JPH0326775A - Emulsion adhesive for vinyl chloride resin - Google Patents

Abstract

PURPOSE:To obtain the subject adhesive exhibiting excellent adhering force to flooring material of vinyl chloride resin without containing a large amount of rubbery substance containing an emulsion of copolymer containing specific ratio of methaorylonitrile component and conjugated diene component as a principal ingredient. CONSTITUTION:The aimed adhesive contains an emulsion of copolymer containing 10-75wt.%, preferably 15-45wt.% methacrylonitrile component and 90-25wt.%, preferably 85-55wt.% conjugated diene component (preferably butadiene or isoprene) as a principal ingredient. Besides, further 10-35wt.% vinyl aromatic compound component such as styrene, <=10wt.% alpha,beta-unsaturated carboxylic acid such as (meth)acrylic acid and 5-20wt.% acrylonitrile are preferably contained.

Description

[Detailed Description of the Invention] The present invention relates to an adhesive for vinyl chloride resin.
For example, it relates to an adhesive that can be suitably used for adhering vinyl chloride resin flooring.

In Jokudankyo-I, solvent-based adhesives such as vinyl acetate and epoxy resin-based adhesives and water-based adhesives such as emulsion-based adhesives are used as adhesives for vinyl chloride resin flooring.

Although solvent-based adhesives have relatively high adhesive strength, the organic solvent evaporates during application, which not only produces a bad odor, but also poses a risk of ignition and pollution of the working environment and air. However, residual solvent may cause the flooring to warp or bulge.

On the other hand, water-based adhesives do not have the above-mentioned problems, but they generally have low adhesion strength, especially low peel adhesion strength, and the flooring material may peel off after adhesion, as well as poor adhesion. Therefore, in order to improve initial performance such as adhesive strength,
Contains a large amount of rubber substances such as natural rubber. However, incorporating such a large amount of rubber material increases the manufacturing cost of the adhesive.

Already, the main ingredients are acrylonitrile and butadiene,
Alternatively, emulsions of copolymers containing acrylonitrile, bucdiene, styrene, and acrylic ester as main components, and in some cases, unsaturated acid components such as acrylic acid and methacrylic acid, and applications of such emulsions to adhesives. For example, Japanese Patent Publication No. 55-27567, Japanese Unexamined Patent Publication No. 145909/1982, Japanese Patent Publication No. 62-1976
This is known as described in Publication No. 4 and the like. Further, Japanese Patent Publication No. 8443/1983 describes the use of copolymer emulsions made of monomers such as acrylonitrile, butadiene, and styrene for coatings and carpet linings.

However, until now, no emulsion-based adhesive with excellent adhesive strength has been known for use with vinyl chloride resin, especially vinyl chloride resin flooring, and there is a strong demand for such an emulsion-based adhesive for vinyl chloride resin flooring. ing.

The present invention has been made in response to such demands, and has not only excellent adhesive strength but also high adhesive strength without the need for compounding a large amount of rubber material. The purpose of the present invention is to provide an emulsion-based adhesive for vinyl chloride resin that has excellent initial performance and oil resistance.

The emulsion adhesive for vinyl chloride resin according to the present invention for
It is characterized by containing as a main component an emulsion of a copolymer containing 10 to 75% by weight of a methacrylonitrile component and 90 to 25% by weight of a conjugated diene component.

The copolymer emulsion used in the present invention contains 10 to 75% by weight of a methacrylonitrile component and 90 to 25% by weight of a conjugated diene component, preferably 15 to 45% by weight of a methacrylonitrile component and a conjugated diene component. 85-5
Contains 5% by weight.

In the copolymer emulsion, when the monomer component contains less than 5% by weight of methacrylic nitrile, the resulting adhesive has poor adhesion to vinyl chloride resin, especially vinyl chloride resin flooring, On the other hand, if it exceeds 75% by weight, the resulting adhesive will not only have poor adhesion to vinyl chloride resin, especially vinyl chloride resin flooring materials, but also the emulsion will lose its rubber elasticity.
The resulting adhesive has poor adhesive strength and poor initial performance.

As the conjugated diene component, butadiene, isoprene, chloroprene, etc. are used, and butadiene or isoprene is particularly preferably used. In the copolymer emulsion, when the conjugated diene component exceeds 90% by weight, the resulting adhesive has poor adhesion to vinyl chloride resin, especially vinyl chloride resin flooring, and when it is less than 25% by weight, The resulting adhesive has poor initial performance.

In the present invention, the copolymer emulsion preferably contains a vinyl aromatic compound component in a range of 40% by weight or less, particularly 10 to 35% by weight, in addition to the methacrylate nitrile component and conjugated diene component. The content is preferably in the range of %.

Here, examples of the vinyl aromatic compound include styrene, methylstyrene, vinyltoluene, etc., and styrene is particularly preferably used.

Furthermore, in the present invention, modifying monomers such as α,β monounsaturated carboxylic acids and unsaturated amides can be added in order to improve mechanical stability, oil resistance, etc. This α
Examples of the 1β monounsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, etc., as well as those having a hydroxyl group such as 2-hydroxyethyl acrylic acid and 2-hydroxybutylopyrmethacrylic acid. can.

Examples of unsaturated amides include N-hydroxymethylacrylamide, acrylamide, and methacrylamide. All of these can be used in an amount of 10% by weight or less based on the total monomer.

In addition, in the present invention, in order to improve the oil resistance of the resulting adhesive, the copolymer contains 5 to 20% acrylonitrile.
It can be contained within a range of % by weight. In particular, 10-20% methacrylonitrile and 1% acrylonitrile
It is preferable to use it in a range of 0 to 20% by weight.

The copolymer emulsion used in the present invention is usually
It can be obtained by emulsion polymerization. Emulsion polymerization is carried out in accordance with a conventional method using an alkali metal salt of rosin acid, sodium dodecylbenzenesulfonate, etc. as an emulsifier, a persulfate such as potassium persulfate, a radical polymerization initiator, or a redox catalyst-based radical polymerization initiator, etc. as a polymerization initiator. Using an alkyl mercabutane such as t-dodecyl mercaptan as a molecular IL-preparing agent, the monomer components may be emulsion-polymerized in an aqueous medium, usually at a temperature of 0 to 100°C.

Polymerization is usually carried out until monomer conversion reaches 95-98%.

In the above emulsion polymerization, in order to make the particle size of the resulting emulsion uniform, a seed polymerization method may be performed in which a small amount of an aromatic vinyl compound, such as styrene, is previously emulsion polymerized and used as a seed. Furthermore, in addition to the batch charging method in which the monomer components are added to the polymerization system all at once, a split polymerization method in which the monomer components are divided and added to the polymerization system can also be used.

As described above, the adhesive according to the present invention is an aqueous adhesive mainly composed of a copolymer emulsion containing a methacrylic mononitrile component, a conjugated diene component, and preferably an aromatic vinyl compound component. An adhesive that has excellent adhesion to vinyl chloride resin, especially vinyl chloride resin flooring materials, without incorporating a large amount of rubber substances, and also has excellent initial performance and oil resistance. .

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 and Comparative Examples 1-4 II equipped with a thermometer and a stirrer! A volumetric autoclave was charged with 4 parts of sodium dodecylbenzenesulfonate and 0.8 parts of sodium persulfate along with 240 parts of deionized water;
Dissolved under stirring, and 56 parts of methacrylic nitrile,
136 parts of butadiene, 8 parts of methacrylic acid and 2 parts of t-dodecylbutane were added, heated to 60 DEG C., and reacted to obtain a copolymer emulsion.

Similarly, as Comparative Examples 1 to 3, as shown in Table 1, copolymer emulsions were prepared in the same manner as above except that acrylonitrile, methyl methacrylate, or styrene was used instead of methacrylic nitrile. Obtained.

Table 1 shows the polymerization rate, total solid content, and particle size of the monomers in the obtained emulsion.

(Test Example 1) Next, each of the copolymer emulsions thus obtained was uniformly mixed with fillers, tackifiers, thickeners, etc. in the weight parts ratios shown below, and an adhesive was prepared. Prepared.

Emulsion (solid content) 1001 Sodium lipolyphosphate 0.5 Calcium carbonate 180 Tackifier 1
80 thickener l') 4 (Note) a) Hi-Resin NO60 (Japan Petrochemical Industry @
) 70% toluene solution b) Aron A7100 (Aronized Industrial @) Adhesion test and initial performance test The adhesive thus obtained was applied to a slate board (
JIS A 5403) using a comb trowel to a width of 75 mm, and after 5 minutes of open time, place a vinyl chloride resin sheet (2.5 x 10 cm) on top of it and apply it with a roller for 3 minutes.
Reciprocating compression (linear pressure 2 kg/cm) was performed, and the initial performance was evaluated by touch. After 7 days, the 90° peel strength was measured at a tensile rate of 2001 l/min.

Oil resistance test The adhesive was applied to a thickness of 0.5 mm on a glass plate, 7 days later it was immersed in dioctyl phthalate, and after 5 days, the dioctyl phthalate resistance of the adhesive coating was visually and by touch. The oil resistance was evaluated.

As Comparative Example 4, an adhesive was similarly prepared using an acrylic emulsion, and its adhesion performance to a vinyl chloride resin sheet was evaluated.

The results are shown in Table 2.

Table 2 (Note) A means very good, B means good, C means slightly poor, and D means very poor.

(Test Example 2) An adhesive was prepared by uniformly mixing the emulsion of Example 1 with fillers, tackifiers, thickeners, etc. in the proportions by weight shown below.

Emulsion (solid content) 100 antifoaming agent 1
0.3 Calcium carbonate l80 Nonionic surfactant b) 3 Tackifier 0
74 Thickener'1
1. 3 (Note) a) Silicon KM
-71 (Shin-Etsu Chemical @) b) Emulgen 930 (Kao @) C) Hi-Resin NO60 (Japan Petrochemical Industry @) 70
% toluene solution d) Aron A7100 (Aron Kakai Kogyo@) The adhesive obtained in this way was used to adhere commercially available vinyl chloride resin flooring with an open time of 10 minutes, and after curing for 7 days, tensile strength was applied. The 90° peel strength was measured at a speed of 20 Qmm/min.

Moreover, adhesives were similarly prepared and evaluated using acrylic emulsions as Comparative Examples 5 to 8.

In addition, the emulsions of Comparative Examples 6 to 8 are commercially available products.

The results are shown in Table 3.

Table 3 (Note) 1) Kg/20w width 2) Kg/25m++ width Examples 2 to 6 and comparative example 9 1z equipped with a thermometer and stirrer in the same manner as in Example 1
A volumetric autoclave was charged with 6 parts of sodium dodecylbenzenesulfonate along with 240 parts of deionized water, dissolved under stirring, and added with 5 parts of butadiene as shown in Table 4.
0 parts, 45 parts by weight of styrene (and methacrylonitrile in total), 5 parts of methacrylic acid and 0.5 parts of t-dodecylmercabutane, 0 parts of cresyl hydroperoxide
．． 4 parts, and an aqueous solution of a mixture of Rongalit, iron sulfate and EDTA (Tetrasodium salt weight ratio of Rongalit/iron sulfate/EDTA 10/0.01/1, 50% aqueous solution)
0.8 part was added and reacted at 40°C to obtain a copolymer emulsion.

Table 4 shows the polymerization rate, total solid content, and particle size of the monomers in the obtained copolymer emulsion.

(Test Example 3) Next, using the copolymer emulsion thus obtained, an adhesive was prepared according to the same formulation as in Test Example 3.

Each adhesive thus obtained was applied to commercially available vinyl chloride resin flooring with an open time of 10 minutes, and after curing for 7 days, the 90' peel strength was measured at a tensile speed of 200 mm/min. did.

The results are shown in Table 5.

In Table 5, Example 1, methacrylonitrile 56f! 28 parts by weight of methacrylonitrile and 2 parts by weight of styrene
An emulsion was prepared in the same manner as in Example 1, except that 8 parts by weight was used, and an adhesive was prepared using the same formulation as in Test Example 1, and peel strength and oil resistance were evaluated. The results are shown in Table 6.

Table 6 Example 7 An emulsion was prepared in the same manner as in Example 1, except that 28 parts by weight of methacrylic nitrile and 28 parts by weight of acrylonitrile were used in place of 56 Ii parts of methacrylic nitrile in Example 1, Using this, an adhesive was prepared with the same formulation as in Test Example 1, and its peel strength and oil resistance were evaluated. The results are shown in Table 6.

Example 8

Claims (5)

[Claims] (1) An emulsion adhesive for vinyl chloride resin, which contains as a main component an emulsion of a copolymer containing 10 to 75% by weight of a methacrylonitrile component and 90 to 25% by weight of a conjugated diene component. (2) The copolymer contains 40% by weight of vinyl aromatic compound component.
The emulsion adhesive for vinyl chloride resin according to claim 1, characterized in that the adhesive is contained in the following range. (3) The copolymer contains 10 α,β-unsaturated carboxylic acid components.
The emulsion adhesive for vinyl chloride resin according to claim 1, characterized in that the content is within a range of % by weight or less. (4) The emulsion adhesive for vinyl chloride resin according to claim 3, wherein the α,β-unsaturated carboxylic acid is acrylic acid or methacrylic acid. (5) The emulsion adhesive for vinyl chloride resin according to claim 1, wherein the copolymer contains 5 to 20% by weight of an acrylonitrile component.