, 0.0001 to 1 mol / L is preferable, and 0 More preferably, it is 0.001 to 0.1 mol / L. It is preferable for the concentration to be in the above range since the reactivity and storage stability are good.

  As for the solvent and the contact method of the solution, the solvent and the contact method mentioned in the solution containing the molecular adhesive represented by the general formula (1) can be exemplified.

  Moreover, as heating conditions, it is preferable to carry out for 1 to 60 minutes at 0-70 degreeC, and for 1 to 60 minutes is more preferable at 20-60 degreeC. It is preferable for the heating condition to be within the above range because the reaction is completed in a short time.

M ⁴ in the general formula (6) is H, Li, Na, K or Cs , and among these, Nae and K are preferable.

Examples of the sulfur compound represented by the general formula (6) include NaSH and Na ₂ S _x (X is a number of 1 to 4).

  Although it does not specifically limit as a density | concentration of the solution containing the sulfur compound shown by General formula (6), It is preferable that it is 0.1-1000 mmol / L, and 0.5-100 mmol / L. More preferably. When the concentration range is within the above range, reactivity and productivity are preferable from the viewpoint. On the other hand, if the concentration is too high, a side reaction due to a nucleophilic substitution reaction of the sulfur compound represented by the general formula (6) with respect to the crosslinking reactive group tends to occur, which is not preferable.

  As for the solvent and the contact method of the solution, the solvent and the contact method mentioned in the solution containing the molecular adhesive represented by the general formula (1) can be exemplified.

  The immersion in the solution containing the reactive solid surface and the sulfur compound represented by the general formula (6) is preferably performed by heating at a solution temperature of 0 to 100 ° C. for 1 to 600 minutes. If the temperature is less than 0 ° C, the reaction may not occur. If the temperature exceeds 100 ° C, the crosslinking reactive group tends to undergo a nucleophilic substitution reaction and decompose.

  In addition, the crosslinking reactive solid surface obtained by the first production method or the second production method is brought into contact with a solution containing the triazine compound represented by the general formula (2) and heated. In the adhesion between the cross-linking reactive solid surface and the rubber, higher adhesive strength can be expressed, which is preferable.

  The concentration of the solution containing the triazine compound represented by the general formula (2) is not particularly limited and may be appropriately selected. For example, 0.0001 to 1 mol / L is preferable, and 0.001 -0.1 mol / L is more preferable.

  About the solvent of a solution, a contact method, and heating conditions, the solvent quoted with the solution containing the molecular adhesive shown by General formula (1), the contact method, and heating conditions can be mentioned.

5. Method for Producing Solid Material-Rubber Cross-Linked Adhesive The thus obtained cross-linking reactive solid surface of the present invention forms a solid material-rubber cross-linked adhesive by contacting and thermocompression bonding with the rubber cross-linking compound. Can do.

  The rubber cross-linking compound used in the present invention contains a rubber material, a filler, a cross-linking agent, a cross-linking accelerator, and a metal activator, and optionally a stabilizer, an anti-aging agent, an anti-ultraviolet agent, a softening agent, and a coloring agent. A retarder or the like can be blended.

  The rubber material is not particularly limited, but soft polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, chloroprene rubber, chlorinated acrylic rubber, brominated acrylic rubber, fluororubber , Epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene- Propylene-diene rubber, acrylic rubber, ethylene-acrylic rubber, urethane rubber, hydrogenated acrylonitrile-butadiene rubber, hydrogenated isoprene rubber, hydrogenated chloroprene rubber, hydrogenated styrene - butadiene rubbers such as the three-dimensionally crosslinked rubber or styrene obtained by heating after the crosslinking formulation additives - butadiene rubber, acrylonitrile - such as thermoplastic rubber butadiene rubber and can be mixtures thereof rubber. Among these, natural rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, and hydrogenated acrylonitrile-butadiene rubber are preferable.

  The filler is added for the purpose of increasing the strength of the rubber or increasing the amount. Fillers include various grades of carbon black such as HAF and FEF, calcium carbonate, talc, clay, kaolin, glass, wet and dry silica, rayon, nylon, polyester, vinylon, steel, Kevlar fiber ( (Registered trademark of DuPont), fibers and fabrics such as carbon fiber and glass fiber, and the like can be used alone or in combination of two or more. Among these, carbon black and silica are preferable.

  As a compounding quantity of a filler, it is preferable that it is 0-200 weight part with respect to 100 weight part of rubber materials, and it is more preferable that it is 10-100 weight part. Rigidity is obtained as the amount of the filler is increased, but when added in excess of 200 parts by weight, the workability tends to be remarkably lowered. Further, if the amount of the filler is too small, the expected rigidity tends not to be obtained.

  Examples of the cross-linking agent include sulfur, peroxide, triazine thiols, tetramethylturum tetrasulfide, dithiomorpholine, and the like. More specifically, triazine trithiol, 2-dibutylamino-1,3,5-triazine-4,6-dithiol, ethylenethiourea, bisphenol A, sulfur, colloidal sulfur, dicumyl peroxide, di-t-butyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di (t-butylperoxyisopropyl) benzene And peroxides such as benzoquinone dioxime, sarigen, dimethylol / phenol, and the like. These can be used alone or in combination of two or more.

  As a compounding quantity of a crosslinking agent, it is preferable that it is 0.1-10 weight part with respect to 100 weight part of rubber materials, and it is more preferable that it is 0.5-5 weight part. A blending amount of the crosslinking agent within the above range is preferable because a sufficient elastic body is obtained and airtightness and sealing properties are exhibited.

  Examples of the crosslinking accelerator include sulfenamides, mercaptobenzothiazoles, thiurams, guanamines and polyfunctional monomers. More specifically, dibenzothiazoyl disulfide, 4-morpholinodithiobenzothia. Thiazoles such as sol, N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothiazoylsulfenamide, N-oxydiethylene-2-benzothiazoylsulfenamide, Sulfenamides such as N-diisopropyl-2-benzothiazoyl sulfenamide, N-dicyclohexyl-2-benzothiazoyl sulfenamide, and tetramethylturum disulfide, tetraethylturum disulfide, tetrabutylturum disulfide, Tulamic cross-linking accelerators such as traoctylturum disulfide and dipentamethyleneturum tetrasulfide, polyfunctional monomers such as triallyl isocyanate, triallyloxytriazine, ethylene glycol diacrylate, pentaethysitol tetramethacrylate, etc. These can be used alone or in combination of two or more.

  The blending amount of the crosslinking accelerator is preferably 0.01 to 20 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber material. A blending amount of the crosslinking accelerator within the above range is preferable because a sufficient elastic body is obtained and airtightness and sealing properties are exhibited.

  The metal activator is added for the purpose of adjusting the crosslinking rate or accepting acid. Metal activators include zinc oxide, magnesium oxide, calcium oxide, barium oxide, aluminum oxide, bell oxide, iron oxide, calcium hydroxide, calcium carbonate, magnesium carbonate, fatty acid sodium, calcium octylate, potassium isooctylate, Toxides, cesium octylate, potassium isostearate and the like can be mentioned, and these can be used alone or in combination of two or more.

  Although the compounding quantity of a metal activator is not specifically limited, It is preferable that it is 0-20 weight part with respect to 100 weight part of rubber materials, and it is more preferable that it is 1-10 weight part. In some cases, a metal activator is not used at all. However, generally, the purpose is achieved at 1 part by weight or more, and adding more than 20 parts is not preferable because the properties of rubber may change.

  The rubber compound obtained as described above is brought into contact with the cross-linking reactive solid surface of the present invention and heated at 80 to 200 ° C. for 1 to 60 minutes at 1 to 30 atm to obtain an adhesive. Is preferred.

  If the pressure is less than 1 atm, bubbles are mixed in the rubber and the adhesive strength tends to decrease. Even if the pressure exceeds 30 atm, only the cost is increased and an excellent effect is not obtained.

  If it is less than 80 ° C., it tends to take too much time to obtain an adhesive, and if it exceeds 200 ° C., the crosslinking proceeds too quickly, and the rubber does not flow sufficiently in the mold, so that the adhesive cannot be obtained. There is.

  If it is less than 1 minute, there is a tendency that sufficient adhesive strength cannot be obtained, and if it exceeds 60 minutes, the cost is increased and no further effect is obtained.

  Since the adhesive obtained in the present invention has higher strength than conventional products, hoses, O-rings, packings, oil seals, adhesives with metals, diaphragms, gaskets, large rubber rolls, rubber rolls for copying machines, conveyor belts It can be used in many fields, such as reinforcing belts, medical rubber products, rubber products for electrical and electronic parts, rubber products for construction, computer products, automobile products, bus / truck products, and airplane products.

  INDUSTRIAL APPLICABILITY The present invention can provide a crosslinking reactive solid surface excellent in adhesiveness to rubber, particularly sulfur crosslinking rubber, and a method for producing the crosslinking reactive solid surface. Furthermore, the present invention can provide a method for producing a solid material-rubber cross-linked adhesive having high adhesive strength between rubber, particularly sulfur cross-linked rubber and solid material.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited to these.

Example 1
(Manufacture of OH group-containing epoxy resin substrate)
Using a corona master PS-1M (manufactured by Shinko Electric Instrumentation Co., Ltd., voltage: 0-14 kV, frequency: 15 kHz), an epoxy resin substrate (1.0 × 30 × 60 mm, manufactured by Daisho Electronics Co., Ltd.) at room temperature For 30 seconds. It was confirmed that the wettability of the solid surface was improved and OH groups were present on the surface.

(Manufacture of rubber cross-linking compound)
1 part by weight of SRF black (Asahi # 50, manufactured by Asahi Carbon Co., Ltd.) and 1 part by weight of stearic acid are added to 100 parts by weight of natural rubber (NR) and mixed with a Banbury mixer at 80 ° C. for 20 minutes. Blended for minutes to make a masterbatch. Next, 1 part by weight of sulfur, 1 part by weight of CBS (crosslinking accelerator, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 5 parts by weight of zinc oxide (ZnO) are blended on a roll to obtain a rubber cross-linking compound (1 ).

(Production of cross-linking reactive solid surface)
The surface-treated epoxy resin substrate was immersed in a 2 mM ethanol solution (25 ° C.) of the molecular adhesive shown in Table 1 for 10 minutes, and then heated and dried by a blow dryer at 160 ° C. for 10 minutes. This solid surface was washed with methanol to remove unreacted molecular adhesives to obtain a cross-linking reactive solid surface.

The solid surface was analyzed by XPS, S2p peak based on sulfur S 4 - derived, Si2p peak based on silicon from S 4 was confirmed by survey spectrum. For comparison, an untreated OH group-containing epoxy resin substrate was also analyzed by XPS, and each peak based on sulfur and silicon was not confirmed.

(Adhesion between cross-linking reactive solid surface and rubber cross-linking compound (1))
A sheet (30 × 60 × 1 mm) comprising the rubber cross-linking compound (1) is placed on the surface of the cross-reactive solid, and subjected to hot press cross-linking at 160 ° C. for 30 minutes at a pressure of 400 kgf / cm ² , and an epoxy resin substrate / NR adhesive was obtained. A 90 ° peel test of the obtained epoxy resin substrate / NR adhesive was performed by the following method. The results are shown in Table 1.

<90 ° peel test method>
The obtained epoxy resin substrate / NR bonded material was allowed to stand for 24 hours, then a 1 cm wide cut was made with a cutter in the NR cross-linked rubber part of the bonded material, and a tensile test was performed at a peel strength of 20 ° C. and a speed of 50 ± 5 mm / min. (JIS K-6854 (1977)) (manufactured by Shimadzu Corporation, Shimadzu Autograph AGS-1kND).

Examples 2-3, Comparative Examples 1 and 2
Except that the molecular adhesive shown in Table 1 was used, an epoxy resin substrate / NR adhesive was obtained in the same manner as in Example 1 to obtain a cross-linking reactive solid surface . When this solid surface was analyzed by XPS, S2p peak based on sulfur derived from S4 and SH and Si2p peak based on silicon derived from S4, SH and epoxy were confirmed in the survey spectrum.
The obtained epoxy resin substrate / NR adhesive was subjected to a 90 ° peel test. The results are shown in Table 1.

Examples 4-6
Crosslinking reactive solid surface in the same manner as in Example 1 except that the molecular adhesive and the triazine compound shown in Table 1 were made into a 2 mM ethanol solution at a molar ratio of 1: 1 (molecular adhesive: triazine compound). Further, an epoxy resin substrate / NR adhesive was obtained using the cross-linking reactive solid surface. The obtained epoxy resin substrate / NR adhesive was subjected to a 90 ° peel test. The results are shown in Table 1.

  When this solid surface was analyzed by XPS, S2p peak based on sulfur derived from S4 and DA and N1s peak based on nitrogen derived from DA, F and DB were confirmed from the survey spectrum. For comparison, an untreated OH group-containing substrate was also analyzed by XPS, and no S2p peak or N1s peak in the survey spectrum was confirmed.

S4: Bis (triethoxysilylpropyl) tetrasulfide (mixture of di- and trisulfides) (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-846)
SH: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
Epoxy: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
F: 1,3,5-triazine-2,4,6-trithiol (manufactured by Sankyo Kasei Co., Ltd., ZISNET-F)
DB: 1,3,5-triazine-2-dibutylamino-4,6-dithiol (manufactured by Sankyo Kasei Co., Ltd., ZISNET-DB)
DA: 1,3,5-triazine-2-diallylamino-4,6-dithithiol TESN: 1,3,5-triazine-2-triethoxysilylpropylamino-4,6-dithiol monosodium salt

  In Comparative Example 1, since the solid surface was not cross-linking reactive, the adhesive did not show any peel strength even after cross-linking. Moreover, in the comparative example 2, although it processed by the conventionally used TESN, the remarkable effect was not acquired. However, it was found that Examples 1 to 3 showed an adhesive force of about 3 times that of Comparative Example 2, and Examples 4 to 6 using a triazine compound in combination also showed 1.2 to 2.0 times the adhesive force. Thereby, it turns out that the solid surface and rubber | gum have adhere | attached strongly.

Examples 7-12, Comparative Examples 3-8
(Manufacture of OH group-containing substrates)
Using a corona master PS-1M (manufactured by Shinko Electric Instrumentation Co., Ltd., voltage: 0-14 kV, frequency: 15 kHz), the target substrate (epoxy resin substrate: 1.0 × 30 × 60 mm, manufactured by Daisho Electronics Co., Ltd.) , Aluminum substrate: 1.0 × 30 × 60 mm, manufactured by Nilaco , SUS304: 0.1 × 30 × 60 mm, manufactured by Nilaco ) was surface-treated at room temperature for 30 seconds. It was confirmed that the wettability of any solid surface was improved and OH groups were present on the surface.

(Production of cross-linking reactive solid surface)
When a 2 mM (mol / L) ethanol solution of the molecular adhesive shown in Table 2 or a triazine compound is included (Examples 8, 10, and 12), the molar ratio is 1: 1 (molecular adhesive: triazine compound). A cross-linked reactive solid surface was obtained in the same manner as in Example 1 except that the solution was added at a ratio of 2 to give a 2 mM ethanol solution and the substrate shown in Table 2 was used.

  When the cross-linking reactive solid surface of Example 7 was analyzed by XPS, an S2p peak based on sulfur derived from S4 and an Si2p peak based on silicon derived from S4 were confirmed by a survey spectrum. Moreover, when the cross-linking reactive solid surface of Example 8 was analyzed by XPS, in addition to the peak of Example 7, a N1s peak based on DA-derived nitrogen was confirmed in the survey spectrum. For comparison, when the surface of an aluminum substrate not subjected to corona discharge treatment (without treatment with a molecular adhesive) was analyzed by XPS, N1s peak, S2p peak, and Si2p peak were not confirmed (FIG. 1). reference). In the other examples, the same peaks as those in Examples 7 and 8 were observed.

(Adhesion between cross-linking reactive solid surface and rubber composition)
A sheet (30 × 60 × 1 mm) made of the same rubber cross-linking compound (1) as in Example 1 is placed on the surface of the cross-reactive solid, and hot press cross-linking is performed at 160 ° C. for 30 minutes at a pressure of 400 kgf / cm ^2. And various substrate / NR adhesives were obtained. A 90 ° peel test was performed on the obtained various substrates / NR adhesives. The results are shown in Table 2.

  As shown in Table 2, in Comparative Examples 3, 5, and 7, since the solid surface was not cross-linking reactive, the adhesive did not show any peel strength even after cross-linking. Further, in Comparative Examples 4, 6, and 8, processing was performed with a conventionally used TESN, but a remarkable effect was not obtained. However, it was found that Examples 7, 9, and 11 showed an adhesive strength of 1.1 to 4.4 times that of TESN, and Examples 8, 10, and 12 that used a triazine compound in addition to that of TESN. Thereby, it turns out that the solid surface and rubber | gum have adhere | attached strongly.

Examples 13-20, Comparative Examples 9-16
When an aluminum substrate (1 × 30 × 60 mm, manufactured by Niraco ) is used as a substrate and a 2 mM ethanol solution of a molecular adhesive shown in Table 3 or a triazine compound is included (Examples 14, 16, 18, and 20) In a molar ratio of 1: 1 molecular adhesive: triazine compound), a 2 mM ethanol solution was used, and the rubber crosslinking compounds (1) to (4) (see Table 5) shown in Table 3 were used. Except for this, an aluminum substrate / various rubber adhesives were obtained in the same manner as in Example 1. The obtained aluminum substrate / various rubber adhesives were subjected to a 90 ° peel test. The results are shown in Table 3.

  In Comparative Examples 9, 11, 13, and 15, since the solid surface was not cross-linking reactive, the adhesive did not exhibit any peel strength even after cross-linking. In Comparative Examples 10, 12, 14, and 16, processing was performed with a conventionally used TESN, but a significant effect was not obtained. However, Examples 13, 15, 17, and 19 show double or more TESN, and Examples 14, 16, 18, and 20 that use a triazine compound together show 1.1 to 1.6 times the adhesive strength. all right. Thereby, it turns out that the solid surface and rubber | gum have adhere | attached strongly.

Examples 21-28, Comparative Examples 17-24
When a 2 mM ethanol solution of the molecular adhesive shown in Table 4 or a triazine compound (Examples 14, 16, 18, and 20) is included, the molar ratio is 1: 1 (molecular adhesive: triazine compound). Addition of 2 mM ethanol solution and use of various rubber compounds (1) and (3) to (5) (see Table 5) shown in Table 5 were performed in the same manner as in Example 1 except that the epoxy resin substrate / Various rubber adhesives were obtained. The obtained epoxy resin substrate / various rubber adhesives were subjected to a 90 ° peel test. The results are shown in Table 4.

CBS: (Ouchi Shinsei Chemical Co., Ltd., CZ)
MBTS: (DM manufactured by Ouchi Shinsei Chemical Co., Ltd.)
TMTD: (Ouchi Shinsei Chemical Co., Ltd., TT)

  In Comparative Examples 17, 19, 21, and 23, since the solid surface was not cross-linking reactive, the adhesive did not exhibit any peel strength even after cross-linking. Further, in Comparative Examples 18, 20, 22, and 24, processing was performed with a conventionally used TESN, but a remarkable effect was not obtained. However, Examples 21, 23, 25, and 27 show an adhesive strength of 2 times or more of TESN, and Examples 22, 24, 26, and 28 using a triazine compound further show 1.3 to 1.9 times or more of the adhesive strength. I understood. Thereby, it turns out that the solid surface and rubber | gum have adhere | attached strongly.

Example 29
(Production of cross-linking reactive solid surface)
The surface of the cross-linked reactive solid obtained in the same manner as in Example 1 was immersed in a 2 mM ethanol solution of a triazine compound (DA) for 10 minutes at 40 ° C. for 10 minutes, and then air-dried at 160 ° C. for 10 minutes. Heat-dried with a machine. This solid surface was washed with methanol to remove unreacted molecular adhesives to obtain a cross-linking reactive solid surface.

  When this solid surface was analyzed by XPS, a DA-derived N1s peak was confirmed from the survey spectrum, and the same result as the analysis value treated with the mixed solution of S4 and DA was obtained.

(Adhesion between cross-linking reactive solid surface and rubber composition)
A sheet (30 × 60 × 1 mm) made of the same rubber cross-linking compound (1) as in Example 1 is placed on the surface of the cross-reactive solid, and hot press cross-linking is performed at 160 ° C. for 30 minutes at a pressure of 400 kgf / cm ^2. And an epoxy substrate / NR adhesive was obtained. A 90 ° peel test was performed on the resulting epoxy substrate / NR adhesive. The results are shown in Table 6.

  In the adhesion method using a molecular adhesive and a triazine, Table 6 shows a method using a premixed solution and a method in which a reactive solid surface is generated by a molecular adhesive and then a triazine treatment is performed as a second-stage reaction. As shown in Fig. 5, there was no significant difference in the adhesive strength, and all of them showed good results.

Example 30
(Production of cross-linking reactive solid surface)
The surface-treated epoxy substrate is immersed in a 2 mM ethanol solution (25 ° C.) of (EtO) ₃ SiC ₃ H ₆ Cl (hereinafter sometimes referred to as TESC) for 10 minutes, and then air-dried at 160 ° C. for 10 minutes. Heat-dried with a machine. This solid surface was washed with methanol to remove unreacted molecular adhesives to obtain a cross-linking reactive solid surface. When this solid surface was analyzed by XPS, a TE2 derived Si2P peak was confirmed by a survey spectrum. Subsequently, this reactive solid surface was immersed in a 20 mM ethanol solution of NaSH at 60 ° C. for 3 hours, washed with water and methanol, and the generated sodium chloride and unreacted NaSH were removed to obtain a crosslinked reactive solid surface. It was.

  When this solid surface was analyzed by XPS, an S2p peak based on sulfur derived from SH was confirmed by a survey spectrum. From this result, it can be seen that the same crosslinkable reactive solid surface as the molecular adhesive described in Example 2 was obtained.

(Adhesion between cross-linking reactive solid surface and rubber composition)
For confirmation, a sheet (30 × 60 × 1 mm) made of the same rubber cross-linking compound (1) as in Example 2 was placed on the surface of the cross-reactive solid, and the pressure was 400 kgf / cm ² at 160 ° C. for 30 minutes. Hot press crosslinking was performed to obtain an epoxy substrate / NR adhesive. A 90 ° peel test was performed on the resulting epoxy substrate / NR adhesive. The results are shown in Table 7.

  As a method for producing a reactive solid surface, a terminal halogen-containing compound was used, and a method through two steps was examined. As a result, it was found that a reactive solid surface similar to that obtained when a molecular adhesive was used was obtained.

  As can be seen from these examination results, a sufficient adhesion effect cannot be obtained by untreated or TESN treatment. However, after activating the surface, the treatment with the molecular adhesive of the present invention makes the adhesion remarkable. The power can be improved. It was also found that by using a triazine thiol compound such as DA in combination, a strong adhesive force that would cause rubber breakage was obtained.

  The present invention includes hoses, O-rings, packings, oil seals, adhesives with metals, diaphragms, gaskets, large rubber rolls, rubber rolls for copying machines, conveyor belts, reinforcing belts, medical rubber products, and rubbers for electrical and electronic parts. It is useful in many fields such as products, rubber products for construction, computer products, automobile products, bus / truck products, airplane products.

The chart of the XPS measurement of the solid surface is shown.

Claims (8)

General formula (1):
[X _a (YO) _{3 -a} SiR ¹ ] _b Z (1)
(In the formula, X and Y may be the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms; R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms; , -NH is an alkylene group -, - CO -, - O -, - S -, - COO- or -C ₆ H ₄ - may contain a .Z is, - SS -, - SSS-or - SSSS- , a is 0, 1 or 2, and b is 2. )
A molecular adhesive having a crosslinking reactivity comprising a compound represented by the formula (2):

(Wherein, R ^{2 -. NR 4 R 5 (R} 4, R 5 may be different even in the same, respectively, an alkyl group or an alkenyl group having a carbon number of 1 to 4), M ^2, M ³ may be the same or different and is an alkali metal or H.)
The molecular-adhesive composition containing the triazine compound represented by these. R of the triazine compound represented by the general formula (2) ² Is -N (C ₄ H ₉ ) ₂ Or -N (CH ₂ CH = CH ₂ ) ₂ The molecular adhesive composition according to claim 1, wherein General formula (1):
[X _a (YO) _{3 -a} SiR ¹ ] _b Z (1)
(In the formula, X and Y may be the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms; R ¹ is an alkylene group or phenylene group having 1 to 18 carbon atoms; , -NH is an alkylene group -, - CO -, - O -, - S -, - COO- or -C ₆ H ₄ - may contain a .Z is, - SS -, - SSS-or - SSSS- , a is 0, 1 or 2, and b is 2. )
A molecular adhesive having a crosslinking reactivity comprising a compound represented by the formula (2):

(Wherein, R ^{2 -. NR 4 R 5 (R} 4, R 5 may be different even in the same, respectively, an alkyl group or an alkenyl group having a carbon number of 1 to 4), M ^2, M ³ may be the same or different and is an alkali metal or H.)
Crosslinking comprising a step of bringing a solution containing a molecular adhesive composition containing a triazine compound represented by the formula into contact with a solid surface having an OH group on the surface, and a step of heating the solid surface in contact with the solution containing a molecular adhesive A method for producing a reactive solid surface. The method for producing a cross-linking reactive solid surface according to claim 3, comprising a step of obtaining the solid surface having the OH group by subjecting the solid surface to corona discharge treatment. The method for producing a cross-linking reactive solid surface according to claim 3 or 4 , wherein the solid surface is a solid surface of metal, ceramics or polymer. A crosslinking reactive solid surface obtained by the method for producing a crosslinking reactive solid surface according to claim 3 or 4 . A solid material comprising a step of contacting and thermocompression-bonding a crosslinking reactive solid surface of a solid material having a crosslinking reactive solid surface obtained by the method for producing a crosslinking reactive solid surface according to claim 3 or 4 and a rubber crosslinking compound. -Manufacturing method of rubber cross-linked adhesive. The method for producing a solid material-rubber crosslinked adhesive according to claim 7 , wherein the rubber crosslinking compound is a compound comprising a rubber material, a filler, a crosslinking agent, a crosslinking accelerator and a metal activator.

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