JPH0747723B2 - Adhesive composition for polyvinyl chloride - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an adhesive composition for polyvinyl chloride, and more particularly to a novel room temperature curing two-part type epoxy resin composition which is excellent in initial adhesion and flexibility. It relates to an adhesive composition.

II Conventional Technology Conventionally, nitrile rubber-based adhesives, urethane resin-based adhesives, and epoxy resin-based adhesives have been widely used as adhesives for polyvinyl chloride.

Nitrile rubber adhesives have poor alkali resistance and water resistance,
Further, the urethane resin-based adhesive has a drawback that it has poor alkali resistance, storage stability and initial tackiness.

Epoxy resin adhesives can be used for metal, wood, concrete,
Although it adheres well to adherends such as mortar and the like, it does not adhere well to polyvinyl chloride, and when using an epoxy resin adhesive, the adhesive surface of the polyvinyl chloride sheet should be pre-coated with a primer. Had to handle. In addition, the epoxy resin adhesive has poor initial adhesiveness, and it is difficult to press it onto concrete etc. until the adhesive is hardened after the polyvinyl chloride sheet is bonded to concrete etc. It was desired that the initial adhesiveness to be adhered to the adherend be applied even if it is not used.

In addition, since the cured product is hard and inferior in elasticity, for example, when a polyvinyl chloride sheet is adhered to concrete or the like, when the concrete cracks, the adhesive cannot follow this change, and the polyvinyl chloride sheet However, there is a drawback in that it is easy to break.

III Object of the Invention The object of the present invention is to provide a novel polychlorinated product which has excellent initial adhesion between polyvinyl chloride and an adherend, good water and alkali resistance, and excellent adhesiveness and flexibility of a cured product. An attempt is made to provide an adhesive composition for vinyl.

IV Specific Configuration of the Invention The present invention comprises, with respect to 100 parts by weight of a urethane-modified epoxy resin, 20 to 80 parts by weight of epoxidized natural rubber, 20 to 80 parts by weight of an adhesiveness imparting polymer for polyvinyl chloride, and a curing agent. Provided is an adhesive composition for polyvinyl chloride containing the same.

The constitution of the present invention will be described in detail below.

(1) Urethane-modified epoxy resin The urethane-modified epoxy resin used in the present invention comprises (a) a compound having an epoxy group and a hydroxyl group, and (b)
It is obtained by reacting a urethane bond-containing compound containing an isocyanate group at the terminal obtained from a polyhydroxyl compound and a polyisocyanate compound.

(A) The compound containing an epoxy group and a hydroxyl group is a compound having 1 to 3 epoxy groups and 1 to 2 hydroxyl groups in the molecule, and preferably a compound having a molecular weight of 70 to 2000. Examples thereof include glycidyl ethers of polyhydric alcohols such as glycidol, ethylene glycol monoglycidyl ether, and glycerin diglycidyl ether, and commercially available epoxy resins having a hydroxyl group.

(B) The urethane bond-containing compound having a terminal isocyanate group is produced by the reaction of (b-1) a polyhydroxyl compound and (b-2) a polyisocyanate compound.

(B-1) Examples of the polyhydroxyl compound include various polyester polyols or polyether polyols used in the production of general urethane compounds.

Examples of the polyester polyol here include a condensate of a polyhydric alcohol and a polybasic carboxylic acid, a condensate of a hydroxycarboxylic acid and a polyhydric alcohol, and the polyhydric alcohol used in these includes, for example, ethylene. Glycol, propylene glycol, butanediol,
Examples include diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and the like, examples of polybasic carboxylic acids include adipic acid, glutaric acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid, dimer acid, and pyromellitic acid. Acid etc. are mentioned.

As the condensate of hydroxycarboxylic acid and polyhydric alcohol, castor oil, castor oil and ethylene glycol,
Reaction products such as propylene glycol are also useful.

Examples of the polyether polyol include ethylene oxide, propylene oxide, butylene oxide,
It is a product obtained by addition-polymerizing one or more alkylene oxides such as tetrahydrofuran with a compound having two or more active hydrogens, and any known polyether polyol used in the production of ordinary polyurethane resins is used. I can. In this case, examples of the compound having two or more active hydrogens include the above-mentioned polyhydric alcohol, polybasic carboxylic acid, ethylenediamine,
Examples thereof include amines such as hexamethylenediamine, alkanolamines such as ethanolamine and propanolamine, polyhydric phenols such as resorcinol and bisphenol, and castor oil.

(B-2) The polyisocyanate compound used in the production of the urethane bond-containing compound having an isocyanate group at the terminal is a compound having two or more isocyanate groups in the molecule and is used in the production of ordinary polyurethane resins. Various compounds can be used, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and triphenylmethane triisocyanate.

The urethane-modified epoxy resin used in the present invention is preferably produced as described below using the above (a), (b-1) and (b-2).

The urethane bond-containing compound having an isocyanate group at the terminal can be obtained by reacting a polyhydroxyl compound and a polyisocyanate compound in the same manner as in the usual method for producing an isocyanate group-containing urethane prepolymer.

The urethane-modified epoxy resin used in the present invention can be obtained by reacting the urethane bond-containing compound having an isocyanate group at the terminal with the epoxy group and hydroxyl group by a conventional method.

(2) Epoxidized Natural Rubber The epoxidized natural rubber used in the present invention is an epoxidized product by oxidizing a part of the double bond of natural rubber latex.

For the oxidation, for example, peracetic acid and the like are commercially available, but these may be used.

Such an epoxidized natural rubber can be compatible with an epoxy resin, and when mixed with the epoxy resin, imparts excellent tackiness to the epoxy resin composition and improves the initial adhesion of the composition.

The epoxidation rate of the natural rubber used in the present invention by oxidation is
20% or more of the double bonds present in natural rubber, preferably 30
It is better to set it to% or more.

This is because if it is less than 20%, the compatibility with the epoxy resin is poor and the tackiness is rather reduced.

The compounding amount of the epoxidized natural rubber is preferably in the range of 20 to 80 parts by weight, and preferably 30 to 70 parts by weight, based on 100 parts by weight of the urethane-modified epoxy resin.

If the epoxidized natural rubber is less than 20 parts by weight, the initial adhesiveness of the composition of the present invention will be insufficient, and if it exceeds 80 parts by weight, the viscosity of the composition itself will be high and the workability will be poor.

(3) Adhesion-imparting polymer for polyvinyl chloride The adhesion-imparting polymer for polyvinyl chloride used in the present invention may be any as long as it has a solubility parameter similar to that of the epoxy resin, but is preferably a thermoplastic urethane resin. , Vinyl chloride-vinyl acetate copolymer, acrylic resin type, NBR, NBR modified product, PVC-NBR blend polymer and the like are used.

The blending amount of the adhesion-imparting polymer for polyvinyl chloride is 20 parts with respect to 100 parts by weight of the urethane-modified epoxy resin.
-80 parts by weight, preferably 30-70 parts by weight.

If it is less than 20 parts by weight, the adhesiveness of the cured product will be insufficient. If it is more than 80 parts by weight, the effect is not particularly improved even if the amount is more than that, and the water resistance and alkali resistance are deteriorated.

(4) Hardener As the hardener used in the present invention, a general room temperature, two-part type hardener for epoxy resin can be used.

For example, aliphatic polyamines, aromatic polyamines, modified aliphatic polyamines, polyamidoamines, various mercaptan-based curing agents, liquid NBR having terminal amino groups, acid anhydrides, latent curing agents, tertiary amines, etc. One kind or two or more kinds are used.

The amount of the curing agent used is not particularly limited, but is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the urethane-modified epoxy resin.

In the present invention, various additives and the like can be added as necessary in addition to the above-mentioned essential components.

For example, solvents, tackifiers, anti-sagging agents, fillers, curing accelerators, pigments, adhesion promoters, defoamers, leveling agents, polymerization agents, rubbers, plasticizers, heat aging inhibitors, and other additives. is there.

As the solvent, xylene, toluene, methyl ethyl ketone and the like, as the tackifier, petroleum resin-based and natural product-based tackifiers, and as the filler, silica, talc, calcium carbonate, clay, calcium silicate and the like. Can be preferably used.

The composition of the present invention may be produced as a two-component type containing only one of a urethane-modified epoxy resin and a curing agent,
Preferably, the epoxidized natural rubber and the solvent are kneaded with a mixer, and then the urethane-modified epoxy resin, the adhesion-imparting polymer, the filler and the like are kneaded as a main component, while the epoxy curing agent and the solvent, the filler and the like are kneaded. As the curing agent, a two-component room temperature curing type adhesive composition may be used.

The adhesive composition of the present invention, polyvinyl chloride as one adherend, any may be used as the other adherend, concrete, mortar slate, metal such as iron,
Good adhesion to wood and plastics such as polyvinyl chloride.

V Example Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In Examples and Comparative Examples, compositions were prepared using the compounding agents and the compounding parts shown in Table 1.

In the examples, the epoxidized natural rubber was masticated with a roll, dissolved in toluene, and then a urethane-modified epoxy resin, a polyvinyl chloride adhesion-imparting polymer and other predetermined raw materials were added and mixed to prepare a liquid A.

Liquid A of Comparative Example was obtained in the same manner as in Examples, with the formulations shown in Table 1.

The liquid B was obtained by adding a curing agent, a solvent, and other predetermined raw materials and mixing them.

Using a polyvinyl chloride sheet as the adherend to be bonded,
As an adherend for these, slate (JIS-A-540
3 flexible board) plate was used.

As shown in Fig. 1b, the polyvinyl chloride sheet 2 has a width of 25
A slate plate having a width of 50 mm, a length of 200 mm and a thickness of 4 mm was used.

The adhesive is obtained by mixing A liquid and B liquid, and is evenly applied on the surface of the slate plate 1 with a combing iron in the combing direction 4, and normal curing (20 ± 2 ° C, 60 ± 10% RH) 48 After a lapse of time, a test piece was prepared, and the following tests were conducted and evaluated. The results are shown in Table 1.

(1) Peel adhesion strength A 90 degree peel test was performed at a pulling speed of 200 mm / min to evaluate the normal adhesion strength.

For the alkali resistance, the test piece was immersed in a 0.1% sodium hydroxide aqueous solution for 48 hours, and a 90 degree peeling test was performed.

(2) Dynamic elastic modulus 20 ° C and -10 ° C, distortion rate 0.5%, frequency 10rad / s
It was measured by DMA (Dynamic Mechanical Analysis) under the condition of ec.

(3) Crack resistance As shown in Fig. 1a, a notch 6 was made in the center of the slate plate 1 surface of the test piece 10 with a metal saw to a depth of 3.5 mm, and the speed was 200 mm / in an atmosphere of -10 ° C. After the tensile load of min was applied, the slate plate 1 was ruptured, and then the presence of rupture of the sheet 2 was further observed when the tensile load was applied continuously for 50 mm between the chucks.

(4) Initial tackiness The polyvinyl chloride sheet 2 is similarly bonded to the slate plate 1 via the adhesive 3, and the test piece immediately after bonding which is not normally cured is subjected to a 90-degree peel test at a pulling speed of 200 mm / min and the initial test. The tackiness was evaluated.

Yes… 90 degree peel test 100g / 25mm or more No… 90 degree peel test less than 100g / 25mm (5) Application workability The workability at the time of applying the adhesive was evaluated.

◯: Viscosity was appropriate and coating work was well done.

X: The viscosity was high and the coating operation was difficult.

In addition, the oven assembly time at the time of bonding, that is, the time from the application of the adhesive to the deposition of the bonding surfaces together was 20 minutes in each of the examples.

VI Effects of the Invention Since the adhesive composition of the present invention contains a urethane-modified epoxy resin, an epoxidized natural rubber, and an adhesion-imparting polymer for polyvinyl chloride, it has the following effects.

(1) Excellent adhesion (2) Excellent flexibility (3) Good water resistance and alkali resistance (4) Excellent initial tackiness (5) Long working life (6) Oven assembly You can take a long time.

As described above, the adhesive composition of the present invention has an advantage that it is suitable for adhesives of soft, semi-rigid polyvinyl chloride and concrete, slate, mortar, wood, iron plate, etc. without treatment with a primer.

As an example of the present invention, it can be used as an adhesive for flexible polyvinyl chloride long floor materials for poolside and condominiums.

Others, tarpaulin, interior decoration, adhesive lining,
It can also be preferably used as an adhesive for non-slip of overpass.

[Brief description of drawings]

FIG. 1a is a sectional view of the test piece. FIG. 1b is a plan view of FIG. 1a. Explanation of symbols 1 ... Slate plate, 2 ... Sheet, 3 ... Adhesive, 4 ...
... comb direction, 5 ... tensile direction, 6 ... notch, 10 ... test piece

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-63-118388 (JP, A) JP-A-63-39975 (JP, A) JP-A-61-108680 (JP, A) JP-A-51- 17298 (JP, A) Japanese Patent Sho 51-10252 (JP, B1)

Claims (1)

[Claims] 1. A resin composition containing 20 to 80 parts by weight of epoxidized natural rubber, 20 to 80 parts by weight of an adhesiveness imparting polymer for polyvinyl chloride, and a curing agent, relative to 100 parts by weight of a urethane-modified epoxy resin. An adhesive composition for polyvinyl chloride.