JPH0721133B2 - Emulsion adhesive composition - Google Patents

Description

The present invention relates to a novel emulsion adhesive composition, and more particularly to an emulsion adhesive composition having excellent initial adhesiveness and adhesiveness after application.

(Prior art) Polished granite, tufted carpet, or polyvinyl chloride flooring is generally used as the flooring for concrete buildings. It is widely used as the mainstream of flooring materials because it is easy and the color and design can be freely selected. And among the polyvinyl chloride flooring materials, the so-called cushion floor, which is composed of a polyvinyl chloride foam layer and a soft polyvinyl chloride layer, is especially good because of its good foot feel and aesthetic appeal when walking. It has come to be prized.

Construction of flooring made of polyvinyl chloride usually requires the addition of a hydrocarbon resin emulsion as a tackifier to a conjugated diene rubber latex, a plasticizer such as process oil, and a filler such as calcium carbonate. If so, it is carried out by directly adhering a polyvinyl chloride flooring material to a concrete floor surface using an emulsion adhesive composition which also contains a dispersant, a defoaming agent, a preservative, a thickening agent and the like. .

However, the emulsion adhesive composition that has been conventionally used has the drawback that the adhesive force is not always sufficient.
Since it takes a long time to obtain the final adhesive strength,
For a while after the floor material was constructed, access to the construction site had to be restricted, which had the problem of affecting the execution of other construction.

On the other hand, in order to improve the adhesive strength, for example, addition of a hydrocarbon resin copolymerized with a C ₅ fraction and styrene as a resin component of an adhesive and an ethylenically unsaturated carboxylic acid or an anhydride thereof. Method using objects (Japanese Patent Publication No. 59-2697),
Methods such as reducing the amount of plasticizer in the adhesive have been proposed.

However, these methods do not provide sufficient initial adhesive strength. That is, the adhesive composition used in these methods lacks the ability to retain sufficient adhesiveness within a certain period of time until the flooring material is adhered after being applied to the concrete floor surface, and the adhesion of the flooring material is little. However, if it is delayed, there is a problem that the adhesion becomes insufficient and the expected adhesive force cannot be obtained. At this time, it is possible to increase the amount of plasticizer in order to improve the initial adhesive strength, but this time the adhesive strength becomes insufficient.

(Problems to be Solved by the Invention) An object of the present invention is to obtain an adhesive composition that is excellent in adhesive strength without impairing the initial adhesive strength and that exhibits a high adhesive strength after construction. The present inventors, as a result of earnest research,
It was found that the above object can be achieved by using a hydrocarbon resin obtained by polymerizing a monomer mixture having a specific composition as the resin component of the adhesive, and the present invention is completed based on this finding. Came to.

(Means for Solving the Problems) Thus, according to the present invention, (A) a conjugated diene rubber latex, (B) as a tackifier, (A) 30 to 85% by weight of a cyclopentadiene monomer, (B) Compounding a hydrocarbon resin obtained by polymerizing a monomer mixture containing 5 to 40% by weight of an aromatic vinyl monomer and (c) 5 to 40% by weight of a chain conjugated diene monomer. An emulsion adhesive composition is provided.

The conjugated diene rubber latex used in the present invention is a latex of a rubber containing a unit derived from a conjugated diene monomer as a main constituent component, and specifically,
Latex of natural rubber, synthetic cis-1,4-polyisoprene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, etc. Is. These rubber latexes may be those directly synthesized by emulsion polymerization, or those obtained by inversion of the rubber obtained by solution polymerization. Among these rubber latexes, a natural rubber latex and a styrene-butadiene copolymer rubber latex having a bound styrene content obtained by emulsion polymerization of 20 to 70% by weight, preferably 30 to 60% by weight, are preferred among these rubber latexes. It

Next, the hydrocarbon resin used as the tackifier in the present invention includes (a) 30 to 85% by weight of a cyclopentadiene monomer, (b) 5 to 40% of an aromatic vinyl monomer, and (c) It is a hydrocarbon resin obtained by polymerizing a monomer mixture containing 5 to 40% by weight of a chain conjugated diene monomer.

The cyclopentadiene-based monomer used in the present invention is cyclopentadiene or a derivative thereof, and specific examples thereof include cyclopentadiene; substituted cyclopentadiene such as methylcyclopentadiene; dimers and codimers thereof. ; And mixtures thereof.

The content of the cyclopentadiene-based monomer in the monomer mixture used in the present invention is 30 to 85% by weight, preferably
40 to 70% by weight. If this content exceeds the upper limit, the softening point of the resin excessively increases, the initial adhesive strength of the emulsion adhesive composition becomes insufficient, and the adhesive strength also becomes low. On the other hand, if the amount is less than the lower limit, the production rate of the resin is significantly lowered and the softening point of the resin is remarkably lowered (this tendency is remarkable in the thermal polymerization), which is sufficient when the resin emulsion adhesive composition is compounded. It is impossible to obtain good adhesive strength and peel strength.

The aromatic vinyl monomer used in the present invention is not particularly limited as long as it is an aromatic compound having a polymerizable vinyl group, and specific examples thereof include styrene and α.
Examples thereof include styrene derivatives such as -methylstyrene, β-methylstyrene and vinyltoluene, and indenes such as indene and methylindene.

In the present invention, the aromatic vinyl monomer may of course be used as a mixture of pure ones. For example, a mixture of benzene; an alkylbenzene such as toluene and xylene; a non-polymerizable aromatic hydrocarbon such as naphthalene; It may be used in the form. As an example of such a mixture, a so-called C9 fraction (a fraction having a boiling point range of 140 to 240 ° C. among cracked oil fractions obtained by thermal decomposition of petroleum) that is industrially easily available is shown. be able to.

The content of the aromatic vinyl monomer in the monomer mixture used in the present invention is 5 to 40%, preferably 10 to 35% by weight. If the content exceeds the above upper limit, the yield of the resin is remarkably lowered, and the hue of the resin is deteriorated, which often adversely affects the hue of the flooring material, which is not preferable. On the other hand, if it is less than the lower limit, the adhesive strength and peeling strength of the emulsion adhesive composition are impaired.

The chain conjugated diene-based monomer used in the present invention is
It is not particularly limited, and specific examples thereof include 1,
Mention may be made of 3-pentadiene, isoprene and 1,3-butadiene. In the present invention, the chain conjugated diene-based monomer does not have to be purified to a high degree of purity and may be used in the form of a hydrocarbon mixture containing other saturated hydrocarbon or unsaturated hydrocarbon.

In the present invention, the chain conjugated diene-based monomer exerts a remarkable effect in adjusting the molecular weight distribution of the resin and improving the initial adhesive strength of the emulsion adhesive composition without impairing the hue of the resin. The content in the monomer mixture used in the present invention is 5 to 40% by weight, preferably 10 to 30%.
It is necessary to be wt%. If this content exceeds the upper limit, the yield of the resin will be greatly reduced, and the softening point will be remarkably lowered, so that sufficient adhesive force cannot be imparted to the emulsion adhesive composition. On the contrary, below the lower limit,
The softening point of the resin excessively increases, the initial tack of the emulsion adhesive composition becomes insufficient, and the adhesive strength becomes low.

In the present invention, other polymerizable unsaturated hydrocarbons may be contained in the monomer mixture in a total amount of up to 20% by weight.

In the present invention, these monomer mixtures are usually prepared in the presence or absence of a known inert solvent such as benzene, toluene, xylene, tetralin, kerosene, etc.
A method of batch or continuous thermal polymerization at 0 to 300 ° C, preferably 230 to 280 ° C for 0.5 to 20 hours is adopted. Although it is also possible to use a chaos polymerization method, thermal polymerization is preferable from the viewpoint of post-treatment of polymerization and the like.
The target hydrocarbon resin is obtained by distilling off the saturated hydrocarbon component, the unreacted unsaturated hydrocarbon component and the by-produced low-volatile fraction in the reaction solution obtained by the polymerization reaction.

The hydrocarbon resin used in the present invention is usually processed into an emulsion and mixed with a conjugated diene rubber latex. The mixing ratio of the hydrocarbon resin is 20 to 5 with respect to 100 parts by weight of the rubber content in the conjugated diene rubber latex.
The amount is 00 parts by weight, preferably 40 to 350 parts by weight. If the mixing ratio is out of this range, an emulsion adhesive composition having sufficient adhesive performance cannot be obtained.

(Effect of the invention) The emulsion adhesive composition obtained by the present invention is
It has the advantages of excellent adhesive strength and rapid development of adhesive strength after construction.

(Example) Hereinafter, the present invention will be described more specifically with reference to Examples. In Examples, Comparative Examples and Reference Examples, parts and% are based on weight unless otherwise specified.

In this example, the resin yield is the ratio of the obtained resin weight to the total weight of the monomer mixture. The softening point of the resin was measured by the ring and ball method specified in JIS K-2531. Further, the hue of the resin was measured by ASTM D-1544-63T and displayed by Gardner chromaticity.

Reference Example 1 A monomer mixture (A to G) having the composition shown in Table 1 was charged in a pressure-resistant autoclave, thermally polymerized at 260 ° C for 3.5 hours in a nitrogen atmosphere, and then distilled under reduced pressure at 250 ° C and 5 mgHg. The unreacted monomer and the oily product were distilled off to obtain the corresponding hydrocarbon resins (A1 to G1). The yield and properties of the resin were measured, and the results are shown in Table 1.

Reference Example 2 After charging 100 parts of benzene and 1.2 parts of aluminum chloride in a pressure-resistant autoclave, the monomer mixture (H) having the composition shown in Table 1 was gradually added and polymerized at 65 ° C. The same post-treatment was performed to obtain a hydrocarbon resin (H1). The yield and properties of the resin were measured, and the results are shown in Table 1.

Example 1 The mixture obtained by adding 25 parts of mineral spirits and 20 parts of aroma oil (Fuji Aromax, Fuji Kosan Co., Ltd.) to 100 parts of each hydrocarbon resin (A1 to H1) fried in Table 1 Was dissolved by stirring. Next, 1.6 parts of a nonionic surfactant (Emulgen 913, Kao Co., Ltd.) was added with stirring,
200 parts of water was gradually added while continuing stirring to invert the phase, and then 100 parts of natural rubber latex containing 33 parts of rubber was added.
Parts and 450 parts of ground calcium carbonate are added, and an emulsion adhesive composition (A2-H
2) got.

3 m of the obtained emulsion adhesive composition is used with a comb iron.
Apply a certain amount on a m-thick slate plate, and after 5 minutes, thickness 2 mm, width
Floor material of 25 mm (Floor Rum, Toyo Linoleum Co., Ltd.)
After curing for a specified time in an atmosphere with an air temperature of 20 ° C and a relative humidity of 65%, a 90 ° peel test (pulling speed: 200m
m / min) to evaluate the adhesive strength. In addition, the slate plate coated with the emulsion adhesive composition should be
Thickness after leaving for 60 minutes in an atmosphere of ℃ and 65% relative humidity
2mm, 25mm wide floor material (same as above) is glued and immediately 1
An 80 ° peel test (pull speed 300 mm / min) was performed to evaluate the initial tack.

Furthermore, a floor material (the same as above) with a width of 2 mm and a width of 50 mm was immediately adhered to the slate plate coated with the emulsion adhesive composition, and this was cured for a predetermined time in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65%. 180 ° peeling test (pull speed 300 mm / min)
Was carried out to evaluate the peel strength.

The results are shown in Table 3.

Example 2 Styrene-butadiene copolymer latex as conjugated diene rubber component (bound styrene content 45%, gel content 30%)
Hydrocarbon resin A1 in the same manner as in Example 1 except that
~ Emulsion adhesive composition A3 corresponding to H1 ~
H3 was prepared and evaluated for adhesion, initial tack and peel strength. The results are shown in Table 4.

From Tables 3 and 4, the emulsion adhesive composition of the present invention is excellent in the expression of adhesive strength, while the hydrocarbon resin obtained from a monomer mixture containing no aromatic vinyl monomer. When using (emulsion adhesive composition E2 and
E3) has a large decrease in adhesive strength and peel strength, and particularly when styrene-butadiene copolymer latex is used as the rubber latex component of the emulsion adhesive composition (emulsion adhesive composition E3), the initial tack also decreases. In the case of using a hydrocarbon resin obtained from a monomer mixture containing no chain conjugated diene monomer (emulsion adhesive compositions F2 and F3), initial tack and peel strength are significantly reduced. That is, when a hydrocarbon resin obtained from a monomer mixture having a cyclopentadiene monomer content outside the range of the present invention is used (emulsion adhesive composition
It can be seen that also in G2 and G3), the adhesive strength and the peel strength are significantly reduced.

Claims (1)

[Claims] 1. A conjugated diene rubber latex (A), and (B) as a tackifier (B) a cyclopentadiene monomer 30 to 100 parts by weight of a rubber component in the conjugated diene rubber latex. ~ 85% by weight, (B) 5 to 40% by weight of aromatic vinyl monomer and (C) 5 to 40 of chain conjugated diene monomer
An emulsion adhesive composition comprising 20 to 500 parts by weight of a hydrocarbon resin obtained by polymerizing a monomer mixture containing 10% by weight.