JPS6295372A - Adhesive resin composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting essentially of an acrylic modified chlorinated polyolefin based copolymer obtained by reacting a chlorinated polyolefin with a liquid rubber in a specific proportion and an isocyanate based compound and having improved adhesive force and solvent resistance. CONSTITUTION:An adhesive resin composition consisting essentially of a hydroxyl group-containing acrylic-modified chlorinated polyolefin produced by reacting (B) one or plural kinds of hydroxyl group-containing acrylic acid ester, e.g. 2-hydroxypropyl acrylate, by adding one or plural kinds of other copolymerizable monomers or without adding in the presence of a chlorinated polyolefin having <=60wt% chlorination degree and (C) a liquid rubber at 99/14n50/50 solid weight ratio of the components (A) to (B) and 99.9/0.1-90/10 solid weight ratio of the components (A) to (C) and one or plural kinds of isocyanate based compounds. EFFECT:Improved softening point. USE:Suitable for coating material components.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides chlorinated polyolefin in the coexistence of liquid rubber.
The present invention relates to an adhesive resin composition having excellent adhesive strength and solvent resistance and containing as main components an acrylic-modified chlorinated polyolefin copolymer obtained by acrylic modification and an isocyanate-based compound.

[Conventional technology]

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

However, these have drawbacks such as poor solvent resistance, insufficient strength of the black film, low softening temperature, poor affinity for the surface of polar substances, and poor adhesion to metals and the like.

Therefore, in order to improve the above-mentioned drawbacks of conventional polyolefins with a chlorine ratio, oxidatively modified chlorinated polyolefins are crosslinked by heating and reacting monomers having ethylenically unsaturated bonds in a solvent in the presence of a radical polymerization catalyst. Polymers have been developed (Japanese Patent Publication No. 51-24316), but although their adhesive strength to difficult-to-adhesive materials such as polypropylene is better than that of unmodified chlorinated polyolefins, their physical properties such as solvent resistance are still insufficient.

Furthermore, there is an invention (Japanese Unexamined Patent Publication No. 58-94959) in which chlorine-containing polyolefin is acrylic-modified to increase its adhesion to difficult-to-adhesive substances such as polyolefin, but even in this invention, it is difficult to adhere to difficult-to-adhere substances such as polypropylene. It is almost impossible to improve the adhesion between these materials and metals, or to dramatically increase properties such as solvent resistance.

[Problem that the invention seeks to solve]

In view of the above, the present invention aims to dramatically improve the adhesive strength between polyolefins or between polyolefins and hard-to-adhesive adherends such as metals, and to significantly improve physical properties such as solvent resistance. The present inventors provide a resin composition in which a single or multiple hydroxyl group-containing acrylic ester or methacrylic ester or a mixture thereof is inflat-polymerized into a chlorinated polyolefin having a chlorine content of 60% or less. By using an adhesive resin composition whose main components are a hydroxyl group-containing acrylic copolymer-modified chlorinated polyolefin obtained by coexisting a liquid rubber and an isocyanate compound, it has excellent compatibility. We have discovered that it is possible to obtain an adhesive that has long-term adhesion between polyolefin base materials and between polyolefin base materials and polar substances such as metals, has high adhesive strength, and has excellent physical properties such as solvent resistance. It was completed.

[Effect]

According to research by some researchers, the addition of the liquid rubber increases the acrylic modification rate (grafting rate), and the addition of isocyanate compounds improves physical properties such as solvent resistance after curing. , we have reached the legal theory that this is to achieve the effects of the present invention, which will be described later.

[Means to solve the problem]

The present invention is a chlorinated polyolefin with a chlorination rate of 60% or less (
a) and liquid rubber (C), with or without the addition of one or more hydroxyl group-containing acrylic esters and one or more other copolymerizable monomers [by burning] ], chlorinated polyolefin (a)/hydroxyl group-containing acrylic ester (6) = 99/
I~so/so (solid content weight ratio, same below) and chlorinated polyolefin (a)/liquid rubber (c) = 99.
Polar substance can such as polyolefin and metal containing as main components hydroxyl group-containing acrylic-modified chlorinated polyolefin produced by reaction at a ratio of 910.1 to 9 o/l O and one or more unconverted isocyanates. The object of the present invention is to provide an adhesive resin composition that has extremely high adhesion to surfaces.

Typical examples of the above-mentioned hydroxyl group-containing acrylic esters include 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydrokine ethyl acrylate + JV-to, and 2-hydroxyethyl methacrylate←
It goes without saying that in addition to these, acrylic esters or methacrylic esters having a water dispersing group can be used in general.

(Of white, typical monomers added depending on the purpose are methyl acrylic, methyl methacrylic,
Examples include acrylic threshold 2-ethylhexyl, methacrylic imitator 2-ethylhexyl, glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, β-methylgly/dyl acrylate, β-methylglycidyl methacrylate.

These can be selected from all acrylic esters and methacrylic esters capable of copolymerization, or two or more of them may be used.

Chlorinated polyolefin (a) includes polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isoprene rubber, ethylene-vinyl acetate copolymer, etc., uniformly chlorinated to a maximum of 60% by weight. For example, chlorinated polyethylene,
These include chlorinated polypropylene, chlorine ratio ethylene propylene copolymer, chlorinated ethylene-vinyl acetate copolymer, and the like.

Furthermore, the liquid rubber of the present invention is a polymer having a number average molecular weight of SOO to 100,000, which is mainly composed of a diene monomer, and is preferably one that exhibits fluidity at room temperature. carboxyl group, hydroxyl group,
1,2-polybutadiene with functional groups such as mercapto group, /S logo, amino group, and epoxy group, 114-
Liquid rubbers such as polybutadiene, polyisoprene, polychloroprene, unsaturated dicarboxylic acid half esters such as terminal hydroxylated 112-polybutadiene, ], 4-polybutadiene, or 1 with a number average molecular weight of 500 to 100.000 without functional groups. .2-polybutadiene, 114-polybutadiene, styrene-butadiene copolymer, etc., and may also be a mixture thereof.

Furthermore, as a reaction medium, fl(a), (b), and (C) are uniformly dissolved. This is because if the reaction of the present invention is performed subsequently, the trouble of solvent separation can be omitted.

The hydroxyl group-containing acrylic modified product (named A) used in obtaining the adhesive composition of the present invention is obtained by copolymerizing the above (b) in the presence of (a) and (C). Rannyb
', (a) / (b) = 99/1~50150
, preferably 98/2 to 70/30, and (a)
/ (c) = 99.910°1~9 o/I O
, preferably 99.510.5 to 9515.

If (b) with respect to (a) is other than 1 to 50 and (e) with respect to (a) is other than O0I to 10, it is difficult to obtain an excellent adhesive resin composition that exhibits the effects of the present invention and does not achieve the above object of the present invention. Can not do it.

In order to obtain the hydroxyl group-containing modified acrylic material of the present invention, known polymerization methods can be used as they are.
In polymerization in the temperature range of °C, it is recommended to use benzoyl peroxide, azobisisobutyronitrile, etc. as a polymerization initiator that generates radicals, and to disperse them uniformly and quickly in the reaction solvent. and polymerize.

Further, in addition to the above-mentioned polymerization initiators, there may be mentioned dialkyl chloride, ketone peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, and the like.

For example, as a product name, from t - Yanistel 0-, 5'-,
2 (Kayaku Nouri Co., Ltd.), Perbutyl D (same as above)
A large number can be mentioned, including Barbutyl Z (same as above).

The isocyanate compound used in the production of the adhesive resin composition of the present invention includes tolylene diisocyanate,
Diisocyanates such as hexamethylene diisocyanate and diphenylmethane diisocyanate, derivatives thereof, and polyisocyanates such as polymethylene polyphenyl polyisocyanate are used.

For example, products such as Coronate-HL (manufactured by Nichifu Polyurethane Industry Co., Ltd.) and Coronate-L (same as above) are suitable.

The proportion of the isocyanate used in the present invention is 1'<Co/-OH=10/I to I/2 (
, %le ratio), more preferably 2/! ~1/2
is within the range of

Outside these ranges, it may be difficult to achieve the object of the present invention.

〔Example〕

Next, misfire (7) will be explained using an example.Example 1
(Example of production of 01 group-containing acrylic modified product a) In a reactor equipped with a stirrer and a cooler,
LBJ (manufactured by Toyo Kasei Kogyo ■, chlorine (hiboripropylene,
190 parts of chlorine (H ratio: 28%, solid content 30%) was charged, the temperature of the liquid in the reactor was raised to 90°C, and then 3 parts of 2-hydroxyethyl acrylate and 1.4-terminal hydroxyl groups were charged.
Add 0.6 parts of polybutadiene, homogenize it, and when the liquid temperature in the vessel stabilizes at 90°CK, drop 0.3 parts of Kayaester O-50 (manufactured by Ueyaku Nouri@), and then add it every hour. 0.1 parts each was added dropwise three times, and then aged for 3 hours at the same temperature to obtain a hydroxyl group-containing acrylic modified product (A-1) with a solid content of 32.4%.

Example 2 (Same as above) "Pardren 14-LLBJ" in Example 1 was replaced with "Pardren 14-LLB, New Type" (Toyo F.Hisei Kogyo)
A hydroxyl-containing acrylic modified product with a solids content of 32.5% was prepared in the same manner as in Example 1, except that the chlorinated low-molecular-weight polypropylene (chlorine ratio: 28%, solid content: 30%) was used.
A-2) was obtained.

Example 3 (same as above) Terminal hydroxyl group in Example 1! , 4-polybutadiene 0.6
A hydroxyl group-containing acrylic modified product (A-3) with a solid content of 32.8% was obtained in the same manner as in Example 1 except that the part was changed to 1.2 parts. Comparative Example 1 (Same as above) Example An OH group-containing a)acrylic modified product (A-4) with a solid content of 29.9% was obtained in the same manner as in Example 1 except that the terminal hydroxyl group 1,4-polybutadiene was not added in Example 1. .

Example 4 Regarding the above A-1-A-4, “Pardrene 14-
Table 1 for "LLBJt Comparative Example 2" , pencil hardness, and softening temperature were tested and summarized in Table 1.

Example 5 In the same manner as in Examples 1 and 2 above, the molecular weight of the chlorine ratio polyolefin and the chlorine content were variously changed, the peel strength was determined, a three-dimensional graph was completed, and the graph was drawn as shown in Figure 1. Like<K7tsuta.

In other words, does the %1 figure affect heat seal strength? As is clear from FIG. 1, which shows the effect of 2-hydroxyethyl thiacrylate modification, the effect of unmodified modification is large, especially in the low molecular weight region.

In FIG. 1, a biaxially stretched polypropylene film 6
0fil Fluminium foil t5)t s-NCO
/-OH=], O (molar ratio) was coated on both sides, and was allowed to self-dry overnight.

ζ-tosil is 130℃, I Kfl /' crj
At a pressure of G, for 1 second, the peeling speed (1) is 2o Ornm/
It's a minute.

From the first JL, the adhesive resin composition of the present invention has coating film performance in all aspects of adhesion to PP (polypropylene film), peel strength, gasoline resistance, pencil hardness, and soft riveting temperature. It can be seen that this is significantly superior to the comparative example.

Example 6 In the same manner as in Examples 1 and 3, the addition rate of 1,4-polybutadiene having terminal OH groups was varied, and the gasoline resistance was shown in FIG. 2.

FIG. 2 shows the effect on the solvent resistance of liquid rubber, which was measured after being left at room temperature for 24 hours using gasoline as a solvent.

? It can be seen from Figure 52 that the effect of acrylic modification by adding rubber is large.

Tree fertilizer/composition using X1 Example 1 in Figure 2.

(G) IDI fat composition using Example 2 [Effects of the invention] The effects of the present invention are summarized as follows. (B) Female adhesive substances such as polypropylene or these The adhesive strength between polar substances such as metals has increased dramatically.

(b) Compared to coating films obtained by conventional methods, four properties such as solvent resistance and softening point are significantly improved, and in terms of applications, it can be used as a top coat on polyolefin surfaces or as a primer. Possible O e → There is an advantage that it can be effectively used as a paint composition.

[Brief explanation of drawings]

Figure 1 shows the effect of 3-thiacrylic r:R-2 hydroxyethyl modification on the heat seal strength of Misfire 1, and shows the molecular weight, chlorine content ((6)
and peel strength<? /CV-), Figure 2 shows the effect on the solvent resistance of liquid rubber, and shows the relationship between the addition rate of liquid rubber (to resin polydisperse) and the gasoline resistance shown by the resin residual rate. 1 Peel strength curve of 151 finished products 2 Peel strength curve of unmodified product

Claims (1)

[Scope of Claims] 1. Chlorinated polyolefin with a chlorination rate of 60% by weight or less (
a) and liquid rubber (c), with or without addition of one or more other copolymerizable monomers to one or more hydroxyl-containing acrylic esters [(b) ). ], (b) to (a)/(b
) = 99/1 to 50/50 (solid content weight ratio, same below)
The main components are a hydroxyl group-containing acrylic-modified chlorinated polyolefin and one or more isocyanate compounds produced by reacting at a ratio of (a)/(c) = 99.9/0.1 to 90/10. An adhesive resin composition comprising: