JPH0623358B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to an adhesive composition used for bonding various synthetic resins and rubbers.

(Prior Art) There are many types of industrial rubber substrates, but especially ethylene-propylene-diene terpolymer rubber (EPDM).
Polyolefin-based vulcanizates such as and ethylene-propylene copolymer rubber (EPM) show outstanding performance in weather resistance, aging resistance, ozone resistance, etc.
Since it is a rubber with excellent features such as a wide range of 50 ° C to 150 ° C, it is now used in various fields.

Also, polyethylene (PE), polypropylene (PP)
Similar to the above-mentioned polyolefin-based vulcanized rubber, polyolefin-based synthetic resins such as show excellent performance in weather resistance, aging resistance, ozone resistance, etc. Is used for.

(Problems to be Solved by the Invention) However, the polyolefin-based vulcanized rubber such as EPDM and EPM or the polyolefin-based synthetic resin such as PP and PE does not contain a polar group in the main chain of the molecule, and thus is reactive. It has a property that the resulting coating film is easily peeled off even if an adhesive is applied to the surface of the base material made of these rubbers or resins. Therefore, there is a problem that it is extremely difficult to bond the base materials made of the above-mentioned rubber or resin, or to bond these base materials to another synthetic resin, rubber, metal or the like.

In spite of various attempts to solve the above-mentioned drawbacks, a satisfactory solution has not yet been found.

On the other hand, in the case of a synthetic resin containing a large amount of plasticizer such as vinyl chloride resin, the plasticizer migrates to the surface with long-term use, so the adhesion of the adhesive applied to the surface There is a problem that power gradually decreases.

As a result of repeated studies in view of the above problems, the present inventor has a strong adhesion to various synthetic resins such as polyolefin vulcanized rubber, polyolefin synthetic resin or vinyl chloride resin, and rubber. The inventors have found an adhesive composition and arrived at the present invention.

Structure of the Invention (Means for Solving Problems) That is, the present invention includes (a) a resorcin resin, (b) an alkali,
(c) Formalin, (d) latex, (e) in the molecule A compound containing a bond (wherein X is halogen) or a halogenating agent selected from any one of alkyl hypohalides, (f) water or an organic solvent, wherein the halogenating agent is 100 parts by weight of water or the organic solvent. N-
The above problem was solved by devising an adhesive composition having a proportion of 0.01 to 10 parts by weight in terms of bromsuccinimide.

(Function) By adding a halogenating agent to the resorcin resin used as an adhesive, the polarity and reactivity of the resorcin resin are improved, and a strong adhesion to a polymer base material such as rubber or synthetic resin. Will be shown.

(Example) Hereinafter, each component of the adhesive composition of the present invention will be described in detail.

The (a) resorcin resin is a resin obtained by subjecting resorcin and formaldehyde to a condensation reaction, and is used as a raw material for an adhesive for wood or an adhesive for fibers and rubber.

The (b) alkali may be selected from hydroxides of various alkali metals and alkaline earth metals, but NaOH, KOH and the like are preferable from the viewpoint of reactivity and cost.

(c) The formalin used in the present invention is 37% by weight of formaldehyde.

As the latex (d), one selected from various synthetic rubber latex such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, chloroprene rubber latex or natural rubber latex is used.

(e) In the molecule as a halogenating agent A compound containing a bond (wherein X is halogen) or an alkyl hypohalide, wherein: The compound containing a bond (in the formula, X is halogen) is specifically a halogenated succinimide such as N-bromosuccinimide; a halogenated isocyanuric acid such as trichloroisocyanuric acid or dichloroisocyanuric acid; and dichlorodimethylhydantoin. Examples of such halogenated hydantoins can be mentioned.

Alkyl hypohalides are normal, secondary or tertiary alkyl hypohalides, especially the use of tertiary alkyl hypohalides such as tertiary butyl and tertiary amyl chloride and bromide. Is preferred.

The mixing ratio of each of the above components is such that the solid content of the resorcin resin is 1 to 25 parts by weight with respect to 100 parts by weight of water as a solvent.
0.1 to 5 parts by weight of alkali in terms of NaOH, 0.5 to 20 parts by weight of formaldehyde in formalin, 7 to 250 parts by weight of latex solids, 0.01 to 10 parts by weight of halogenating agent in terms of N-bromosuccinimide, preferably Is 0.5 ~
5 parts by weight.

When the solid content of the resorcinol resin is less than 1 part by weight or 25 parts by weight or more, the amount of alkali is less than 0.1 part by weight or 5 parts by weight or more, the formaldehyde content in formalin is 0.
If the solid content of the latex is less than 5 parts by weight or 20 parts by weight or more and the solid content of the latex is less than 7 parts by weight or 250 parts by weight or more, the adhesion is lowered.

Further, when the amount of the halogenating agent is 0.01 part by weight or less, the adhesive force is lowered, and even when the amount of the halogenating agent is 10 parts by weight or more, the adhesive force is not improved, and the halogenating agent may be precipitated as crystals. .

Next, a method for producing the adhesive composition of the present invention will be described.

First, resorcin and formaldehyde are subjected to a condensation reaction under an acidic condition according to a conventional method to obtain a resorcin resin. Next, this resorcin resin and the above alkali, formalin, and latex are mixed at a predetermined ratio with water as a solvent, and they are reacted according to a conventional method.

After that, the above-mentioned predetermined amount of the halogenating agent is added to the obtained composition and mixed, whereby the adhesive composition of the present invention can be obtained.

On the other hand, the application target of this adhesive composition is the E
Polyolefin vulcanized rubber such as PDM and EPM, styrene-butadiene rubber (SBR), butyl rubber (II
R), chloroprene rubber (CR), nitrile rubber (NB
R) and various synthetic rubbers and natural rubber (NR),
Or polyolefin synthetic resin such as PP or PE, vinyl chloride resin, ABS resin, styrene resin (PS),
It is various synthetic resins including ethylene-vinyl acetate copolymer resin (EVA).

Further, the NR, SBR, IIR, C in the above-mentioned polyolefin-based vulcanized rubber is contained in such an amount that the properties thereof are not lost.
Rubber components such as R and NBR, ABS resin, PS, PE,
Those containing resin components such as PP and EVA are also included.

Furthermore, the above-mentioned polyolefin-based vulcanized rubber, and the compound usually used in those obtained by adding the above-mentioned various rubber components and resin components, that is, sulfur as a vulcanizing agent, morpholine disulfide, dicumyl peroxide, 2-Mercaptobenzothiazole, zinc dimethyldithiocarbamate, tetramethylthiuram disulfide as a vulcanization accelerator, antioxidant / antioxidant, phenyl-α-naphthylamine as an ozone deterioration inhibitor, 2,6-di-t-butyl- In some cases, p-cresol, carbon black, magnesium carbonate, clay as a filler, dioctyl sebacate as a plasticizer, mineral oil and the like are added.

Examples will be described below, but the present invention is not limited to the following examples.

Example-1 Resorcin resin 1.0 g (as solid content, the same below) in 100 g of water), NaOH 1.0 g, formaldehyde 0.5 g, SBR
7 g of latex (as solid content, the same below) was added and reacted. Next, 0.01 g of N-bromosuccinimide was added to this reaction solution, and the mixture was stirred and mixed to obtain an adhesive composition. As SBR latex, manufactured by Japan Synthetic Rubber Co., Ltd.
JSR-0561 (specification of solid content 69%) was used.

Table 1 shows the formulations of the adhesive compositions of Examples-2 to 10 obtained by the same production method.

All of the SBR latexes used were those manufactured by Japan Synthetic Rubber Co., Ltd., and the NBR latexes were manufactured by Hiker Co., Ltd.
Neoprene latex is manufactured by Showa Neoprene.

Next, the following tests were conducted in order to investigate the adhesive strength of the adhesive compositions of Examples 1 to 10 above.

EPDM having the composition shown in Table 2 was vulcanized at 160 ° C. for 20 minutes to produce a 150 mm × 10 mm × 0.5 mm thick test piece, and 6,6-nylon resin was injection-molded to produce 150 mm × 10 mm.
A test piece with a thickness of 0.5 mm was manufactured.

Then, the adhesive composition of Example-1 was applied to the surfaces of the above-mentioned two kinds of test pieces and air-dried at room temperature for 30 minutes, and then the applied surfaces were pasted together and a pressure of 100 to 150 kg / cm ² was applied. It was applied and adhered at 100 ° C. for 15 minutes. Then, the bonded test piece is left to stand at room temperature for 24 hours,
The tensile shear strength of the adhesive surface was measured at a tensile speed of mm / min, and the results shown in Table 1 were obtained. Moreover, Examples 2-1
The tensile shear strength was similarly measured for the adhesive composition No. 0, and the results shown in Table 1 were obtained.

On the other hand, as a comparative example, a composition having the composition shown in Table 3 was produced by the same method as each of the above-mentioned Examples (Comparative Example-1
~ 6) and a commercially available adhesive (Comparative Example-7) were applied to the test pieces, and the results of the tensile shear test are shown in Table-3.

The composition of Comparative Example-1 had a reduced tensile shear strength because it did not contain a resorcin resin. Further, since Comparative Example-2 does not contain a latex and Comparative Example-3 does not contain a halogenating agent, Comparative Example-4 further contains formaldehyde, Comparative Example-5 a latex, and Comparative Example-6 a halogenated compound. Since each of the agents was excessively compounded, the tensile shear strength was lowered in each case.

From the above test results, each contact of Examples-1 to 10 It has been found that the adhesive composition exhibits strong adhesion to EPDM and nylon resin, and exhibits excellent effects as an adhesive for the rubber and resin.

Further, the above adhesive composition is not limited to EPDM and nylon resin, and also exerts an excellent effect as an adhesive for various synthetic resins, synthetic rubber, and the like, and further, adhesion between rubber and fiber and wood-to-wood bonding. It can also be used for bonding.

The present invention is not limited to the above embodiment,
For example, an organic solvent may be used instead of water as the solvent.

Effect of the Invention As described above in detail, in the present invention, the halogenating agent is 0.01 to 10 parts by weight in terms of N-bromosuccinimide with respect to 100 parts by weight of water or the organic solvent.
It is an excellent invention as an adhesive that can be applied to a wide range of applications, exhibiting the effect of exhibiting a strong adhesive force when used for bonding various rubbers and resins including polyolefin rubbers and polyolefin synthetic resins. is there.

Claims (3)

[Claims] 1. A resorcin resin (a), an alkali (b), a formalin (c), a latex (d), and (e) in a molecule. A compound containing a bond (wherein X is halogen), or a halogenating agent selected from any one of alkyl hypohalides, (f) water or an organic solvent, wherein the halogenating agent is water or an organic solvent 100
0.0 in terms of N-bromosuccinimide with respect to parts by weight
An adhesive composition having a ratio of 1 to 10 parts by weight. 2. The adhesive composition according to claim 1, wherein the alkali is NaOH, the halogenating agent is N-bromosuccinimide, and the solvent is water. 3. The solid content of resorcin resin is 1 to 25 parts by weight, NaOH is 0.1 to 5 parts by weight, the solid content of latex is 7 to 250 parts by weight, and N-bromosuccinimide is 0.01 to 100 parts by weight of water. The adhesive composition according to claim 2, which comprises 10 parts by weight.