JPH0635572B2 - Amide group-containing adhesive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an amide group-containing acrylic modified chlorinated polyolefin and isocyanate obtained by polymerizing an amide group-containing acrylic compound in the coexistence of chlorinated polyolefin and liquid rubber. The present invention relates to an amide group-containing adhesive resin composition containing a mixture of a series compound or an isocyanate compound as a main component and having excellent adhesive strength and solvent resistance. In the present invention, all of the acrylic groups also include methacrylic groups unless otherwise specified.

[Conventional technology]

Conventionally, chlorinated polyolefins have excellent solubility in organic solvents, and films obtained from the solutions have excellent acid resistance, alkali resistance, weather resistance, etc., and have been put to practical use in various fields as paints, printing inks, adhesives, etc. .

However, chlorinated polyolefins have drawbacks such as poor solvent resistance, inadequate film strength, low softening temperature, poor affinity for polar substances, and poor adhesion to metals.

In order to improve the above-mentioned various drawbacks of conventional chlorinated polyolefins, a post-chlorinated polyolefin can be thermoplastically crosslinked by reacting with a monomer having an epoxy group, a hydroxyl group or a carboxyl group in the presence of a radical generator. Resin production method (Japanese Patent Publication No. 51-24316) or chlorinated polyolefin is dissolved in an organic solvent, and solution polymerization reaction is carried out in the presence of one or more mixed monomers of acrylic monomers and a polymerization initiator. There are inventions of acrylic-modified chlorinated polyolefin coating compositions (Japanese Patent Laid-Open No. 194959/1983), which have improved solvent adhesion to non-adhesive substances such as polypropylene, but solvent resistance. The physical properties such as are not yet sufficient.

[Problems to be solved by the invention]

In view of the above, the present invention is an amide group-containing adhesive for the purpose of improving the adhesive strength between polar substances such as polyolefin and difficult-to-adhesive substances and solvent and solvent resistance, and softening temperature. As a result of intensive studies conducted by the present inventors, one or more amide group-containing acrylic compounds or amide group-containing methacrylic compounds are grafted onto a chlorinated polyolefin having a chlorination rate of 60% or less. When polymerized, an amide group-containing adhesive resin composition containing an amide group-containing acrylic or methacrylic copolymer-modified chlorinated polyolefin and an isocyanate compound or a mixture thereof, which are obtained by coexisting a liquid rubber, is used. By using it, it has excellent compatibility and long-term adhesion to the polyolefin base material and the polyolefin base material or the polyolefin base material. Adhesion between polar materials such as Refuin base material and the metal and solvent resistance, ItaruTsuta completed the present invention which is excellent in physical properties such as softening temperature.

[Means for solving problems]

The present invention is a chlorinated olefin (a) having a chlorination rate of 60% by weight or less.
And, when copolymerizing one or more kinds of amide group-containing acrylic compound or amide group-containing methacrylic compound (b) optionally containing other copolymerizable monomer, in the coexistence of the liquid rubber (c), ( a) / (b) = 99/1 to 50/50 (solid content weight ratio, the same applies below) and (a) / (c) = 99.9 / 0.1 to 90/10, and the resulting amide group Containing acrylic or amide group-containing methacrylic modified chlorinated polyolefin (hereinafter abbreviated as amide group-containing acrylic modified product (A)) and an isocyanate compound or a composition of an isocyanate compound
An amide group-containing adhesive resin composition comprising (B) as a main component.

Here, a typical example as (b) is acrylic acid amide,
Methacrylic acid amide, Nt-octyl acrylamide, Nt-octyl methacrylamide, N, N'-
Dimethylaminopropyl acrylamide, N, N'-dimethylaminopropyl methacrylamide, diacetone acrylamide, diacetone methacrylamide,
N, N'-Methynylene bisacrylamide, N, N'-
Methylene bis methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and the like, and typical monomers added to the amide group-containing acrylic compound or the amide group-containing methacrylic compound according to the purpose are methyl acrylate and methacrylic acid. Methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl actylate, butyl methacrylate, 2-ethylhexyl actylate, 2-ethylhexyl methacrylate, glycidyl acrylate, glycidyl methacrylate,
Acrylic acid, methacrylic acid, β-methylglycidyl acrylate, β-methylglycidyl methacrylate,
2-hydroxyethyl acrylate, 2-methacrylic acid
Such as hydroxyethyl, it includes all copolymerizable monomers.

Polyethylene as the chlorinated polyolefin (a),
Polypropylene, ethylene-propylene copolymer, natural rubber, ethylene vinyl acetate copolymer, synthetic isoprene rubber, polybutadiene, etc., which are uniformly or heterogeneously chlorinated up to 60% by weight by a known method, for example, a typical Examples thereof include chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-vinyl acetate copolymer and the like.

Further, the liquid rubber (c) is preferably a polymer containing a diene monomer as a main component and having a number average molecular weight of 500 to 100,000 and showing fluidity at room temperature.

Examples of the liquid rubber (c) as described above include 1,2-polybutadiene, 1,4-polybutadiene, and poly-butadiene having a functional group such as a carboxyl group, a hydroxyl group, a mercapto group, a halogen group, an amino group and an epoxy group in the molecule. Isoprene,
Liquid rubbers such as polychloroprene and unsaturated hydroxylated 1,2-polybutadiene such as terminal hydroxylated 1,2 polybutadiene and 1,4-polybutadiene, and 1,2-polybutadiene having a number average molecular weight of 500 to 100,000 without functional groups, 1, 4-polybutadiene, styrene-butadiene copolymer and the like, and further, the above mixture may be used.

The reaction medium is one that uniformly dissolves the above three components (a), (b) and (c). Industrially, it is a chlorinated solvent such as carbon tetrachloride or methylene chloride, or an aromatic such as toluene or xylene. Hydrocarbons or mixed solvents thereof are effectively used.

The reason for this is that if the method of the present invention is carried out after the chlorination of polyolefin, unnecessary steps for solvent separation can be omitted.

The amide group-containing acrylic modified product (A) used when producing the amide group-containing adhesive resin composition of the present invention is the same as (b) above.
(a) and (c) are copolymerized in the presence of (c). In this case, as described above, (a) / (b) = 99/1 to 50/50, preferably
99/1 to 90/10 is good, and (a) / (c) = 99.9 / 0.
1, 90/10, preferably 99.5 / 0.5 to 95/5.

When (b) is 1 or less with respect to 99 of (a), physical properties such as film strength, adhesive strength and solvent resistance of the product of the present invention are deteriorated.
When (b) is 50 or more with respect to 0, an acrylic homopolymer insoluble in the reaction solvent is produced, and gelation is likely to occur at around room temperature, so that the object of the present invention cannot be achieved.

Further, in order to obtain the amide group-containing acrylic modified product (A), a known polymerization method can be directly used.

For example, a polymerization initiator that generates radicals at a polymerization temperature of 60 to 110 ° C, such as a benzoyl peroxide, azobisisobutyronitrile, and a dialkylperoxide, which are well-dissolved in a reaction solvent and dispersed uniformly and rapidly. Oxide, ketone peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, etc. are used.

There are many commercially available polymerization initiators such as Kayaester O-50 (manufactured by Kayaku Nouri Co., Ltd.), Barbutyl D (manufactured by NOF Corporation), Perbutyl A (the same).

As the isocyanate compound used in the present invention, diisocyanates such as tolylene diisocyanate, hexalene diisocyanate, and diphenylmethane diisocyanate, and derivatives thereof, and polyisocyanates such as polyethylene polyphenyl polyisocyanate can also be used. is there.

Examples of commercially available products include Coronate-HL (manufactured by Nippon Polyurethane Co., Ltd.) and Coronate-L (same as above).

The ratio of the isocyanate compound (including the mixture) used in the present invention is -NCO / -CONH ₂ (molar ratio) of 10/1 to 1/2,
It is preferably 2/1 to 1/2. In the range other than this, it becomes difficult to achieve the object of the present invention.

In this case, according to the study by the present inventors, isocyanate reacts with active hydrogen to crosslink, It is considered that the formation of such a bond effectively contributes to various physical properties of the amide group-containing adhesive composition of the present invention.

〔Example〕

 Next, the present invention will be described with reference to examples.

Example 1 [Production of amide group-containing acrylic modified product (A)] "Hardlene 14-
LLB ”(chlorinated polypropylene manufactured by Toyo Kasei Co., Ltd.,
Chlorination rate = 28%, solid content 15%) 100 parts was charged to raise the liquid temperature in the reactor to 90 ° C, and then acrylamide 0.75
Parts, terminal OH groups, 0.3 parts of 1,4-polybutadiene were added and homogenized, and when the liquid temperature in the container became stable at 90 ° C, 0.14 parts of Kayaester O-50 (manufactured by Kayaku Nouri Co., Ltd.) Dripping,
Drop 0.05 times 3 times every 1 hour, then for 3 hours,
The mixture was aged at the same temperature to obtain an amide-containing acrylic modified product (Ai) having a solid content of 15.9%.

Example 2 (same as above) “Hardlen 14-LLB” in Example 1 was replaced with “Hardlen 14
-EV "(chlorinated ethylene-vinyl acetate copolymer manufactured by Toyo Kasei Co., Ltd., chlorination rate = 28%, solid content 20%), and 100 parts, acrylamide 1 part, terminal O
H device 1, 0.4 polybutadiene 0.4 parts, Kayaester O
The amide group-containing acrylic modified product (A-2) having a solid content of 21.1% was obtained in the same manner as in Example 1 except that the charged amounts of -50 were changed to 0.18 parts and 0.06 parts, respectively.

Comparative Example 1 Solid content 1 in the same manner as in Example 1 except that the terminal OH group 1,4-polybutadiene was not added.
5.6% amide group-containing acrylic modified product (A-3) was obtained.

Example 3 With respect to the above-mentioned A-1 to A-3, the amide group-containing acrylic modified product and the isocyanate compound were blended at the blending ratios shown in Table 1, and the adhesion, peeling strength, gasoline resistance, and hardness were obtained. , The softening temperature was tested, and the results are summarized in Table 1.

From Table 1, as compared with "Hardlene 14-LLB", the adhesiveness, peeling strength, gasoline resistance, hardness and softening temperature of the resin composition obtained from the products (A-1) and (A-2) of the present invention It can be seen that the coating film performance is significantly improved over all of the above.

Example 4 The amide group-containing acrylic modified product prepared in the same manner as in the above Example 1 was used with a hardened product manufactured by Toyo Kasei Kogyo Co., Ltd. having different chlorine contents to obtain resin compositions obtained from the modified products. Was obtained and shown in FIG.

FIG. 1 is a three-dimensional graph showing the effect of acrylamide modification on the heat seal strength. From FIG. 1, it can be seen that the effect of amide group-containing acrylic modification is greater than that of the unmodified product.

Figure 1 uses a biaxially oriented polypropylene film 60 microns / Aluminum off oil _{15μ, -NCO / -CONH 2 = 1.0} ( molar ratio) in dual coated, overnight drying at room temperature, heat-sealing 130 ℃, 1Kg / cm ² The G pressure is maintained for 1 second, and the peeling speed is 200 mm / min.

It can be seen from FIG. 1 that the effect of the amide group-containing acrylic modification (4) is significantly greater than that of the unmodified product (3).

Example 5 The softening temperature of chlorinated polyolefin in the same manner as in Example 4 and the amide group-containing acryl-modified chlorinated polyolefin prepared as in Example 1 are shown in FIG.

FIG. 2 shows the effect of acrylamide modification on the softening temperature.

(1) is a 5% acrylamide denaturing softening temperature curve, (2) is an undenaturing softening temperature curve, and it can be seen from FIG. 2 that the denaturing effect of the present invention is good.

EFFECTS OF THE INVENTION In the amide group-containing adhesive resin composition of the present invention, (a) the adhesive force between so-called olefins or other non-adhesive substances such as polypropylene or these and polar substances such as metals is dramatically increased.

(B) Compared to the coating film obtained by the conventional method, the physical properties such as solvent resistance is remarkably improved and the coating composition is used as a top coat as a coating composition, and is used as a primer for the surface of a polyolefin base material. Significantly expanded.

[Brief description of drawings]

FIG. 1 shows the effect of acrylamide modification on the heat-sealing strength of the present invention. The chlorine content% and the compounding ratio (%) of acrylamide to chlorinated polypropylene when synthesizing an amide group-containing acrylic modified product are shown. Peel strength (G / cm) and three-dimensional graph, Fig. 2 shows the effect of acrylamide modification at softening temperature. The chlorine content and softening of chlorinated polyolefin and amide group-containing acrylic modified chlorinated polyolefin of the present invention are shown. It is a relationship diagram with temperature. 1. The amide group-containing acrylic modified chlorinated polyolefin of the present invention. 2. Unmodified chlorinated polyolefin. 3. Peel strength curve of unmodified product. 4. The peel strength curve of the present invention.

Claims (1)

[Claims] 1. An amide group-containing acrylic compound or methacrylic compound containing (a) a chlorinated polyolefin having a chlorination ratio of 60% by weight or less and (b) optionally other copolymerizable monomer ( c) In the presence of liquid rubber, (a) / (b) = 99/1 to 50/50 (same as the solid weight ratio) and (a) / (c) = 99.9 / 0.1 to 90/16 It is characterized in that it contains as a main component an amide group-containing acrylic modified chlorinated polyolefin or an amide group-containing methacryl modified chlorinated polyolefin obtained by reacting at a ratio and an isocyanate compound or a composition of an isocyanate compound. An amide group-containing adhesive resin composition.