JPH0291141A - Adhesive composition - Google Patents

Abstract

PURPOSE:To improve adhesiveness of metal-metal and metal-plastic by compounding a vinyl chloride copolymer contg. phosphoric acid group, an ethylene-vinyl acetate copolymer, a pressure-sensitive resin and an org. solvent. CONSTITUTION:50-90wt.% (hereinbelow merely %) vinyl chloride copolymer (A) contg. 1X10<-6>-5X10<-4>mol/g phosphoric acid group (e.g., vinyl chloride-vinyl acetate-acid phosphoxyethyl acrylate copolymer), 5-30% ethylene-vinyl acetate copolymer (B) which is an ethylene-vinyl acetate-carbon monoxide copolymer compatible with the component A and pref. consisting of 40-80% ethylene, 15-60% vinyl acetate and 5-30% carbon monoxide, 5-20% pressure-sensitive adhesive (C) which is pref. an alicyclic petroleum resin and has a softening temp. of 150 deg.C or lower, an org. solvent (D) (e.g., methyl ethyl ketone) and, if necessary, another thermoplastic resin, a thermosetting resin, a plasticizer, a pigment, a filler, etc., (E) are compounded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to metal/metal, metal/polyvinyl chloride (PVC)
) related to solvent-type vinyl chloride adhesives used for plastics etc.

[Conventional technology]

Conventionally, vinyl chloride copolymers have been used as raw materials for adhesives for forming, filling and packaging pharmaceuticals, foods, etc., and adhesives for PVC-coated steel plates. Typical vinyl chloride copolymers include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, and vinyl chloride-vinyl acetate-vinyl alcohol copolymer, but they have poor metal adhesion. Among them, vinyl chloride-vinyl acetate-maleic acid copolymer is superior. In addition, vinyl chloride with a phosphate group-
It has been reported in JP-A-63-112 that a carboxylic acid vinyl ester copolymer has a higher adhesive strength than a vinyl chloride-vinyl acetate-maleic acid copolymer having a carboxyl group.
It is disclosed in Japanese Patent No. 675.

However, since sufficient adhesive strength cannot be obtained with these copolymers alone, the adhesive strength has been supplemented by blending thermoplastic resins, thermosetting resins, nidistomers, various additives, etc.

JP-A-62-212483 discloses that vMCH (vinyl chloride-vinyl acetate-maleic acid copolymer UCC) is blended with an ethylene-based high molecular weight polymer, an alicyclic saturated hydrocarbon resin, and a thermoplastic acrylic resin. , discloses an adhesive mixed and dissolved in an organic solvent. It has been shown that excellent adhesive strength and oil resistance can be obtained by using this adhesive for bonding metal and plastic.

As described above, various studies have been made to improve the adhesive strength of solvent-based vinyl chloride adhesives, but no adhesive has yet been found that provides satisfactory adhesive strength.

[Problem to be solved by the invention]

Conventional solvent-based vinyl chloride adhesives have insufficient adhesion of metal/metal or metal/plastic.

[Means to solve the problem]

The present invention provides I X 10-' to 5 X 10-' mol/
This is an adhesive composition comprising a zincyl chloride copolymer having a phosphoric acid group of &, an ethylene-vinyl acetate copolymer adhesive resin, and an organic solvent.

The present invention will be explained in detail below.

The amount of phosphoric acid groups in the vinyl chloride copolymer having phosphoric acid groups used in the present invention is I x 10-' to 5 x 10''
It is 4 mol/g. Phosphate group content is I x 10-'
If it is less than mol/g, the adhesive strength of the adhesive will be insufficient, and if it exceeds 5X10-4 mol/g, the water resistance of the adhesive will be insufficient.

Vinyl chloride copolymers with phosphoric acid groups may be those having acidic phosphoric acid groups in the molecule, such as vinyl chloride-vinyl acetate, vinyl chloride-vinyl propionate, vinyl chloride-vinyl acetate-vinyl alcohol. Any of the vinyl chloride-vinylidene chloride type and vinyl chloride-acrylic acid ester type can be used. Preferably,
It is a vinyl chloride-vinyl acetate-acid phosphooxyalkyl acrylate copolymer. As Ashitsu V phosphooxyalkyl acrylate, 2-acid phosphooxyethyl acrylate, 6-chloro-2-acid phosphooxyzolobyl acrylate, 2-acid phosphooxypropyl acrylate, 2-acid phosphooxyethyl methacrylate, 6-chloro- Examples include 2-acid phosphooxypropyl methacrylate and 2-acid phosphooxypropyl methacrylate.

As the ethylene-vinyl acetate copolymer used in the present invention, any copolymer can be used as long as it is compatible with the above-mentioned vinyl chloride copolymer, but ethylene-vinyl acetate-carbon oxide copolymer may be used. is particularly preferred. The composition of this copolymer is 40 to 80% by weight of ethylene, preferably 6% by weight of ethylene.
0-70% by weight, weight vinyl 15-60% by weight, preferably 20-65% - carbon oxide 5-60% by weight.

Preferably it is 5 to 15% by weight.

As adhesive resins, rosin-based resins such as rosin, polymerized rosin, rosin-glycerin ester, rosin-pentaerythritol ester, and hydrogenated products thereof; β-pinene polymer, α-pinene polymer, modified pinene polymer, and , terpene resins such as mixed pinene polymers; terpene-modified phenolic resins; aliphatic petroleum resins and alicyclic petroleum resins having unsaturated bonds from C5 to C9 petroleum fractions.

Examples include aromatic petroleum resins; chroman resins; chroman-indene resins; and xylene resins, and alicyclic petroleum resins are particularly preferred. The softening temperature of the adhesive resin is 150°C or lower, preferably 50 to 150°C.

The ratio of each component is 50 to 90% by weight of the vinyl chloride resin having a phosphoric acid group, 5 to 60% by weight of the ethylene-vinyl acid acetate copolymer, and 5 to 20% by weight of the adhesive resin.

When the vinyl chloride resin having a phosphoric acid group is less than 50% by weight, and when the ethylene-vinyl acetate copolymer is more than 30% by weight.

If the adhesive resin is less than 5% by weight, if it exceeds 120, if the ethylene-vinyl acetate resin is less than 5% by weight, or if the adhesive resin is more than 30% by weight, the temperature is 180℃ or higher. The strength of high-temperature bonding may not be sufficient.

The adhesive composition of the present invention can be used by dissolving a vinyl chloride copolymer having a phosphoric acid group, an ethylene-vinyl acetate copolymer, and an adhesive resin in an organic solvent. By other thermoplastics, thermosets, plasticizers, pigments.

Fillers, anti-aging agents, and other additives that are commonly added to adhesives of this type can be added.

The thermoplastic resins to be blended include vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, and vinyl chloride/vinylidene chloride copolymer. vinyl chloride copolymers such as, fibrous resins such as nitrocellulose,
Thermoplastic acrylic ester resin, thermoplastic methacrylic ester resin, polyurethane resin, polyester resin, nitrile rubber, styrene/butadiene rubber, etc. are used.

Further, as the thermosetting resin, polyisocyanate, urethane prepolymer, phenol resin, epoxy resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic reactive resin, etc. can be blended.

Suitable organic solvents used in the present invention include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene, and esters such as ethyl acetate.

The type and amount of other resins to be added must be carefully determined so as not to reduce the adhesive performance of the adhesive.

When using the adhesive of the present invention, the substrate to be bonded, such as metals such as aluminum (Aj), steel, PvC
The adhesive of the present invention may be applied to plastics such as, and after drying, heat and pressure may be applied to bond the base materials together. The amount of adhesive to be applied to the above substrate varies depending on the type of substrate to be applied, etc., but is usually 5 to 100. ! It may be applied at a rate of il/m2. As the coating method, any conventionally known method can be employed. Examples include a dipping method, a coating method, a roll coating method, and a spray method. Further, as a drying method, normal temperature drying, heating drying, etc. can be adopted. The conditions for the heat and pressure treatment after drying are preferably 80 to 250°C and approximately 0.1 to 10 Yu/mouth 2.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Examples 1 to 7 Adhesives were prepared according to the formulations shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 12 Adhesives were prepared according to the formulations shown in Table 1, and the same tests as in Examples were conducted.

Raw material resin A-H in Table 1 A: Vinyl chloride-vinyl acetate-2 acid phosphooxyethyl acrylate phosphate group I
According to the method described in No. 12675.

B: Vinyl chloride-vinyl acetate-2-acid phosphooxyethyl methacrylate phosphate group I X 10-' mol/11. Unexamined Japanese Patent Publication 1986-
According to the method described in No. 112675.

C: Vinyl chloride-vinyl acetate-2 acid phosphooxypropyl acrylate phosphate group IX 10-3 mol/g, JP-A-63-1
According to the method described in No. 12675.

D: Vinyl chloride-vinyl acetate-carbodacyl maleate group 2 X 10-4 mol/g, UCC'■ UCARVMCH E: Ethylene-vinyl acetate-carbon oxide 66/24/1
0 (weight ratio), melt 70-rate MFR35, Mitsui DuPont Chemical Elvaloy 741 F: Alicyclic petroleum resin softening temperature 100°C, Arayo Forestry Chemical Industry ■, Alcon M-
100G Niacrylic Resin Mitsubishi Rayon ■, Dianal BR Resin BR-106H: Acrylonitrile Loop Kuji. En 33/67 (weight ratio), B, F, Gcod Rich
.

(Test 1) Az/Az (hard AI foil with a thickness of 20 μm) was used as the base material, and adhesive was applied to these base materials (25 mm x 125 mm) for 16 minutes. ! It was applied at a ratio of i'/m and dried at 180°C for 10 seconds. The base materials coated with the adhesive were then glued together and pressed together at 180°C and 2#/cm2 for 1 second. Adhesive peel adhesion strength test method (J-Ks K-
6854), the T-peel strength was determined.

(Test 2) The same base material as in Test 1 was used, and after bonding under the same conditions, the test piece was left in a constant temperature and humidity chamber at 50° C. and 80% RH for 120 hours. Using this test piece, the T-peel strength was determined in the same manner as Test 1.

(Test 6) As the base material, AI (thickness 20 mm, czm hard M foil) /
P'VC (non-plasticized PVC sheet with a thickness of 0.3 mm) was used. Adhesion was performed under the same conditions as Test 1, and the T-peel strength was determined.

(Test 4) Using steel plates/steel plates (thickness 1.8 PCC-8D) as the base materials, adhesive was applied to these base materials (25+u x 12.5 cranes) at a rate of 40 g/m'', After drying at 80℃ for 5 minutes, the base materials were combined and dried at 100℃ for 1k.
Pressure bonding was carried out at g/cm2 for 5 minutes. The tensile shear strength was determined according to the method for testing tensile shear strength of adhesives (JK-SK-6850).

(Test 5) As the base material, steel plate (thickness 1 dragon, 5PCC-8D)/
Using ffC (thickness imm, soft PVC' sheet), 40g/r of adhesive was applied to these base materials (25cm x 125cm).
After coating at a ratio of n2 and drying at 80°C for 5 minutes, the substrates were brought together and pressed together at 100°G and 1 kg7cm2 for 5 minutes. The 180 degree peel strength was determined according to the adhesive peel strength test method.

〔Effect of the invention〕

The adhesive composition of the present invention has significantly superior adhesion performance for metal/metal, metal/plastic such as polyvinyl chloride, etc., compared to conventional solvent-based vinyl chloride adhesives, and is therefore very useful.

Patent applicant Denki Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] Contains a vinyl chloride copolymer having phosphoric acid groups of 1, 1 x 10^-^6 to 5 x 10^-^4 mol/g, an ethylene-vinyl acetate copolymer, an adhesive resin, and an organic solvent. adhesive composition.