JPH05140522A - Moisture-crosslinkable polychloroprene based adhesive - Google Patents

Abstract

PURPOSE:To obtain the subject one-pack type adhesive consisting of a specific modified polychloroprene, tackifier and organic solvent, and excellent in heat resistance. CONSTITUTION:The objective adhesive consists of (A) a modified polychloroprene obtained by subjecting (i) a carboxyl-containing polychloroprene to condensation reaction with (ii) an active silyl compound containing >=2 alkoxysilyl bond (e.g. tetraalkoxysilane), (B) a tackifier and (C) an organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a moisture-crosslinkable polychloroprene-based adhesive, and more specifically to a modified polychloroprene in which a hydrolyzable alkoxysilyl group is introduced into a molecule of polychloroprene through a carboxyl group or the like. The present invention relates to a one-pack type moisture-crosslinkable polychloroprene-based adhesive having excellent heat resistance, which is particularly required for integral molding and adhesion processing by using components.

[0002]

2. Description of the Related Art In recent years, in automobile interior parts, for the purpose of imparting a high-class feeling, integral molding and bonding of polyolefin foam by various methods such as vacuum molding is often used. Is becoming By the way, since excellent heat resistance is required for such integrally molded adhesive processing, a two-component polychloroprene adhesive in which an isocyanate curing agent is combined is used. Due to the reduction of the heat resistance, the development of a one-component type adhesive having excellent heat resistance is being demanded.

[0003]

[Means for Solving the Problems] The inventors of the present invention have made earnest studies to provide an adhesive satisfying the above demands. As a result, a hydrolyzable alkoxy group is introduced into a molecule of polychloroprene through a carboxyl group or the like. If modified polychloroprene containing a silyl group is the main component, and a tackifying resin and an organic solvent are added to this, a cross-linking reaction occurs due to moisture in the atmosphere even though it is a one-component type, and it exhibits excellent heat resistance. The present invention has been completed and the present invention has been completed.

That is, according to the present invention, a modified polychloroprene obtained by subjecting a carboxyl group-containing polychloroprene to a condensation reaction of an active silyl compound having two or more alkoxysilyl bonds (hereinafter referred to as an alkoxysilyl modified polychloroprene) A moisture-crosslinkable polychloroprene-based adhesive comprising a tackifier and an organic solvent.

The carboxyl group-containing polychloroprene used in the present invention includes polychloroprene having a carboxyl group introduced by copolymerization which is generally commercially available, and polychloroprene having a carboxyl group introduced by treatment with an oxidizing agent such as oxygen or ozone. Is called.

In the present invention, the active silyl compound having two or more alkoxysilyl bonds to be condensed with the carboxyl group-containing polychloroprene is:
Specifically, (i) all of the alkoxysilyl compounds having various functional groups such as dialkoxysilane, trialkoxysilane or tetraalkoxysilane having two or more alkoxysilyl bonds capable of reacting with a carboxyl group are applicable. And: alkyltrialkoxysilanes such as methyltrimethoxysilane, n-propyltrimethoxysilane; aminomethyltriethoxysilane, N- (β-
Aminoethyl) aminomethyltrimethoxysilane, aminomethyldiethoxysilane, N- (β-aminoethyl) methyltributoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminoisobutyltrisilane Methoxysilane, N-
(β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ
-Amino-β-methylpropyltrimethoxysilane and other aminodi- or trialkoxysilanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxylane and other mercaptodi- or trialkoxysilanes; γ-glycidoxypropylmethyldimethoxysilane , Γ-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, epoxydi- or trialkoxysilane such as 3,4-epoxycyclohexylethylmethyldimethoxysilane; γ-isocyanatopropyltriethoxysilane, polyisocyanate And the above-mentioned aminodi or trialkoxysilane, mercaptodi or trialkoxysilane or epoxydi or trialkoxysilane Isocyanate di- or trialkoxysilanes such things like,

(Ii) Di- or trialkoxysilanes having a vinyl group: eg vinyltrimethoxysilane,
Vinylmethyldimethoxysilane, vinyltriethoxysilane, etc.

(Iii) A di- or trialkoxysilane having a (meth) acryloxy group (referred to as an acryloxy group or a methacryloxy group, hereinafter the same): for example, γ- (meth)
Acryloxypropyltrimethoxysilane, γ- (meth)
Acryloxypropylmethyldimethoxysilane, γ-
(Meth) acryloxypropyltriethoxysilane, γ-
(Meth) acryloxypropylmethyldiethoxysilane, etc., or (iv) tetramethoxysilane, tetraethoxysilane, etc.
One or more active silyl compounds selected from (i) to (iv) are used.

Condensation reaction of the above-mentioned carboxyl group-containing polychloroprene and active silyl compound [reaction ratio is 100
1 to 50 parts, preferably 1 to 30 parts with respect to parts (parts by weight, the same applies hereinafter) is 40 to 40 parts in a suitable reaction solvent.
It may be carried out at 100 ° C. for 1 to 24 hours, whereby the alkoxysilyl-modified polychloroprene used in the present invention can be obtained.

Examples of the tackifying resin used in the present invention include a terpene phenol copolymer, an alkylphenol resin, a coumarone-indene resin, a rosin resin, a petroleum resin and the like, and an alkylphenol resin (t-butylphenol resin and the like) and a metal oxide ( (Eg magnesia) and chelation reaction products. The amount of the tackifying resin used is usually selected in the range of 5 to 100 parts with respect to 100 parts of the carboxyl group-containing polychloroprene before the modification.

Examples of the organic solvent in the present invention include aromatic solvents such as toluene and xylene; n-hexane,
Aliphatic system such as octane and pentane; acetone, ME
Ketones such as K and MIBK; Alicyclic systems such as cyclohexane; Chlorinated hydrocarbons such as trichlorethylene;
Examples thereof include ester systems such as ethyl acetate and butyl acetate. In addition, these organic solvents can be used as a reaction solvent in the production of the above-mentioned alkoxysilyl-modified polychloroprene, and can be directly used for adhesive preparation after the reaction.

The moisture-crosslinkable polychloroprene-based adhesive according to the present invention comprises the above-mentioned alkoxysilyl-modified polychloroprene, a tackifying resin and an organic solvent, and if necessary, magnesia, zinc white, etc. as a stabilizer when kneading rubber. , Other such adhesives include fillers, dehydrating agents, plasticizers,
You may mix | blend an antiaging agent etc. with an appropriate amount. The storage stability is improved by adding methanol or the like. The preparation of such an adhesive may be carried out according to a usual roll kneading method or a direct dissolution method. Further, in the alkoxysilyl-modified polychloroprene, general polychloroprene and polychloroprene modified with the amino mono, di or trialkoxysilane or isocyanate mono, di or trialkoxysilane (the modification in this case is about 6% in polychloroprene). 2% of 1,2-chloroprene which is mixed with the 2-position-Cl may be used together in an appropriate amount range.

[0013]

The adhesive of the present invention can be applied to various adherends such as metals, woven fabrics, fiber materials, wood, leather, and plastic materials.
It can be applied to adhesion and lamination of (sheets, films, foams), etc. and exhibits particularly excellent heat resistance.

[0014]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Examples 1 to 4 and Comparative Examples 1 and 2 (1) Preparation of Adhesives The number of parts of the polychloroprene containing a carboxyl group shown in Table 1 below (Neoprene A manufactured by Showa Denko Dupont Co., Ltd.)
F), if necessary, polychloroprene (manufactured by the same company, Neoprene W) and surface-treated calcium carbonate (manufactured by Shiraishi Industry Co., Ltd.,
After stirring and mixing (white sinter flower CC) with a mixing roll,
Toluene, dissolved in a mixed solvent of n-hexane and cyclohexane, added active silyl compound (vinyltrimethoxysilane or methyltrimethoxysilane) to this,
The mixture is heated and stirred at 60 ° C. for 4 hours to be reacted, and after cooling, a terpene phenol copolymer (YS Polystar T115, manufactured by Yasuhara Chemical Co., Ltd.) is blended as a tackifier to obtain an adhesive. In the comparative example, the reaction with the active silyl compound was omitted.

(2) Performance test A polyolefin foam (Toray PPX manufactured by Toray Industries, Inc.) and a hard board were used as the adherends, and the adhesive of the above (1) was applied to each of the adherends in an amount of 100 g / m ² . Spray coating in an amount, dry for 1 minute at 80 ° C, then overlay the coated surfaces,
It was pressed with a 5 kg roller.

The test pieces thus produced were subjected to the tests of the following performance items, and the measurement results are also shown in Table 1. Performance item Initial peel strength: 5 minutes after laminating Normal peel strength: After curing at 20 ° C, 65% RH x 24 hours After heat aging Peel strength: After normal curing at 80 ° C x 168 hours After aging Heat-resistant creep: After normal curing, 80 100g in atmosphere
/ 25 mm load is applied in the 90 ° angle direction and the peel length is measured after 24 hours (the peel strength is measured at a tensile speed of 200 mm / min and a 180 ° angle)

[0017]

[Table 1]

Claims (2)

[Claims] 1. A moisture comprising a modified polychloroprene obtained by subjecting a carboxyl group-containing polychloroprene to a condensation reaction with an active silyl compound having two or more alkoxysilyl bonds, a tackifier and an organic solvent. Crosslinkable polychloroprene adhesive. 2. An active silyl compound containing two or more alkoxysilyl bonds is a compound having a dialkoxysilyl group or trialkoxysilyl group or a tetraalkoxysilane capable of undergoing a condensation reaction with a carboxyl group. Glue.