JPH0776333B2 - Adhesive for flooring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a composition having the functions of an adhesive and a pressure-sensitive adhesive, and does not require adjustment of the time until the floor material is laminated after being applied to an adherend. The present invention also relates to an adhesive for flooring having a removability function that can be easily peeled off when the flooring is removed after adhesion.

(Prior Art) In recent years, among the adhesives, an aqueous dispersion type that does not use an organic solvent has been demanded from the viewpoints of economy and environmental hygiene. The range of the aqueous dispersion type adhesive is wide, and there are starch type, vinyl acetate type, ethylene-vinyl acetate type, styrene type, acrylic type, synthetic rubber type, natural rubber type and the like. In addition, there are a method of bonding the adherends immediately after coating and a method of bonding after a certain period of time. It is known that the time until bonding is limited regardless of the type of adhesive and that it is used under appropriate conditions.

(Problems to be Solved by the Invention) The aqueous dispersion as described above requires a time from coating to laminating, that is, open time in the adhesive industry. However, these open time restrictions are industrially inefficient tasks. In addition, even if it is attempted to be peeled off during replacement, it cannot be easily peeled off, and the adherend or the floor material often breaks, often impairing the work.

Therefore, as another method, there is a method in which a tacky adhesive is applied and water is evaporated to bond them when the tackiness is obtained.

However, it is difficult to take an appropriate open time in the field construction at the environmental temperature and the skill level.

From the above, it is an object of the present invention to provide a composition which does not require an open type after being applied to an adherend and has a removability function.

(Means for Solving the Problem) As a result of intensive studies to achieve the above object, the inventors of the present invention invent a floor adhesive having an excellent function by utilizing the composition and physical properties of various polymers. Came to.
That is, the present invention relates to [A] an aqueous adhesive composition composed of a synthetic resin-based, natural rubber-based, synthetic rubber-based, etc. adhesive composition alone or in a mixture of 100 parts by weight in terms of nonvolatile content, and [B].
(A) 70 to 99.9% by weight of (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms, (b) α, β
A protective colloid of incompletely saponified polyvinyl alcohol containing a monomer component consisting of 0.1 to 10% by weight of an unsaturated carboxylic acid and (c) 0 to 29.9% by weight of a vinyl compound other than the components (a) and (b). 10 to 100 parts by weight of a removable pressure-sensitive adhesive composition containing the fine particles of the pressure-sensitive adhesive polymer obtained by aqueous suspension polymerization in the presence of And / or a floor material adhesive comprising 3 to 100 parts by weight of an aqueous dispersion of a petroleum resin in terms of nonvolatile content.

In the present invention, the adhesive includes tackiness. In addition, the removability is defined as the performance that does not cause any trouble even if the peeling-sticking is repeated again immediately after the flooring is once stuck to the floor or after the passage of time.

The adhesive composition of the component (A) in the present invention is not particularly limited, but may be a commercially available one as long as it does not impair the removability. (B) having an alkyl group having 4 to 12 carbon atoms, which is used in the production of the removable adhesive composition of the component (meth)
As the acrylic acid alkyl ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
There are t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and the like. α, β
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
Examples of the vinyl monomer as the component (c) include vinyl acetate, vinyl propionate, methyl (meth) acrylate, ethyl (meth) acrylate, styrene, acrylonitrile, 2-hydroxyethyl (meth) acrylate, N, N.
-Dimethylaminoethyl acrylate, acrylamide, diacetone acrylamide, N-methylol acrylamide, glycidyl (meth) acrylate, aziridinyl ethyl (meth) acrylate and the like. As the natural resin and petroleum resin as the component [C], aliphatic hydrocarbon resin, aromatic petroleum resin, cyclopentadiene resin, polyterpene resin, terpene modified product, rosin, rosin ester, hydrogenated rosin ester, phenol resin , Styrene resin, xylene resin, etc. In preparing the component [A] which is an adhesive composition, it is necessary to change the composition depending on the material of the flooring material and the blending amount of the component [B]. For example, in the case of vinyl chloride, it is necessary to consider the plasticizer, and in the synthetic resin composition, it is necessary to copolymerize a large amount of unsaturated carboxylic acid. In the case of natural rubber or synthetic rubber, the tackifying resin used must have a low melting point. Further, in the case of a material which is difficult to adhere, it is desirable that the adhesive composition is made soft by using a polymer having a low glass transition point so as to have an adhesive force like an adhesive. Then, by adding a large amount of the component (B), it is possible to obtain a product that is more strongly adhered and has a high removability. The tacky polymer fine spheres of the component [B] can be easily prepared by an ordinary aqueous suspension polymerization method, but it is preferable to polymerize the anionic surfactant alone as a dispersant or in combination with a protective colloid. . The average particle size of the adhesive polymer fine spheres can reach the object in the range of 5 to 150 µ, but about 20 to 60 µ is preferable. The particles can be easily prepared by using a surfactant and a protective colloid, but can also be prepared by a polymerization reaction method. For example, a desired particle diameter can be obtained by devising a monomer dropping method, an emulsion dropping method or the like by a seed polymerization method or a multi-stage polymerization method. The elastic modulus of the adhesive polymer microspheres can be easily adjusted by using divinylbenzene, trimethylolpropane triacrylate or the like.

It is customary to use the adhesive polymer microspheres as an aqueous suspension, but only the adhesive polymer microspheres are taken out from the aqueous suspension with a filter, and after drying at low temperature, toluene, ethyl acetate, alcohol are used. There is also a method of adding a swelled and dissolved material to the adhesive composition. The component [B] is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the nonvolatile content of the component [A], but preferably 10 to 50 parts by weight is desirable for imparting adhesive strength and removability. The polymer microspheres are arranged on the surface of the adherend after adhesion and play an important role in adjusting the adhesion force. Aqueous dispersions of natural resin and petroleum resin as the component [C] are necessary for adjusting the adhesive force, and the adhesive force, the drying property and the adhesion which cannot be achieved by the adhesives of the synthetic resin type and the rubber type only. It provides anchorage and penetration to the body.

The floor material corresponding to the floor adhesive of the present invention is preferably a tile floor material such as a ceramic tile, a plastic tile, or a tile carpet, and is also suitable for a wooden floor or a floor material that is not flexible and long with plastic. Is.

The above floor material can be applied after the adhesive is applied to the floor base without considering the open type.

In the past, when replacing a floor material, there was a problem that a strong force that would cause pain when peeling off an old floor material was required, or the adhesive strength was too strong to damage the floor base. Also, if the adhesiveness is extremely weak, the floor material may peel off during walking.

(Operation) The present invention is an invention that solves the above-mentioned problems. Since the adhesive polymer microspheres used in the present invention are rich in elasticity, they deform to a flattened shape when a load is applied to the adherend. The adhesion area with and increases the adhesive strength. On the other hand, if the load is removed, it will return to the original spherical shape, so the physical properties of easy peeling can be obtained only by applying a certain force.

With the above-mentioned constitution, removability and shift prevention are obtained, and it is very useful as an adhesive for flooring. The effects of the present invention will be described in more detail with reference to the following examples. In the examples, "part" and "%" are based on weight.

Example 1 An acrylic tacky adhesive [Cybinol AC-60 (manufactured by Saiden Chemical Co., Ltd.), non-volatile content 50%, viscosity 6,000 cps / 25 ° C] is used as the component A.

Then water 10 in a container prepared for the production of sticky microspheres.
0 parts, 3 parts of a solution of 20% polyvinyl alcohol incompletely saponified solution previously dissolved, 1 part of anionic surfactant are charged and well stirred, then 45 parts of 2-ethylhexyl acrylate, 5 parts of butyl acrylate, Acrylic acid 1.5
And 0.5 part of benzoyl peroxide are dissolved by stirring in another container. Next, the mixed liquid of the monomers is added to the previously prepared aqueous solution and stirred.

Stirring 100 rpm, the reaction temperature is 70-75 ℃, the polymerization reaction starts and the temperature rapidly rises to 85-95 ℃. Then, the mixture is cooled to 81 to 82 ° C and reacted for 2 hours. An aqueous suspension with a uniform particle size is produced in the reaction vessel. Then, the next polymerization step is started. 50 parts of 2-ethylhexyl acrylate in a separate container,
0.5 part of an anion activator, 1.5 parts of acrylic acid, 0.5 part of benzoyl peroxide and 50 parts of water are well mixed with stirring. Next, all of these are added dropwise over 30 minutes and the reaction is continued at 80 to 83 ° C for 4 hours. Then, the solution was cooled and taken out, and the evaporation residue, viscosity and particle size of the aqueous suspension were confirmed. Nonvolatile component 40%, viscosity
The average particle size was 1,300 cps / 25 ° C and 20 to 50 µ. Let these be a [B] component. Next, as an adhesive for flooring, 100 parts of the above [A] component, 50 parts of the [B] component and 20 parts of an aqueous dispersion of a glycerol esterified product of hydrogenated rosin as the [C] component (nonvolatile content 50%). A suitable defoamer, antioxidant,
It was adjusted by adding it together with a preservative and stirring for 60 minutes. The obtained floor adhesive had a nonvolatile content of 46.7% and a viscosity of 3,000 cps / 25 ° C.

The floor adhesive prepared in Example 1 was applied to a concrete surface in a stripe shape so that the coating amount was 100 g / m ^2, and a carpet tile having a back surface made of vinyl chloride was adhered under the following conditions to obtain a coating. After one month, peeling was performed, and the adhesive force, removability, and the state of adhesion of the adhesive to the back surface of the carpet tile were examined. Adhesive strength is good enough to withstand practical impact, and removability makes adhesive strength good for peeling old flooring materials without causing pain, and stain resistance is good for carpet tile surfaces. The state in which the adhesive did not adhere was defined as good. The results are shown in the table as good (◯), slightly good (Δ), and bad (×).

Example 2 A rubber adhesive prepared by blending hydrogenated rosin ester with natural rubber latex [Cybinol AT-15, manufactured by Saiden Chemical Co., Ltd., nonvolatile content 50%, viscosity 4,000 cps / 25 ° C] An applied adhesive was prepared by adding 50 parts of an aqueous suspension containing sticky microspheres of the component [B] produced in 1 and 20 parts of an aqueous dispersion of a glycerol ester of hydrogenated rosin of the component [C].

The floor adhesive obtained in Example 2 was examined for adhesive strength, removability and stainability in the same manner as in Example 1.

Comparative Example Example 1 except that the component (B) was removed from Example 1 and Example 2.
The same compounding as in Example 1 was carried out to obtain adhesives of Comparative Examples 1 and 2. Then, the same performance test as in Example 1 was performed.

The following table shows the test results of the above Examples and Comparative Examples.

(Effects of the Invention) As described above, the adhesive for flooring material of the present invention provided good removability without considering the open time after coating on the floor base. For these effects, the composition balance of the respective components [A], [B], and [C] is important, but the adhesive polymer fine spheres of the component [B] are arranged on the surface layer of the adherend to improve the adhesive strength. Since it works effectively for removability, it is useful as an adhesive for flooring, which has an adhesive force even in a state close to that of green sticking or after drying and has a removability function. In addition, the floor base was not damaged during re-peeling, and the adhesive was not transferred to and adhered to the back surface of the floor material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Tanimoto 7-14-2 Tsuji, Urawa-shi, Saitama, Saiden Chemical Co., Ltd. (56) Reference JP 62-158769 (JP, A) JP 59 -159868 (JP, A)

Claims (1)

[Claims] 1. An aqueous adhesive composition comprising [A] a synthetic resin-based, natural rubber-based, or synthetic rubber-based adhesive composition alone or as a mixture, in an amount of 100 parts by weight in terms of non-volatile content, [B] ( a) 70 to 99.9% by weight of (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms,
(B) 0.1 to 10% by weight of α, β-unsaturated carboxylic acid, and (c) vinyl compound other than both components (a) and (b) 0
~ 29.9% by weight of the monomer component in the presence of a protective colloid of incompletely saponified polyvinyl alcohol in the presence of an aqueous suspension polymerization, resulting in adhesive polymer fine spheres removable adhesive 10 to 10 in terms of nonvolatile content
An adhesive for flooring, which comprises 100 parts by weight and [C] an aqueous dispersion of a natural resin and / or a petroleum resin in an amount of 3 to 100 parts by weight in terms of nonvolatile content.