JPS626987B2 - - Google Patents

Description

[Detailed description of the invention]

a. Industrial Application Field The present invention relates to a laminate. More specifically, the present invention relates to a laminate in which a fluorine-containing polymer layer and a diene polymer layer or a halogen-containing polymer layer are bonded together. b. Prior art Conventionally, fluorine-containing polymers have always had excellent heat resistance,
It has characteristics that are significantly different from other synthetic rubbers and synthetic resins, such as solvent resistance, chemical resistance, and oxidation resistance, and is preferably used when these performances are required. c Problems to be Solved by the Invention However, due to the low surface energy and low reactivity of fluorine-containing polymers, strong adhesion with other materials is extremely difficult, and lamination with other polymeric materials is extremely difficult. There were restrictions on its use as a structure. d Means for Solving the Problems An object of the present invention is to strengthen the fluorine-containing polymer layer with the diene polymer layer and the halogen-containing polymer layer without impairing the excellent performance of the fluorine-containing polymer. This was achieved by blending a specific compound into the fluorine-containing polymer layer for adhesion and lamination. That is, the present invention provides (A) a 2-substituted-4,6-dithiol-S-triazine derivative (hereinafter simply abbreviated as TTA), (B) an oxide, hydroxide, or carbonate of an alkaline earth metal; and (C) at least one compound selected from the following compound group (a) N,N-dimethyldodecylamine, 1,
8-Diazabicyclo(5,4,0)-undecene or its phenol or 2
-ethylhexylate, and/or (b) polyethylene glycol or its mono- or di-alkyl ether, quaternary ammonium salt, dimethylformamide,
A laminate in which a fluorine-containing polymer layer containing dimethyl sulfoxide or hexamethylphosphoramide and a diene polymer layer or a halogen-containing polymer layer are firmly adhered by heating. e. Detailed Description of the Invention The laminate of the present invention is basically composed of a fluorine-containing polymer layer containing a specific compounding agent and a diene polymer layer. Fluorine-containing polymer layer The fluorine-containing polymer layer used in the laminate of the present invention includes 4-fluorinated ethylene, 6-fluorinated propylene, 3-fluorinated chlorinated ethylene, fluorinated vinyl, and fluorinated ethylene. Used is a polymer such as vinylidene or a copolymer containing these as main components, which is formed into a sheet or film by adding the additives described below. Compounding Agents The following compounding agents may be included in the fluorine-containing polymer used in the laminate of the present invention. (A) 2-substituted-4,6-dithiol-S-triazine derivatives (hereinafter simply abbreviated as TTA) (B) oxides, hydroxides, or carbonates of alkaline earth metals, and (C) the following: at least one selected from the group of compounds of
Species compounds (a) N,N-dimethyldodecylamine, 1,8
-diaza-bicyclo(5,4,0)-undecene or its phenol or 2-ethylhexylate, and/or (b) polyethylene glycol or its mono-
Alternatively, di-alkyl ether, quaternary ammonium salt, dimethylformamide, dimethyl sulfoxide, or hexamethylphosphoramide [component (A)] The TTA of component (A) has the general formula [M is hydrogen, alkali metal or alkaline earth metal, R is OR ₁ , NR ₁ , R ₂ or SR ₁ , R ₁ and
R ₂ is the same or different and represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, or an alkylaryl group. ] It is a compound represented by Alkyl groups in the above formula include methyl, ethyl, n-propyl, butyl, t-butyl, amyl, hexyl, octyl, 2-ethylhexyl,
Nonyl, dodecyl and octadecyl groups, allyl and oleyl groups as alkenyl groups, benzyl, methylbenzyl, phenylethyl and phenylpropyl groups as arylalkyl groups, phenyl and naphthyl groups as aryl groups, and alkylaryl groups can be exemplified by ethyl phenyl, butylphenyl, octylphenyl, nonylphenyl, 4-hydroxy-3,5-di-t-butylphenyl groups, and the like. Specific compounds include 2-dibutylamino-4,6-dithiol-S-triazine, 2-morpholino-4,6-dithiol-S-triazine, dimorpholine, and 2-piperidine-4,6-dithioltriazine ditriazine. Ethanol, 2-dilaurylamino-4,6-dithiol-S-triazine calcium, 2-ethylphenylamino-
4,6-dithiol-S-triazine dilithium, 2-(δ-carboxylpropylamino)-
4,6-dithiol-S-triazine calcium, 2-octylamino-4-butylamino-6
-thiol-S-triazine copper, 2-anilino-
4,6-dithiol-S-triazine, 2,4-
dianilino-6-thiol-S-triazine,
2,4-bisdimethylamino-6-thiol-S
-Triazine, 2-butoxy-4-octadecylamino-6-thiol-S-triazine, 2-
Examples include (p-dimethylamino)-4-methoxy-6-thiol-S-triazine and 2,4,6-trithiol-S-triazine. [Component (B)] Also, the above component (B), an alkaline earth metal oxide,
Hydroxides or carbonates include magnesium oxide, calcium oxide, zinc oxide, barium oxide,
Examples include magnesium hydroxide and calcium carbonate. [Component (C)] TTA in these formulations can be used alone or in the coexistence with an acid acceptor of an alkaline earth metal compound to react with chlorine-containing polymers such as polyvinyl chloride or chlorinated polyethylene. When blended, the chlorine atoms in the chlorine-containing polymer are extracted as hydrogen chloride, and then a carbon-sulfur bond is formed, thereby acting as a crosslinking agent. However, the reactivity of these chlorine-containing polymers and the above-mentioned fluorine-containing polymer is significantly different, and the fluorine-containing polymer has poor reactivity, so it can only be used in the presence of thiol-S-triazine and alkaline earth metal compounds. cannot form sufficient carbon-sulfur bonds. However, according to the present invention, the following compounds, namely (a) N,N-dimethyldodecylamine, 1,8-
Diazabicyclo(5,4,0)undecene or its phenol or 2-ethylhexylate; and (b) polyethylene glycol (molecular weight 106~
40,000) or their mono- or di-alkyl ethers (alkyl having 1 to 12 carbon atoms), quaternary ammonium salts such as tetraalkylammonium halogenides, trialkylbenzylammonium halogenides, dimethylformamide, dimethylsulfoxide, hexa The fluorine-containing polymer is blended with one or more compounds selected from at least one group (a) or (b) consisting of methyl sulfoxide and hexamethylphosphoramide while heating. Like polymers, it promotes the formation of carbon-sulfur bonds and can be used for crosslinking reactions. [Amount] The amount of TTA coexisting in the fluorine-containing polymer layer is preferably 0.1 to 7 parts by weight (
(based on 100 parts by weight), particularly preferably 1 to 3 parts by weight. If TTA is less than 0.1 parts by weight, sufficient co-crosslinking between the fluorine-containing polymer and the halogen-containing polymer or diene polymer cannot be achieved, and if it exceeds 7 parts by weight, co-crosslinking within the fluorine-containing polymer may occur. Crosslinking proceeds more than necessary, which adversely affects the physical properties of the fluorine-containing polymer. Alkaline earth metal compounds used with TTA are
A sufficient effect can be obtained by adding 0.1 to 20 parts by weight, and 0.01 to 5 parts by weight of the compounds of the above groups (a) and/or (b). When the fluorine-containing polymer reacts with TTA, the alkaline earth metal compound, which is a receptor for the generated hydrogen fluoride, does not have a sufficient effect as a receptor when it is less than 0.1 part by weight, and the reaction is slow. In addition, hydrogen fluoride remains in the laminate, causing adverse effects such as corrosion of metals, and if it exceeds 20 parts by weight, it becomes extremely difficult to mix it into the fluorine-containing polymer. Regarding the amount of compound of group (a) and/or (b) added, if it is less than this range, sufficient effect will not be observed, and if it is more than this range, it will be difficult to mix into the fluorine-containing polymer and Adversely affects the physical properties of elementary polymers. On the other hand, TTA can also react with diene-based polymers and form carbon-sulfur bonds, so TTA present on the surface of the fluorine-containing polymer layer reacts with the surface of the butadiene-based polymer layer to produce butadiene. It can be firmly adhered to the polymer layer. Therefore, the laminate of the present invention utilizes the reactivity of TTA to fluorine-containing polymers and mutual reactivity to halogen-containing polymers or diene polymers,
Both are bonded together by co-crosslinking. Diene-based polymer layer or halogen-containing polymer layer In the laminate of the present invention, the diene-based polymer layer laminated on the fluorine-containing polymer includes butadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, etc. So-called diene polymers such as rubber, chloroprene rubber, isoprene rubber, natural rubber, butyl rubber, butadiene resin, acrylonitrile-butadiene-styrene resin, butadiene-styrene resin, ethylene-propylene-ethylidenenorbornene copolymer, ethylene-propylene- A double bond-containing polymer such as a dicyclopentadiene copolymer, a double bond-containing acrylic rubber, or a mixture of at least one of these may be formed into a sheet or film shape. Further, examples of the halogen-containing polymer used in the laminate of the present invention include polyvinyl chloride, polyvinyl chloride copolymer, polyepichlorohydrin rubber,
Epichlorohydrin copolymer, polychloroprene rubber, chloroprene copolymer, poly 1-chlorobutadiene, 1-chlorobutadiene-butadiene copolymer, chlorinated butyl rubber, chlorsulfonated polyethylene, polyvinylidene chloride, vinylidene chloride copolymer, Chlorinated polyethylene, chlorinated polypropylene, brominated butyl rubber, polyvinylidene bromide, vinylidene bromide copolymer, brominated polyethylene, and mixtures of at least one of these, formed into sheets or films. used. Other additives Depending on the purpose, other known stabilizers, colorants, plasticizers, lubricants, fillers, etc. may be added to the fluorine-containing polymer layer used in the laminate of the present invention. Of course you can. In addition, in the case of fluoro rubber-based materials that require crosslinking, TTA, alkaline earth metal compounds, and
In addition to the compounding agent of at least one compound selected from (a) and/or (b), if necessary, an aliphatic polyamine derivative, a peroxide compound,
A crosslinking agent such as a dithiol compound may also be added. In addition, in the halogen-containing polymer layer and the diene polymer layer, similarly to the fluorine-containing polymer layer,
Conventional stabilizers, plasticizers, fillers, crosslinking agents, crosslinking accelerators, crosslinking accelerators and the like can be added as necessary. Further, the halogen-containing polymer layer and the diene-based polymer layer also contained the fluorine-containing polymer layer.
By adding TTA and, if necessary, an alkaline earth metal oxide, it is possible to co-crosslink with the fluorine-containing polymer layer more effectively and to perform lamination. In particular, when laminating with a fluorine-containing polymer, TTA is also applied to the halogen-containing polymer layer and diene polymer layer.
It is desirable to add 0.1 to 10 parts by weight per 100 parts by weight of the polymer. In addition, in the diene polymer layer, -N=N-
group, -S-S- group, -N-S- group or -O-O
It is also possible to contain a compound containing a - group. Such compounds include 2-(o-nitrophenylazo)-p-cresol, benzeneazo-α
- Naphthylamine, azodicarboxamide, dibenzothiazyl disulfide, tetraalkylthiuram disulfide (alkyl group is CH ₃ , C ₂ H ₅ , t
-C ₄ H ₉ ), bis[2,4-bis(amino)-6-
Triazinyl] disulfide, bis-(2-dibutylamino-4-thiol-6-triazinyl)
Disulfide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide,
N,N'-diisopropyl-2-benzothiazolesulfenamide, N,N'-dithiomorpholine, dicumyl peroxide, 2,5-dimethyl-
Representative examples include 2,5-di-t-butylperoxyhexane. At least one of these is generally added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the diene polymer.
Used in parts by weight. Even when added in a large amount exceeding 5 parts by weight, no particular enhancement of the effect is observed. Laminate In the laminate of the present invention, a fluorine-containing polymer layer and a halogen-containing polymer layer containing TTA, an alkali earth metal compound, and at least one compound in the above group (a) and/or (b) are used. There are various embodiments of the laminate in which the diene polymer layer and the diene polymer layer are laminated in contact with each other. Typical examples include (1) an uncrosslinked fluororubber layer and an uncrosslinked halogen-containing rubber layer; Or a laminate with an uncrosslinked diene rubber layer. (2) A laminate of an uncrosslinked fluorine rubber layer and a crosslinked halogen-containing rubber layer or a crosslinked diene rubber layer. (3) A laminate of an uncrosslinked fluororubber layer and a halogen-containing resin layer or a diene resin layer. (4) A laminate of a crosslinked fluororubber or fluororesin layer and an uncrosslinked halogen-containing rubber layer or an uncrosslinked diene rubber layer. (5) A laminate of a crosslinked fluororubber or fluororesin layer and a crosslinked halogen-containing rubber layer or a crosslinked diene rubber layer. (6) A laminate of a crosslinked fluororubber or fluororesin layer and a halogen-containing resin layer or diene resin layer. (7) A laminate in which a fluorine-containing polymer layer is coated with a halogen-containing polymer or a diene polymer. (8) A laminate in which a halogen-containing polymer layer or a diene polymer layer is coated with a fluorine-containing polymer. A laminate such as the following can be exemplified. All of these are laminates in which each layer is laminated and then each polymer layer is firmly adhered in a laminated form by heating. A combination in which at least one material of these laminates is in an uncrosslinked state is preferred. f Examples Examples of the laminate of the present invention are shown below, but the present invention is not limited thereto. Examples 1 to 11 Fluorine rubber, acrylonitrile-butadiene rubber (NBR) or polybutadiene rubber (BR) were kneaded on a roll at 40°C according to Table 1.
Further, the fluorine-containing resin powder or polyvinyl chloride powder was mixed in a kneader according to Table 1. In Examples 1 to 6, the mixture was kneaded according to Table 1 and made into a 2 mm thick sheet.
The material combinations shown in are brought into contact with each other in an uncrosslinked state, and after being press-crosslinked and laminated at 170°C for 30 minutes,
A 1 cm wide piece was punched out and a T-peel test was performed according to the method specified in JIS-K6854-1973. The results are shown in Table-2. In addition, in Example 7, material H shown in Table 1 was press-vulcanized into a 2 mm thick sheet at 150°C for 20 minutes.
The vulcanized sheet and uncrosslinked material B (2 mm thick sheet) were stacked and press-crosslinked at 170°C for 30 minutes to laminate them. The results are shown in Table-2. Furthermore, in Example 8, material B shown in Table 1 was used.
Formed into a 2 mm thick sheet, cross-linked by press at 150℃ for 30 minutes, layered the crosslinked sheet with unvulcanized material H (2 mm thick sheet) shown in Table 1, and heated at 170℃ for 30 minutes.
It was press-crosslinked and laminated for minutes. The results are shown in Table-2. In addition, in Example 9, material B shown in Table 1 was formed into a 2 mm thick sheet and further press-crosslinked at 150°C for 30 minutes, and material H shown in Table 1 was formed into a 2 mm thick sheet.
The sheets were formed into thick sheets, which were further press-crosslinked at 150°C for 20 minutes, then stacked together, and then press-heated again at 170°C for 30 minutes to laminate them. The results are shown in Table-2. Furthermore, in Example 10, powder of material J shown in Table 1 was placed on a 2 mm thick uncrosslinked sheet of material B shown in Table 1, and the powder was press-crosslinked in a 3 mm thick mold at 200°C for 20 minutes to laminate. did. The results are shown in Table-2. In Examples 11 and 12, powder of material F shown in Table 1 was placed on a 2 mm thick unvulcanized sheet of material H shown in Table 1, and heated at 300°C in a 3 mm thick mold.
Lamination was carried out by press crosslinking for 15 minutes. The results are shown in Table-2. In Examples 7 to 11, as in Examples 1 to 6, after laminating the material combinations shown in Table 2,
A 1 cm wide piece was punched out and a T-peel test was performed according to the method specified in JIS-K6854-1973. The results are shown in Table-2. Comparative Examples 1 to 3 Materials E, G, H, and I shown in Table 1 were kneaded in the same manner as in Example 1 and formed into a 2 mm thick sheet, and then mixed with the combination of materials shown in Table 2. They were stacked in a crosslinked state and then press-crosslinked at 170°C for 30 minutes to form a lamination. Then punch out the laminate into 1cm wide pieces.
T according to the method specified in JIS-K6854-1973
A mold peel test was conducted. The results are shown in Table-2.

【table】

【table】

【table】

[Table] Examples 13 to 15 N,N-dimethyldodecylamine shown in Table 1 of Example 1 was mixed with 1,8-diazabicyclo(5,
4,0) Example except that undecene (K), the phenol salt of 1,8-diazabicycloundecene (L), and the 2-ethylhexylate salt of 1,8-diazabicycloundecene (M) were changed, respectively. A laminate was obtained in the same manner as in Example 1, and a T-peel test was conducted in the same manner as in Example 1. The results are shown in Table-3. Examples 16-18 The polyethylene glycol shown in Table 1 of Example 1 was changed to trialkylbenzylammonium bromide (N), dimethylformamide (O), dimethyl sulfoxide (P) and hexamethylphosphoramide (Q), respectively. A laminate was obtained in the same manner as in Example 1 except for the above, and a T-peel test was conducted in the same manner as in Example 1. The results are shown in Table-3.

【table】

[Table] g Effects of the Invention As is clear from the Examples and the like, the laminate of the present invention has a high peel strength and is firmly bonded, and has extremely excellent heat resistance and solvent resistance of the fluorine-containing polymer. By taking advantage of its properties such as hardness, chemical resistance, and oxidation resistance, it can be extremely usefully used, for example, in industrial materials such as hose materials for fuel transportation or chemical transportation.

Claims (1)

[Claims] 1 (A) 2-substituted-4,6-dithiol-S
- a triazine derivative; (B) an oxide, hydroxide, or carbonate of an alkaline earth metal; and (C) at least one selected from the following group of compounds:
Species compounds (a) N,N-dimethyldodecylamine, 1,8
-Diazabicyclo(5,4,0)-undecene or its phenol or 2-ethylhexylate, and/or (b) polyethylene glycol or its mono-
Alternatively, the fluorine-containing polymer layer containing di-alkyl ether, quaternary ammonium salt, dimethylformamide, dimethyl sulfoxide, or hexamethylphosphoramide and the diene polymer layer or halogen-containing polymer layer are solidified by heating. A laminate that is bonded to 2 The fluorine-containing polymer layer contains 2-substituted-4,6-dithiol-S based on 100 parts by weight of the fluorine-containing polymer.
- 0.1 to 7 parts by weight of a triazine derivative, an alkaline earth metal oxide, hydroxide, or carbonate
2. The laminate according to claim 1, which contains 0.1 to 20 parts by weight and 0.01 to 5 parts by weight of a compound of group (a) and/or (b).