HU199162B - Adhesive composition comprising polyolefin or pvc binding material with at least 61 percent by mass of chlorine - Google Patents

Abstract

The invention relates to a single-film-forming agent chlorinated polyolefin-containing adhesive for bonding hard and soft PVC and other substrates. The adhesive of the invention is characterized by having 100 parts by weight of solvent, 5-65 parts by weight, preferably 15-45 parts by weight, chlorinated polyolefin having a chlorine content of at least 50%, but preferably at least 60%, 0.02-0.15 parts heat stabilizer and optionally at most 45 parts filler , 10 parts by weight of plasticizer, 5 parts by weight of epoxidized ester and 20 parts by weight of adhesion-improving additives.

Description

FIELD OF THE INVENTION The present invention relates to adhesive compositions comprising at least 61% chlorine-containing chlorinated polyolefin or PVC film-forming adhesives, hard and softened PVC, and other substrates. The composition can also be used to make self-adhesive products.

Adhesive compositions containing chlorinated polyethylene (CPE) or chlorinated polypropylene (CPP) as an additional component are known.

Japanese Patent No. 77,44465 mentions CPE grafted with a vinylsilane derivative which is used together with butyl rubber as a crosslinkable adhesive.

Japanese Patent Application 78 01 993 discloses a composition of a similar composition but in a foamable embodiment.

U.S. Patent No. 1,002,333 mentions the use of a polyolefin having a chlorine content of up to 40% by weight.

U.S. Pat. No. 367,708 describes the use of a chlorinated polyolefin that is thermally vulcanized by the action of a catalyst mixed in the composition.

U.S. Pat. No. 4,263,419 discloses a two-component adhesive: one component is a mixture of CPE or chlorosulfonated polyethylene and a monomer which forms a compatible polymer and the other component is an activator which polymerizes the monomer after mixing.

The most commonly used adhesives for self-adhesive products are polyesters (as in French Patent No. 2,265,835), acrylates (as in British Patent No. 1,393,982), and various chlorine rubbers. Of these, polychloroprene is disclosed in U.S. Patent No. 3,951,722.

Said adhesives are thus reactive systems which, although capable of providing high strength adhesives, contain catalysts and other costly excipients, and, as is generally the case with reactive adhesives, are marketed in either two-component formulations which render their handling difficult or of limited shelf life.

In non-reactive systems, the chlorinated polyolefin is used in combination with other polymers or copolymers. Thus, U.S. Pat. No. 3,934,056 discloses that CPE with a chlorine content of 45% by weight and 200,000 molar mass is used to bond metal and wood in an ethylene / vinyl acetate (E / VAc) copolymer. In U.S. Patent No. 23,665,851, CPE is used in combination with PVC or a vinyl chloride / vinyl acetate (VC / VAc) copolymer for laminating thermoplastic sheets. U.S. Patent 4,055,698 proposes a solution of a mixture of CPP and E / VAc copolymer for priming polypropylene tape before bonding. German Patent Specification No. 23,64,806 describes the use of a medium molecular weight (20,000 to 200,000) CPE containing less than 50% chlorine by weight to supplement a PVC solution for bonding plastics and metals.

In the latter inventions, the chlorinated polyolefin is used only as a modifier in addition to polymers which are themselves film-forming and also known as adhesives; their admixture improves their adhesion to only some substrates, such as PVC, but does not allow technological (eg significantly pressure-resistant) adhesives.

It is an object of the present invention to provide adhesive compositions of chlorinated polyolefins or chlorinated PVC as the only film forming components suitable for hard and softened PVC as well as other substrates such as paper, wood, metals, rubber, leather, textile materials, other plastics. , as well as to meet the strength requirements for bonding concrete, gypsum and other masonry structures, with adequate durability (heat resistance, etc.) and for the production of self-adhesive products.

The polymer is readily soluble in all proportions of lacquer solvents or mixtures thereof, having a viscosity of 5 to 65% by weight on a dry basis, and is well compatible with additives that provide good adhesion and stability of the adhesive.

The adhesive composition of the invention comprises 100 parts by weight of organic solvent, 5 to 65 parts by weight of chlorinated polyolefin or chlorinated PVC containing at least 61% by weight, 0 to 45 parts by weight of filler, 0 to 10 parts by weight of an adhesive, 3 to 60 parts by weight of plasticizer. Contains 5 parts by weight of epoxidized soybean oil, 0.002 to 0.15 parts by weight of the heat stabilizer and 0 to 0.3 parts by weight of the light stabilizer.

Adjustment of the film-forming chlorine content within certain limits provides optimum adhesive properties. In this way, an adhesive composition can be applied by any conventional method which, after application, adheres well to metals, wood, concrete, textiles, hard and softened PVC.

The solvent used in the composition is lacquer solvents in which the chlorinated polyolefin is completely soluble, such as ethyl acetate, butyl acetate, tetrahydrofuran, cyclohexanone, toluene.

Suitable plasticizers are additives which are not film-forming per se but which favorably modify the physico-mechanical properties of the films formed, in particular monomeric esters containing longer chains, chlorinated hydrocarbons (waxes).

Phthalic acid esters (e.g., dioctyl phthalate), chlorinated paraffins (e.g., Cereclor) may be used, preferably in a maximum amount of 3 to 10 parts by weight of stone.

It is not advisable to use less than 3 parts by weight because the mechanical properties of the adhesive are thus inadequate.

Suitable fillers are silicate-type mineral product (eg quartz flour), carbonate (calcium carbonate). The amount of filler should preferably not be greater than 45 parts by weight, as this will not provide sufficient adhesive strength.

Low molecular weight resins which, as such, have no film-forming properties, but which improve both the cohesion of the composition and its adhesion to various surfaces, may be used as adhesion enhancing additives. Pine resin (e.g., rosin) may be used.

Preferably, the amount of adhesive additive should not be greater than 10 parts by weight, as this will result in insufficient compatibility.

As a stabilizer, additives are used which increase the thermal, thermo-oxidative stability of the adhesive. Preferably, tin or cadmium salts, optionally epoxidized oils, are used as heat stabilizers.

The following examples illustrate the composition of the invention and its preparation.

Example 1

35 parts by weight of 70,000 molar chlorinated polyethylene (CPE), 4 parts by weight of dioctyl phthalate (DOP), 1 part by weight of epoxidized soybean oil (epoxy equivalent 258, Reoplast 39, Advence, N, N) are dissolved in 100 parts of ethyl acetate or toluene. 1 part by weight of di (n-octyl) tin bis (isooctyl thioglycolate) (Ongrostab OS8T, BVK, Hungary) and stirring for 5 minutes at 1000 rpm to obtain a homogeneous adhesive composition having a viscosity (MSZ 8650 / 3)

Measuring cup 4 at 20 ° C: 112s.

Adhesives adhered by a thin layer of brush or knife applied to both surfaces to be glued after an open time of 3-5 minutes, after 24 hours, meet the following ratings:

a) Bonding of softened PVC to concrete

PVC flooring ("Hungelastik, manufactured by Hungária Plastics Processing Company):

Shear tensile strength (MSZ 7481 / 2-82)> 6.25 N / cm ²

Peel strength (MSZ 7482 / 5-68) 28.4 N / cm ²

After aging according to MSZ 7481/2-S2:

Shear tensile strength> 6.25 N / cm ²

Slope strength 32.2 N / cm

Roofing foil (manufactured by Hungária Plastics Processing Company)

Shear tensile strength> 6.25 N / cm ² Peel strength after 15.0 N / cm aging:

Shear tensile strength> 6.25 N / cm ²

Peel strength 16.1 N / cm

b) Bonding mosaic parquet to concrete I

Shear tensile strength 162 N / cm ²

After Aging 34-72:

Shear tensile strength 155 N / cm ²

c) Bonding paper wallpaper to concrete

Shear tensile strength (EMISZ 269-69)> 0.3 N / cm ²

Adhesion at Perpendicular Cutting (MSZ 9640 / 30-75):

“A layer of paper remains on the concrete

After aging according to ÉMISZ 269-69: the above parameters are unchanged.

d) Gluing wood with wood (Beech lumber) 20 Shear tensile strength (MSZ 7481 / 2-82) 184 N / cm ²

After Aging 34-72:

Shear and tensile strength 180 N / cm

Example 2

All proceed as in Example 1, except that instead of 35 parts by weight, 55 parts by weight of Example 1 CPE is used and 5 parts by weight of rosin resins are added.

The composition has a viscosity of MSZ 9650/3. s. standard (drain time from measuring cup 4 at 20 ° C): 145 s.

Adhesives are rated as follows:

a) Bonding of softened PVC to concrete:

PVC floor

Shear tensile strength (MSZ 7481/2)> 6.5 N / cm ²

Peel strength (MSZ 7482/5) 42 N / cm

After aging according to MSZ 7481/2: the above parameters are unchanged.

Roof insulation film ⁴⁵ Shear tensile strength (MSZ 7481/2)> 6.5 N / cm ²

Peeling strength (MSZ 7482/5) 20 N / cm

After aging according to 5q MSZ 7481/2:

Shear tensile strength> 6.5 N / cm ² Peel strength 18 N / cm

b) Bonding mosaic parquet to concrete:

₅₅ Shear tensile strength (MSZ 7481/2) 185 N / cm ²

After Aging 34-72 NSA: Tensile strength 180 N / cm ²

- (c) Bonding paper wallpaper to concrete:

Shear tensile strength (EMISZ 269-69)> 0.3 N / cm ²

Adhesion at Perpendicular Tear (MSZ 9640/30) "leaves a layer of paper on the concrete after aging according to ÉMISZ 269-69:

the above parameters are unchanged.

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d) Bonding wood to wood:

Shear tensile strength (MSZ 7481/2) 215 N / cm ²

After aging according to EMISZ 34-72:

Shear tensile strength 210 N / cm ²

Example 3

In 100 parts by volume of solvent mixture (60 parts by weight cyclohexanone + 35 parts by weight tetrahydrofuran - (- 5 parts xylene) 25 parts by weight 80,000 molar 66% chlorine CPE, 0.1 parts Reoplast 39et and 0.1 Ongrostab OS 8T- The viscosity of the composition according to MSZ 9650/3 is 265 s. The product is primarily suitable for gluing hard PVC: the surfaces to be glued are matted with abrasive paper and then washed with trichlorethylene or carbon tetrachloride twice, one after the other. The surface is etched with a drying time of 15 to 15 minutes and finally with a THF brush, before the adhesive is completely dried, the adhesive is applied and the surfaces are bonded together immediately Standard fittings are designed to pinch the surfaces by pinching them together. The bonding strength is 24 hours r under formation.

Adhesives are rated as follows:

a) Flat sheets (hard PVC)

Tensile shear strength (MSZ 7481/2) 400-800 N / cm ² depending on plate composition

b) Pipes (hard-PVC water pipe)

Hydrostatic pressure test (homemade, measured by water pump): maintained at 3 MPa for 15 minutes and then increased to fracture. The fracture occurred at a pressure of 9.5 to 10 MPa, where the PVC pipe cracked or opened and the adhesive remained intact.

Example 4

Each was prepared as in Example 1, except that 35 parts by weight of chlorinated polyethylene (CPE) instead of 35 parts by weight of 64% chlorine, 25 parts by weight of chlorinated polyethylene 62 parts by weight, 15 parts by weight of calcium carbonate (OMYA, Plush-Stauffer AG) and mixing 25 parts by weight of quartz flour with the solvent and homogenizing the additives with 2,000 rpm for 5 minutes with vigorous stirring.

The composition has a viscosity of MSZ 9650/3. s. standard (outflow time from 6-gauge glass at 20 ° C) 155 s. Adhesives adhered by brushing in a thin layer on both surfaces to be glued after an open time of 2 to 4 minutes, after 24 hours, meet the following ratings.

(a) Bonding mosaic parquet to concrete (Fig. B)

200 quality) 212 N / m ² shear-tensile strength after aging according to ES 34-72

Shear and tensile strength (MSZ 7481/2) 194 N / m ²

b) Gluing a wooden board with a wooden board (beech timber)

Shear and tensile strength (MSZ 7481/2)

282 N / m ² after aging according to 34-72 NSA

Shear and tensile strength (MSZ 7481/2)

Example 5 (Comparative)

All were carried out as in Example 1, except that 42% chlorinated polyethylene was used instead of 64% chlorinated polyethylene. We try to glue a soft PVC floor to concrete, and after 24 and 48 hours the layers do not stick together and can be pulled apart.

Example 6 (Comparative)

In each case, the procedure of Example 2 was followed except that 25 parts by weight of rosin resin were used instead of 5 parts by weight of rosin. The composition has a viscosity of MSZ 8650/3. s. standard (drain time from measuring cup 4 at 20 ° C): 175 s.

Adhesives are rated as follows:

a) Bonding of softened PVC to concrete

PVC floor

Shear tensile strength (MSZ 7481/2) <6.5 N / cm ²

Peel strength (MSZ 7482/5) 3 N / cm ²

After aging according to MSZ 7481/2

Shear tensile strength (MSZ 7481/2) 3.2 N / cm ²

Peel strength (MSZ 7482/5) 1.0 N / cm ²

b) Bonding mosaic parquet to concrete

Shear tensile strength (MSZ 7481/2) 31 N / cm ²

34-72 after aging

Shear tensile strength (MSZ 7481/2) 20 N / cm ² .

It is apparent from the above data that an increase in the amount of adhering rosin over a given range causes a deterioration of the strength properties.

Example 7 (Comparative)

All proceed as in Example 4 but using 25 parts by weight instead of 15 parts by weight of calcium carbonate and 30 parts by weight instead of 25 parts by weight of quartz flour.

The bonding experiments are repeated in the same way.

-4199162

a) Bonding mosaic parquet to concrete Shear tensile strength (MSZ 7481/2) 32 N / m ²

After aging according to ESZ 34-72 Shear tensile strength (MSZ 7481/2) 20 N / m ²

b) Bonding of wooden boards to wooden boards Shear tensile strength (MSZ 7481/2) 38 N / m ²

After aging according to ESZ 34-72 Shear tensile strength (MSZ 8481/2) 22 N / m ²

From the above data, it is apparent that increasing the amount of filler above a given limit impairs the strength properties.

Example 8

In 100 parts by weight of solvent mixture (10 parts by weight cyclohexanone + 40 parts by weight tetrahydro-Jurane + 20 parts by weight ethyl acetate + 30 parts by weight butyl acetate) 15 parts by weight of 65,000 molar weight 68% chlorinated polyethylene (CPE), 4 parts by weight chlorine S 52, ICI, England), 1 part by weight of epoxidized soybean oil (Reoplast 39, Advence, Germany), 0.05 di- (isooctoxycarbonylmethanethiolate) -di (-n-octyl) -one (Irgastab 17, Ciba) -Geigy, Switzerland), and the mixture was stirred for 2 minutes at 1500 rpm. This gives a homogeneous, colorless, transparent adhesive composition having a viscosity (MSZ 9650/3) in a 4-gauge glass at 20 ° C: 45 seconds.

The composition is particularly suitable for spray application due to its low viscosity.

Spray the composition onto both surfaces to be glued and then, after drying for 30 minutes, glue the two surfaces together by hand pressure.

Adhesives are rated as follows:

a) Bonding hard PVC board to wood

Shear and tensile strength (MSZ 7481/2) 285 N / cm ²

b) Bonding of ceramic tiles to concrete (B 200) 195 N / cm ² (breaking of concrete)

c) Bonding hard polystyrene foam to wood

Shear and tensile strength (MSZ 7481/2) 18 N / cm ²

d) Bonding softened PVC to a steel plate

PVC floor shear tensile strength (MSZ 7481/2) <6.5 N / cm ²

Peeling strength (MSZ 7482/5) 31 N / cm ²

Roof insulation foil:

Shear tensile strength (MSZ 7481/2) <6.5 N / cm ²

Peeling strength (MSZ 7482/5) 25 N / cm ²

e) Bonding cotton fabric to concrete Peeling strength (MSZ 7482/5) 28 N / cm ²

f) Bonding wallpaper to aluminum Shear tensile strength (EMISZ 269-69)

When perpendicular tearing off adhesion (MSZ 9640/3 0) <0.003 N / cm ^{2 of} paper remains on the aluminum

Example 9

In 100 parts by weight solvent mixture (30 parts by weight cyclohexanone, 40 parts by weight toluene, 20 parts by weight ethyl acetate, 10 parts by weight butyl acetate) 50 parts by weight of 80,000 molar weight, 65% by weight chlorinated polypropylene (CPP), 8 parts by weight of chlorinated paraffin ), 2 parts by weight epoxidized soybean oil (Reoplast 39), 0.10 parts by weight Irgastab 17, 20 parts by weight quartz flour. The mixture was stirred for 2 minutes at 2000 rpm.

This gives a homogeneous, lump-free adhesive composition having a viscosity (MSZ 9650/3) of 8 in a measuring cup at 20 ° C: 122 s.

Because of its high viscosity, the composition is particularly suited for application with a lubricating pad.

Apply the composition to both surfaces to be glued, and after 90 minutes drying, glue the two surfaces by hand pressure.

Adhesives are rated as follows:

a) Bonding of artificial leather to gypsum Peeling strength (MSZ 7482/5) 28 N / cm ₂

b) Bonding mosaic parquet to concrete

Shear and tensile strength (MSZ 7481/2)

After Aging 34-72 NSA 422 N / cm ² Shear tensile strength (MSZ 7481/2) 395 N / cm ²

Example 10

100 parts by weight of ethyl acetate are dissolved in 60 parts by weight of 64% by weight chlorinated polyethylene (CPE), 50 parts by weight of dioctyl phthalate (DOP), 0.15 parts by weight of Ongrostab OS 8T ', (di (n-octyl) bis (flavor octyl thioglycolate), product of Borsodi Chemical Plant) and 0.5 parts of epoxy ₅ g of song soybean oil (epoxy equivalent 258, Reoplast 39, Advence, Germany) and stirring at 1000 rpm for 2 minutes. This produces a homogeneous adhesive composition having a viscosity (MSZ 8650/3)

5θ) with 4 measuring cups at 20 ° C: 143 s. The resulting adhesive can be applied to the back of the PVC floor covering {smeared, 20-50 minutes after drying (depending on temperature, ventilation), and can be laid down at any later time with an instant adhesive covering with shear-tensile strength (MSZ 7481 / 2-82

-5199162): 4.25 N / cm ² , and the limit remains unchanged after aging according to MSZ 7481 / 2-82.

Example 11

In the same manner as in Example 10, 35 parts by weight of 70,000 molar chlorinated polyethylene, 35 parts by weight of 64% chlorine, 35 parts by weight of dioctyl phthalate and 0.05 parts by weight of Ongrostab OS 8T stabilizer are dissolved in 100 parts of butyl acetate. The homogeneous solution is applied in a uniform layer to one surface of the aluminum foil, and after drying for 8 days at room temperature, a solvent-free, self-adhesive film can be applied to the various surfaces by loose pressure. Flammability class according to MSZ 10383-80: HB. Peeling strength according to MSZ 7482 / 5-68:

After freshly aged at 60 ° C for 200 hours, cardboard paper 4.8 N / cm 4.5 N / cm soft PVC 6.8 N / cm 6.9 N / cm aluminum 3.9 N / cm 3.5 N / cm

-12. example

All in all. The procedure is as in Example 1, except that 35 parts by weight of Celeclor 52 (manufactured by ICI, GB) and 120,000 molar chlorinated paraffin are added to 35 parts by weight of dioctyl phthalate. The self-adhesive aluminum thus obtained has a degree of flammability according to MSZ 10383-80: VO. Peeling strength according to MSZ 7482 / 5-68:

Freshly 60 ° C 200 hours paperboard on soft PVC after aluminum oregiting

4.5 N / cm 7.3 N / cm

3.5 N / cm

4.2 N / cm 6.9 N / cm

3.2 N / cm

Example 13

Dissolve 30 parts of 63% by weight of chlorinated 40,000 molar PVC, 40 parts of Cereclor S52 chlorinated paraffin, 0.5 parts of Ongrostab OS 8T stabilizer and 1 part of Reoplast 39 epoxidized soybean oil in 100 parts of butyl acetate and stir for 500 minutes / turn. minutes intensity. 5 parts by weight of CaCO ₃ precipitate filler were distributed in a homogeneous solution at an even rate of 2000 rpm. A homogeneous adhesive composition having a viscosity (according to MSZ 8650/3) is thus obtained.

Measuring cup 4 at 20 ° C: 105 s.

The resulting composition is applied evenly to the back of the PVC floor covering. After drying for 24 hours, the flooring foil can be stored in a roll-up, easy-to-unwind, ready-to-lay at any later time. Shear tensile strength on concrete as measured by MSZ 7481 / 2-82: <6.25 N / cm ² .

Example 14 (Comparative)

One proceeds according to Example 10 is ₁₅ except in that a chlorinated polyethylene containing 42% by weight instead of 64 parts of chlorine / chlorine-containing aqueous chlorinated polyethylene. After 24 hours, the chlorinated polyethylene was not dissolved and thus no adhesive composition could be prepared.

EXAMPLE 15 (Comparative) All of Example 13 was repeated except that 100 parts by weight were used instead of 5 parts by weight of calcium carbonate.

The resulting composition is applied in a uniform coat to the back of the PVC floor covering. After 24 hours' drying the coating ₃₀ is flattened against a watchman Β-200 concrete surface. Shear tensile strength on concrete (measured according to MSZ 7481 // 2-82: 1.12 N / cm ²⁾ .

Claims (2)

1. Chlorinated polyolefin or chlorinated PVC with 3 to 60 parts by weight of plasticizer, 0.1 to 5 parts by weight of epoxidized soybean oil, 0.02 to 0.15 parts by weight of heat stabilizer, 0 to 45 parts by weight of filler, 0 to 10 parts by weight of adhesive, 0- An adhesive composition containing 0.3 parts by weight of a light stabilizer, characterized in that it contains from 5 to 65 parts by weight of a chlorinated polyolefin or chlorinated PVC containing 100 to ⁴⁵ parts by weight of an organic solvent as a film-forming agent. Composition according to claim 1, characterized in that it is 61 to 68% by weight of chlorine as chlorinated polyolefin. Contains chlorinated polyethylene.