JPH03231983A - Adhesive composition for flooring material and bonding of flooring material - Google Patents

Abstract

PURPOSE:To obtain the subject composition having a proper open time and applicable without causing shrinkage, peeling and joint staining by compounding a specific film-forming assistant to an emulsion of an acrylic polymer polymerized in the presence of protective colloid. CONSTITUTION:The objective composition is produced by compounding (A) an emulsion of an acrylic polymer surrounded by protective colloid with (B) preferably 3-50 pts.wt. (based on 100 pts.wt. of the non-volatile component of the component A) of a film-forming assistant compatible to the protective colloid of the component A and composed of preferably a (co)polymer of amine, ammonia or a univalent metal salt of styrenesulfonic acid.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a water-based dispersion adhesive useful for adhering flooring materials, particularly vinyl chloride flooring materials. = Ru.

(Prior art) In recent years, emulsion-type adhesives that do not use organic solvents have been required from the Ministry of Economic Affairs and environmental hygiene points of view, and have actually been used particularly in the field of vinyl chloride flooring materials. There is.

However, the adhesive strength of these water-based dispersion adhesives may decrease due to the influence of the plasticizer in the vinyl chloride of the vinyl chloride flooring material (hereinafter referred to as flooring material), the influence of alkaline water from the underlying concrete and mortar, etc. This has caused the flooring to shrink, peel, and stain the joints.

To solve this problem, the composition of the adhesive is made harder to improve plasticizer resistance, and large amounts of fillers (calcium carbonate, talc, asbestos, etc.) are used to improve alkali resistance. However, the reality is that these methods are not sufficiently effective, and the time from coating to bonding, ie, open time, is extremely short, and 3- operational troubles are likely to occur.

(Problems to be Solved by the Invention) The purpose of the present invention is to prevent shrinkage, peeling, and staining of the joints of flooring materials by improving plasticizer resistance, water resistance, and alkali resistance, and to provide appropriate open time. An object of the present invention is to provide an aqueous dispersion adhesive for flooring having the following properties.

(Means and effects for solving the problem) As a result of intensive studies to achieve the above object, the present inventors found that an emulsion of an acrylic polymer polymerized in the presence of a special protective colloid has a specific function. By blending a film-forming aid with as a wet tack adjuster, shrinkage of flooring
We have now invented an emulsion-type adhesive for flooring that has an appropriate open time without peeling or staining the joints.

That is, the gist of the present invention is an adhesive composition for flooring material 4 comprising an acrylic polymer emulsion surrounded by a protective colloid and a film forming aid having an affinity for the protective colloid.

If component (A) is a single or copolymer emulsion of an acrylic polymer, the (meth)acrylic acid alkyl ester monomer having an alkyl group of 1 to 12 carbon atoms constituting component (A) is, for example, (meth) ) Methyl acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)
Examples of copolymerizable monomers include 2-ethylhexyl acrylate and lauryl (meth)acrylate. Examples of other copolymerizable monomers include (meth)acrylic acid, crotonic acid, maleic acid, acrylamide, N-methylolacrylamide, vinyl acetate, Examples include acrylonitrile, styrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, and alkoxyvinylsilane.

- Specifically, the above acrylic polymer emulsion is formed in the presence of a protective colloid as described below, and is finally contained in the film.

Examples of protective colloids include homopolymers or copolymers of amine, ammonia, or -valent metal salts of styrene sulfonic acid; examples of styrene sulfonates include triethylamine, diethylamine, triethanolamine, and amine salts; Examples include jetanolamine, stearylamine, etc.
In the case of valent metal salts, sodium, potassium, etc. are shown.

In addition, (meth)acrylic acid alkyl ester monomers copolymerized with styrene sulfonic acid salts include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. Examples include 2-ethylhexyl, isononyl (meth)acrylate, and lauryl (meth)acrylate.

6. The amount of the independent polymer or copolymer such as styrene sulfonate as a protective colloid is preferably 0.5 to 20% by weight based on the (meth)acrylic monomer.

Polyvinylpyrrolidone, which has an affinity with other film-forming aids,
Copolymers of polyvinyl alcohol-based styrene and carboxyl group-containing substances, East Germany polymers or copolymers of acrylamide, cellulose derivatives, etc. can also be used alone or in combination.

The acrylic polymer emulsion used in the present invention is
An acrylic polymer emulsion is polymerized and formed simultaneously with the protective colloid in the presence of the bipedal protective colloid-forming component, and is contained in the protective colloid.

When the above-mentioned component (A) of the present invention is used as an adhesive composition for flooring, it exhibits excellent performance with no decrease in adhesive strength and no shrinkage of the flooring.

For example, in the product of the present invention, which uses polystyrene sulfonate with a high degree of polymerization as a protective colloid, the polystyrene sulfonate, which is a protective colloid component, absorbs the plasticizer from the flooring material and plasticizes the acrylic polymer. It prevents the influence of plasticizers and reduces the softening of the entire polymer, while at the same time increasing adhesive strength by absorbing a suitable amount of plasticizers.
It can demonstrate excellent performance with no decrease in adhesive strength and little shrinkage of the flooring material.

In the present invention, it is especially important to add component (B), a film-forming aid.

The compounds represented by the general formula C3H3-X-OH of component (B) include glycol monophenyl ethers (C61(50ROH) monoethylene glycol monophenyl ether C
3H50CH2CH20H polyethylene glycol monophenyl ether C6H60 (C2H40) n
H (n = integer from 2 to 10) Propylene glycol monophenyl ether
C6H5OcBr-t6oH polypropylene glycol monophenyl ether C6H50(CBH60)n
H (integer from n-2 to 10) Phenyl alcohols (C685ROH) Phenylethyl alcohol C3H3CH2CH20H Phenylpropyl alcohol C4H5C3H60H Phenylbutyl alcohol C6H3C4H80H Phenylhexyl alcohol c6 H5c6 H120H Phenyl octyl alcohol C6H5Cog HI50 H Phenylcal Bonic acid esters (C6HsCOOROH) Benzoic acid Ethylene glycol heptanoester C6H3C,
00C82CH20H Benzoic acid propylene glycol monoester
C6H6C00C8H6oH Benzoic acid hexylene glycol monoester C6H3CQOC6H
1゜oI] Benzoic acid polyethylene glycol monoester C6H5COO(C2H40)nH (n=2~
(integer of 10) Benzoic acid polypropylene glycol monoester C
6H3C○O (CB H60) n H (n=2~10
) Oxycarboxylic acid phenyl ester (C6H500CROH) Oxyacetic acid phenyl ester C6H500CCH20H Oxypropionic acid phenyl ester 06 summer-1500C (l(z CH20tl Lactic acid phenyl ester C6H500CC:HOHCH8, etc.).

Component (B) is the non-volatile content of component (A) 100 times 10- It is desirable to use 3 to 50 parts by weight based on the weight of the part.

Since the obtained component (B) has a high affinity with the protective colloid film of component (A), it can be plasticized and swelled to promote fusion of emulsion particles, which has the effect of increasing the wet tack force. .

When adhering flooring materials to a substrate, the initial adhesion is strong even if drying is insufficient, and prevents dimensional and shape changes such as shifting, warping, and shrinkage after adhesion of the flooring materials. Moreover, since the coating film is plasticized even after a certain degree of drying, the adhesive composition has a long open time and provides sufficient adhesive strength.

Furthermore, when the adhesive composition applied to the floor subsurface evaporates water and dries, a large proportion of the film-forming aid evaporates, resulting in the formation of a tough film of the floor adhesive.

When an aqueous dispersion of a natural or petroleum resin is blended into the adhesive composition, the performance is further improved. These resins include a wide range of resins such as aromatic petroleum resins, cyclopentadiene resins, polyterpene resins, modified terpenes, rosins, rosin esters, hydrogenated rosin esters, phenolic resins, styrene resins, and xylene resins. . These resins can be commercially available aqueous dispersion types, or aqueous dispersion types prepared by dissolving the resin in a solvent and dispersing it with a surfactant. This aqueous dispersion of petroleum resin or the like improves adhesion and permeability to the back surface of the flooring material, so it is not only effective in increasing the adhesive strength between the flooring material and the base material, but also improves water resistance.

This aqueous dispersion of natural or petroleum resin has a non-volatile content of 0 to 10 parts by weight based on 100 parts by weight of the non-volatile content of component (A).
Preferably 0 copies.

In addition, in the present invention, fillers such as calcium carbonate, talc, and clay are added in an amount of 0 per 100 parts by weight of non-volatile content of component (A).
The cost is reduced by adding ~250 parts;
Benefits include ease of brush handling, excellent workability on site, and ability to dry quickly and control open time.

Another invention of the present application is to apply a wet tack adhesive consisting of an emulsion composed of acrylic polymer particles surrounded by a protective colloid and a film-forming aid having an affinity for the protective colloid to a subfloor. The gist of this paper is a method for adhering flooring materials, in which the flooring material is adhered after developing its properties.

FIG. 1 is a sectional view of the construction state of the flooring material, and when constructing the flooring material 1 on the subfloor G, an adhesive 2 is applied to the subfloor G.

In the present invention, the polymer particles 3 in the acrylic polymer emulsion are surrounded by a protective colloid 4 such as styrene sulfonate, and a common surfactant (emulsifier)
An emulsion with finer particles and a higher degree of polymerization can be obtained compared to an emulsion using the same method, and has excellent water resistance.

For this reason, it has excellent drying properties after being applied to a substrate (concrete, mortar), and at the same time has excellent adhesion to the substrate.

Furthermore, it is resistant to attack by alkaline water from the base and provides strong adhesive strength.

6 is the emulsion solvent/water.

In the present invention, the protective colloid component 4, for example, polystyrene sulfonate, and the film-forming aid 5, for example, the component (B) containing a phenyl group, have a very strong affinity and are therefore abundant on the outside of the particles. Component (B), which is a film-forming aid, is selectively dissolved, plasticized, and swollen in polystyrene sulfonate, which is a protective colloid, to provide strong wet tack properties.

As a result, strong adhesive strength and dimensional and shape stability of the flooring material can be obtained.

For example, in the product of the present invention, which uses polystyrene sulfonate with a high degree of polymerization as a protective colloid, the 14-polystyrene sulfonate, which is a protective colloid component, absorbs the plasticizer from the flooring material and converts it into an acrylic polymer. It prevents the effects of plasticizers and reduces the softening of the entire polymer, while at the same time increasing adhesive strength by absorbing a moderate amount of plasticizer, there is no decrease in adhesive strength and less shrinkage of the flooring material. It can demonstrate excellent performance.

In the present invention, performance is further improved when an aqueous dispersion of a natural or petroleum resin is blended into the adhesive composition. These resins include a wide range of resins such as aromatic petroleum resins, cyclopentadiene resins, polyterpene resins, modified terpenes, rosins, rosin esters, hydrogenated rosin esters, phenolic resins, styrene resins, and xylene resins.

This aqueous dispersion of petroleum resin or the like improves adhesion and permeability to the back side of the flooring material, so it is not only effective in increasing the adhesive strength between the flooring material and the base, but also improves water resistance.

This aqueous dispersion of natural or petroleum resin has a non-volatile content of 0 to 100 parts by weight based on 100 parts by weight of the non-volatile content of component (A).
part is preferable.

In addition, in the present invention, fillers such as calcium carbonate, talc, and clay are added in an amount of 0 per 100 parts by weight of non-volatile content of component (A).
The cost is reduced by adding ~250 parts;
Benefits include ease of brush handling, excellent workability on site, and ability to dry quickly and control open time.

Further, when the adhesive composition applied to the floor subsurface evaporates water and dries, a large proportion of the film-forming agent evaporates, and as a result, the floor adhesive is formed as a tough film.

(Effects of the invention) - The dimensional stability and shape stability of the flooring material have been improved, and the performance of the flooring material in preventing shrinkage, peeling, joint clearance, joint staining, warping, etc. has been improved.

■Water resistance, chemical resistance, plasticizer resistance, etc. have been improved, and in particular, it has shown extremely excellent durability against alkaline water generated from the mortar base.

■Excellent wet tack properties improve the adhesive strength between the flooring material and the subfloor, and the adhesive binder forms a strong film after drying.

■Long-term open time was obtained.

■Workability was excellent.

(Example) Hereinafter, the effects of the present invention will be described in more detail with reference to Examples. In the Examples, parts and percentages are based on weight.

Example 1 50 parts of ion-exchanged water, 1.0 part of nonionic surfactant (Nonion NS-230, polyoxyethylene alkyl phenyl ether type manufactured by NOF ■), anionic surfactant (Neogen T, Daiichi Kogyo Co., Ltd.) 0.5 part of sodium dodecylbenzenesulfonate (manufactured by Pharmaceutical Co., Ltd.) was added and dissolved with stirring.

Next, a 17-monomer mixture consisting of 30 parts of n-butyl acrylate, 10 parts of methyl acrylate, 58 parts of methyl methacrylate, and 2 parts of acrylic acid, and 0.2 parts of ammonium persulfate as a polymerization initiator were added to mix and emulsify. A monomer emulsion was prepared.

Next, 18 parts of ion-exchanged water and 3 parts of a homopolymer of sodium styrene sulfonate were charged into a reaction vessel, the mixture was filled with nitrogen, and heated with stirring.When the internal temperature reached 80°C, 0.2 parts of ammonium persulfate was added. In addition, a monomer emulsion prepared in advance was successively added to start the polymerization reaction, and the dropwise reaction continued for 2.5 hours.

After the dropwise addition was completed, stirring was performed at the same temperature for 1.5 hours.

Thereafter, it was cooled and 0.3 part of aqueous ammonia was added to obtain an acrylic emulsion with an evaporation residue of 60.5%, a viscosity of 2,500 cps, and a pH of 6.5.

After that, the thickener Cypinol AZ-1 (Siden Chemical ■
1.0 part of Aqueous Ammonia) and 0.5 part of aqueous ammonia were added to obtain an emulsion with an evaporation residue of 60.0%, a viscosity of 30,000 cps, and a pH of 8.1.

10 parts of propylene glycol monophenyl ether was added to 100 parts of the above acrylic emulsion, and the desired adhesive composition was obtained.

Example 2 An adhesive composition was obtained in the same manner as in Example 1, except that 10 parts of propylene glycol monophenyl ether was replaced with 10 parts of monoethylene glycol monophenyl ether.

Example 3 An adhesive composition was obtained in the same manner as in Example 1, except that 10 parts of propylene glycol monophenyl ether was replaced with 15 parts of phenylpropyl alcohol.

Example 4 100 parts of the adhesive composition of Example 1, 30 parts of an aqueous 19-dispersion (nonvolatile content 50.0%) of a glycerin ester compound of hydrogenated rosin, and 10 parts of micronized calcium carbonate were mixed and evaporated. Residue 63.0%, viscosity 32,
An adhesive composition with a pH of 8.3 and a pH of 8.3 was obtained.

Example 5 The same method as in Example 1 was used except that 3 parts of sodium styrene sulfonate methyl methacrylate copolymer containing 5% methyl methacrylate was used instead of the sodium styrene sulfonate homopolymer. A polymerization reaction and adjustment were performed to obtain the desired adhesive composition.

Comparative Example 1 The same polymerization reaction as in Example 1 was carried out except for the sodium styrene sulfonate homopolymer.

Then add 0.5 part of ammonia water, thickener (Cypinol A
Z-1,) 1.0 part was added.

Evaporation residue 59.5%, viscosity 29,500 cps, PH8
, 0 was obtained.=20- Comparative Example 2 10 parts of propylene glycol monophenyl ether was added to 100 parts of the emulsion obtained in Comparative Example 1 to prepare an adhesive composition.

Comparative Example 3 An adhesive composition was obtained in the same manner as in Example 1 except that propylene glycol monophenyl ether was removed.

Adhesive sample preparation method Each adhesive composition of Examples 1 to 5 and Comparative Examples 1 to 3 was
Using an IS brush (JIS G-31101), clean a flexible slate board (8 mm thick, JIS A-540
3) at a coating amount of 220 g/rrr (Wet), and after a predetermined open time, homogeneous PVC floor tiles (JIS A-5705) and vinyl floor sheets (JIS A5707) were bonded together and used as a sample. It was used for each test.

In the present invention, the wet tack test was conducted as follows.

Immediately after bonding the PvC tile and the slate board 8 having a thickness of 8n+m as shown in FIG. 2, a load W of 40g was applied and the falling time was measured. The "viscosity" of the adhesive, that is, the wet tack force, was determined from the relationship between the time (open time) for bonding the PVC tiles 7 after applying the adhesive 6 and the falling time. The falling time was measured up to 300 seconds, after which it was stopped because it did not fall.

1) Shrinkage rate test After applying each adhesive composition to a flexible slate board, take an open time of 50 minutes and paste a homogeneous PVC floor tile (size = width 50 mm x length 100 mm) to 23 ± 1' C165 ± After being left at 5% RH for 7 days, the bonded sample was heated at 70° C. for 7 days. The size of the homogeneous PVC floor tiles at the initial stage and after drying was measured using calipers, and the shrinkage rate was calculated.

22- The greater the effect of the plasticizer on the PVC floor tiles, the greater the shrinkage rate.

2) Adhesion test After applying the adhesive composition to a flexible slate board, take an oven time for 20 minutes, paste a vinyl floor sheet (size = width 30 m x length 150 mm), and
After being left at 3±i° C. and 65±5% RH for 7 days, the bonded sample was heated at 70° C. for 70 hours.

The peel strength when peeled off in a 90 degree direction was measured for those that had been left at 23±1°C and 165±5% RH for 7 days and those that had been heated at 70°C for 7 days. (Peeling speed: 300 nn+/min) 3) Alkaline water resistance test Each bonded sample prepared for shrinkage measurement was heated at 23±1°C for 6
After being left at 5±5% RH for 7 days, it was immersed in a calcium hydroxide saturated aqueous solution and taken out after 7 days, and the state of adhesion was determined by peeling it off by hand.

O: Good adhesion △: Poor adhesion X: Poor adhesion The obtained results and examples are shown in Table 1. are shown in Table 2.

Comparative Example Table 1 Comparing the obtained Examples and Comparative Examples, Examples 1 to 5 have a low shrinkage rate of 0.3 to 0.8%, while Comparative Examples 1 to 4 have a shrinkage rate of 2.0 to 3.9%. %, which was a maximum shrinkage rate of 13 times.

25- Regarding adhesive strength, in the examples, approximately 2.5 to 3.5 kg was obtained both when left at room temperature and when heated at 70°C, whereas in the comparative example, approximately 1.2 to 2.2 kg was obtained at room temperature. At 70°C, the weight decreased dramatically to 0.7 to 1.2 kg.

Regarding alkaline water resistance, the examples had good adhesion, whereas the comparative examples had poor adhesion.

Regarding the open time, no tiles fell in the example, but all tiles fell within 280 seconds in the comparative example, making it clear that the example had better wet tack properties.

[Brief explanation of drawings]

FIG. 1 is a sectional view of the construction method of the present invention, and FIG. 2 is an explanatory diagram of the wet tack test method. 1 is a flooring material, 2 is an adhesive layer, 3 is a polymer particle, 4 is a protective colloid, and 5 is a film-forming aid. I”d

Claims (1)

[Scope of Claims] 1. An adhesive composition for flooring comprising an acrylic polymer emulsion surrounded by a protective colloid and a film-forming aid having an affinity for the protective colloid. 2. The film-forming aid is a compound represented by the general formula C_6H_5-X-OH (however, in the above chemical formula, X represents either OR, R, COOR, or OCO-R, and R represents monoethylene, polyethylene, 2. The adhesive composition for flooring according to claim 1, characterized in that it consists of any one of ethylene oxide, monopropylene, polypropylene oxide, monobutylene, polybutylene oxide, monohexylene, or polyhexylene oxide. 3. The adhesive composition for flooring according to claim 1, wherein the protective colloid is a homopolymer or copolymer of a styrene sulfonic acid amine, ammonia, or a monovalent metal salt. 4. The composition according to claim 1 or 2, which contains an aqueous dispersion of a natural resin and/or a petroleum resin. 5. The composition according to claim 1 or 2, which contains calcium carbonate, talc, clay, etc. as a filler. 6. Applying an adhesive consisting of an emulsion composed of acrylic polymer particles surrounded by a protective colloid and a film-forming agent having an affinity for the protective colloid to the subfloor;
A flooring adhesive installation method in which the flooring material is adhered after developing wet tack properties.