JPS5896550A - Manufacture of laminate with layer containing halogen polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a laminate having a halogen-containing resin layer, and more specifically, a method for producing a laminate having a halogen-containing resin layer, and more specifically a method for manufacturing a laminate having a halogen-containing rubber layer or a halogen-containing resin layer and a polymer containing a carbon-carbon double bond (hereinafter referred to as non-halogen-containing rubber layer or a halogen-containing resin layer). (abbreviated as saturated polymer)).

Recently, there has been an increasing demand for the production of multifunctional composite materials that take advantage of the properties of rubber, plastic, etc., that is, composite products. However, when processing adhesion between dissimilar materials (e.g. vulcanization adhesion), it is important to balance these chemical (differences in reaction points between the two) and physical (compatibility between the two) properties. The technology is difficult, and it has been extremely difficult to obtain strong adhesion between dissimilar materials. For example, when bonding a halogen-containing resin layer, nitrile rubber,
Epoxy resin-based or vinyl chloride resin-based adhesives are widely used, but these adhesives rely on physical forces such as electrical adsorption between polar groups to adhere to the adherend. There were many cases where it was not possible to obtain a sufficiently satisfactory adhesion force. As an alternative to this, a new technique was developed in which a halogen-containing polymer and an unsaturated polymer are layered using a thiol-8-triazine derivative (JP-A-55-160071; 159975).

However, even these examples do not provide sufficiently strong adhesion, and especially when the halogen-containing polymer is a fluorine-containing polymer, it is difficult to say that a practical adhesive strength has been achieved.

The inventors of the present invention have intensively studied methods for improving the method, and found that the method for adhering the rogen-containing polymer layer and the unsaturated polymer layer is as follows.
Dithiol-5-) in halogen-containing polymer! The present invention was achieved by discovering that strong adhesion can be obtained by containing a J azine derivative and containing an oxidizing agent and/or an oxygen absorber in the unsaturated polymer. That is, the present invention has 2-
A halogen-containing polymer layer containing a substituted-4,6-sithio-〇-triazine derivative is brought into contact with a polymer layer containing a carbon-carbon double bond containing an oxidizing agent and/or an oxygen absorber. This is a method for producing a laminate having a halogen-containing polymer layer, which is characterized in that the laminate is laminated.

The present invention will be explained in detail below.

The halogen-containing polymer referred to in the present invention is polyvinyl chloride, polyvinyl chloride copolymer, polychloroprene rubber, chloroprene copolymer, chlorinated butyl rubber, chlorinated butyl copolymer, polyvinylidene chloride, and vinylidene chloride. Copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene bromide, vinylidene bromide copolymer, brominated polyethylene, polybrominated butadiene rubber, brominated butadiene copolymer and 4-fluorinated ethylene, 6-fluorinated Polymers such as fluoropyrene, 3-fluorochlorinated ethylene, vinyl fluoride, vinylidene fluoride, copolymers containing these as main components, and halogen-containing polymers obtained by mixing at least one pole of these. do.

Examples of unsaturated polymers include butadiene rubber, styrene-butadiene copolymer rubber, 7-IJ0 nitrile-butadiene copolymer rubber, chloroprene rubber, imprene rubber,
So-called diene polymers such as natural rubber, butyl rubber, butadiene resin, acrylonitrile-butadiene-styrene resin, butadiene-styrene resin, ethylene nipropylene-ethylidene 7-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer Typical examples include double bond-containing polymers such as acrylic rubber containing double bonds, and mixtures of at least one of these.

2-substituted-4, which is contained in the halogen-containing polymer of the present invention,
The 6-sithio-s-) riazine derivative (hereinafter abbreviated as TTA) is a compound represented by the following general formula.

[However, R is OR', SR', NR'R'', NHC6
H4NHC6H5, N(i-C3H7)CsH4NHC
6Hs, NHC6H2(t-C4H9)OH.

NHC6H2(CH3)(t-C4H9)OH,5C6
H2(t-C4H9)OH.

NHC6H4N(C6H5)2.0C6H5(OH)C
OC6H5; R' and R'' are the same or different and are a hydrogen atom, an alkyl group (1 to 18 carbon atoms), an alkenyl group (1 to 18 carbon atoms), a phenyl group, a phenylalkyl group, an alkylphenyl group, Naphthyl group, cycloalkyl group or morpholino group; M is a hydrogen atom, Na, K,
Li, lca, 'AMg, lBa, 14Sr,
%Zn, %Ni and %Ni represent μCu] The amount of TTA used to coexist with the rogen-containing polymer varies depending on various factors such as the type of polymer, the type of partner to be combined, and bonding conditions. A suitable amount is appropriately selected depending on the aspect.

The amount is usually 01 to 7 parts by weight, particularly preferably 1 to 3 parts by weight, per 100 parts by weight of the halogen-containing polymer. TTA is 0
．． If it is less than 1 part by weight, the co-crosslinking between the halogen-containing polymer and the unsaturated polymer will not be sufficient, and if it exceeds 7 parts by weight, the crosslinking within the halogen-containing polymer will proceed more than necessary.
It has an adverse effect on the physical properties of halogen-containing polymers.

Examples of the oxidizing agent and/or oxygen absorbing agent to be added to the unsaturated polymer include hydroquinone, methoquinone, p-inzoquinone, t-butylhydroquinone, methylhydroquinone, chloranil, phenothiazine, N, N->-
2-Naphthyl-p-phenylenediamine, p-phenylenediamine, diphenylamine, N-nitrosodiphenylamine, 4-oxydiphenylamine, chromic acid, sodium-N-chloro-p-)luenesulfonamide, sodium-chloridebenzenesulfonamide , perbenzoic acid, trichloroperbenzoic acid, monoyloxyphthalic acid, performic acid, trifluoroperacetic acid, diethyl azodicarboxylate, and pyrogallol. Oxygen is also effective as an oxidizing agent.

The amount of the oxidizing agent and/or oxygen absorbent added is 0.
0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight. If the amount added is less than 0.01 part by weight, the effect will be small; 5.
Even if it exceeds 0 parts by weight, the adhesive strength will be reduced.

In the present invention, TTA is added to the halogen-containing polymer layer,
It is important to add the oxidizing agent and/or oxygen absorber to the unsaturated polymer layer; if the reverse is the case, very strong adhesion will not be obtained.

The reason for this is not clear, but it is completely unexpected.

In addition, if necessary, MgO, CaO1Bad:, ZnO, Ca(O
H)2, Ba(OH)2, Na2CO5, CaCO
Oxides, hydroxides or carbonates of metals of Group 1, Group 2 of the periodic table, such as 3, etc., and/or the following a
), b) By adding at least one compound selected from the group of compounds, it is possible to co-crosslink with an unsaturated polymer more effectively.

a) N,N-dimethyldodecylamine, 1.13-
azabicyclo(5,4,0)-undecene or its phenol or 2-ethylhexylate, or 2,3,5-)diphenyl-2H tetracine b) polyethylene glycol or its mono- or di-alkyl ether; Quaternary ammonium salt, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoramide, especially when the halogen-containing polymer is a fluorine-containing polymer, an oxide consisting of a metal from Group 1 or Group 2 of the periodic table, water It is preferable to contain an oxide or carbonate and at least one compound in groups a) and b) above.

Amount of metal oxide, hydroxide or carbonate of Group 1 or Group 2 of the periodic table used with TTA Fi0.
A sufficient effect can be obtained at 1 to 20 parts by weight.

Further, sufficient effects can be obtained by adding the compounds of groups a) and b) used together with TTA in an amount of 0.01 to 5 parts by weight.

In the present invention, other known stabilizers, colorants, plasticizers, etc. may of course be added to the halogen-containing polymer depending on the purpose. Also, the material itself requires crosslinking...0
In the case of a 771 compound type, a crosslinking agent such as an aliphatic polyamine conductor, a peroxide compound, or a dithiol compound may be added as necessary. Similarly, for unsaturated monomers, the usual f rule, plasticizer, filler, crosslinking agent,
A crosslinking accelerator and a crosslinking accelerator may be added as necessary.

In the present invention, there are various ways to bring the Homare-logen polymer into contact with the unsaturated polymer, but representative examples include 1) uncrosslinked logene rubber layer and uncrosslinked diene thread rubber layer; contact.

2) Bringing the uncrosslinked location rubber layer into contact with the crosslinked diene rubber layer.

3) Bring the uncrosslinked ..logen rubber layer into contact with the diene resin layer.

4) Bringing the crosslinked rogen-containing rubber or the rogen-containing rubber layer into contact with the uncrosslinked diene rubber layer.

5) Bringing the crosslinked diene rubber layer into contact with the crosslinked diene rubber layer.

6) Bringing the crosslinked rogen-containing rubber or rogen-containing S layer into contact with the diene resin layer.

7) Coating the diene-based polymer on the nitrogen-containing polymer layer.

8) Coating the diene polymer layer with a halogen-containing polymer.

Examples of methods include: Among these, combinations in which at least one material is in an uncrosslinked state are particularly preferred.

After contacting these, each polymer layer can be firmly adhered in a laminated form by heating.

The laminate obtained according to the present invention is used, for example, as a material for a hose for transporting fuel or medicine.

Examples will be shown below, but the present invention is not limited thereto.

Examples 1 to 8 and Comparative Examples 1 to 9 Acrylonitrile-butadiene rubber or ethylene-
Propylene rubber and fluorine rubber were kneaded on a roll at 40°C according to Table 1.

Further, the fluorine-containing resin or polyvinyl chloride powder was mixed in a kneader according to Table 1.

In Examples 1 to 8 and Comparative Examples 1 to 8, according to Table 1, sheets of ##) L2 thickness were brought into contact with each other in an uncrosslinked state, and press crosslinked at 170°C for 30 minutes. The specimens were punched out and subjected to a T-peel test in accordance with J.K. S-6854-1973. The results are shown in Table 2.

1) Polyvinyl chloride Vinicron 3000M Mitsui Toatsu Chemical Co., Ltd. 2) Daiel G501, manufactured by Daikin Industries, Ltd. 5) Guiflon Molding Powder, manufactured by Daikin Industries, Ltd. 4) Acrylonitrile-butadiene rubber N2308, manufactured by Japan Synthetic Rubber Co., Ltd. 5) Ethylene-propylene rubber EP65 Manufactured by Nihon Gosei Rubber Co., Ltd. 6) In the general formula: R-8H, M=H 7) In the general formula: R=SH, M = Na 3) N-t-Butyl-2-benzothiazole + 77-phenamide 9) N, N'- Dicinnamylidene-1,6-hexanediamine 10) Dioctyl phthalate 11) Dibutyltin dilaurate Table 2 The results in Table 2 are summarized as shown in Table 5.

Table 3 Comparing the peel strength of combinations of laminates with those of comparative examples (conventional bonding methods) as shown in Table 3, it is clear that the bonding method of the present invention provides strong bonding. be.

Claims (1)

[Claims] The 2-substituted-4,6-dithiol-S-triazine derivative-containing polymer layer is treated with an oxidizing agent and/or
Alternatively, a method for producing a laminate having a halogen-containing polymer layer, which is laminated in contact with a polymer layer containing a carbon-carbon double bond containing an oxygen absorber.