JPH10237406A - Adhesive composition and wallpaper prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive compsn. which does not generate a toxic gas nor a substance polluting the work environment, exhibits an excellent flame retardance, and is excellent in storage stability, adhesive properties, etc., and to provide a fabric-based wallpaper produced by using the same. SOLUTION: This compsn. comprises 100 pts.wt. (resin basis) vinyl acetate resin emulsion, 6-12 pts.wt. titanium oxide, 6-18 pts.wt. aluminum hydroxide, and 10-20 pts.wt. expandable graphite and/or silicone powder. The fabric-based wallpaper is prepd. by bonding a base fabric to a liner with the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition having excellent flame retardancy, and a textile wallpaper produced using the adhesive composition.

[0002]

2. Description of the Related Art In general, most adhesive compositions are mainly composed of organic high molecular substances such as elastomers and plastics. Therefore, their dry films are flammable. In applications, it is required to impart flame retardancy (hereinafter simply referred to as “flame retardancy of the adhesive composition”) to the dried film of the adhesive composition.

[0003] Methods of imparting flame retardancy to the adhesive composition include a method using a halogen-containing organic polymer as a main component, a method of adding a flame retardant, and a method of combining these.

The flame retardants include halogen-containing compounds, antimony-containing compounds such as antimony trioxide,
Examples include hydrated metal hydroxides such as aluminum hydroxide and magnesium hydroxide, phosphorus compounds such as red phosphorus, and metal oxides, which are generally used.

[0005] However, although the above halogen-containing compounds can impart high flame retardancy to organic polymer substances, they generate toxic gases during processing and combustion, so that they are toxic to the human body and corrosive to equipment. There are problems such as
With the recent rise in social needs related to health and safety and environmental protection, there is a strong demand for the establishment of halogen-free flame retardant technology.

[0006] If the antimony-containing compound is incorporated in an emulsion-based adhesive such as a vinyl acetate resin emulsion or an ethylene-vinyl acetate copolymer resin emulsion in a sufficient flame-retardant amount, the antimony-containing compound can be stored during storage. There is a problem that precipitation occurs in the emulsion, which impairs storage stability and increases costs.

Further, although the above hydrated metal hydroxide does not generate toxic gas during processing or combustion, it generally has a small flame-retarding effect. Has a problem that a large amount of addition is required, and the resulting adhesive composition becomes brittle and the mechanical strength is remarkably reduced.

In order to cope with these problems of the conventional flame retardants, various flame retarding techniques have been studied. For example, Japanese Patent Application Laid-Open No. 3-41163 discloses "(A) alkaline earth metal compound or It is coated with a metal hydroxide and (B) a film-forming resinous material, wherein the content of (A) is 0.1 to 50% by weight and the content of (B) is 0.01 to 5% by weight. Thermoplastic resin composition containing thermally expandable graphite "
However, in order to impart sufficient flame retardancy to the thermoplastic resin, it is necessary to add a large amount of heat-expandable graphite, and on the safety side, a large amount of expanded graphite is scattered during combustion. There is a problem.

In Japanese Patent Application Laid-Open No. 62-275138, "20 to 200 parts by weight per 100 parts by weight of polyolefin"
A flame retardant composition comprising 1 part by weight of a non-halogen flame retardant, 1 to 50 parts by weight of graphite and 1 to 50 parts by weight of a phosphorus-based flame retardant (for example, red phosphorus) has been proposed. In order to impart sufficient flame retardancy to polyolefins, it is necessary to add a large amount of a non-halogen flame retardant, graphite and expensive red phosphorus. There is a problem that it becomes high.

Japanese Patent Application Laid-Open No. 60-152542 discloses that "a polyethylene-based resin or a copolymer resin mainly composed of ethylene is added with a phosphorus-based flame retardant which does not impair the transparency of these resins and triphenylantimony. A flame-retardant transparent polyolefin resin composition "has been proposed, but also in this proposal, in order to impart sufficient flame retardancy to the polyolefin resin, a large amount of a phosphorus-based flame retardant and triphenylantimony are added. However, there is a problem that the physical properties of the obtained molded article are significantly reduced.

Further, Japanese Patent Application Laid-Open No. 6-256737 discloses that "water-soluble or water-based emulsion-based adhesive component: gypsum powder has a water-soluble or gypsum powder ratio of 1: 0.5 to 1: 4. A flame-retardant, heat-insulating adhesive composition prepared by mixing gypsum powder with an aqueous emulsion-based adhesive component has been proposed.

However, in the case of the adhesive composition proposed above, since the gypsum powder undergoes a hydration reaction with time in a water-soluble or aqueous emulsion, the adhesive composition becomes putty-like or solid and becomes fluid. And loses practical use.

As described above, the addition of a small amount of a flame retardant to such an extent that the storage stability and the adhesive properties of the adhesive composition are not impaired makes it possible to obtain an excellent flame retardancy for an adhesive composition, especially an emulsion adhesive composition. At present, no practical technology for imparting properties has been established.

[0014]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention exhibits excellent flame retardancy without generating toxic gas or substances polluting the working environment, and exhibits stable storage. Adhesive composition with excellent properties and adhesive properties,
It is another object of the present invention to provide a woven wallpaper produced using the adhesive composition.

[0015]

The adhesive composition according to the first aspect of the present invention (hereinafter referred to as "first invention") comprises titanium oxide 6 per 100 parts by weight of a vinyl acetate resin emulsion resin. ~ 12 parts by weight, aluminum hydroxide 6
~ 18 parts by weight and 10 ~ 20 parts by weight of thermally expandable graphite.

The adhesive composition according to the second aspect of the present invention (hereinafter referred to as "second invention") comprises 6 to 12 parts by weight of titanium oxide based on 100 parts by weight of a vinyl acetate resin emulsion resin. , 6 to 18 parts by weight of aluminum hydroxide,
And, it is characterized by containing 10 to 20 parts by weight of silicone-based powder.

Further, the woven fabric wallpaper according to the invention of claim 3 (hereinafter referred to as "third invention") is characterized in that the raw fabric and the backing material are adhered by the adhesive composition according to the first invention. Features.

The vinyl acetate resin emulsion used as a main component in the adhesive composition according to the first or second invention may be a vinyl acetate monomer alone or a polymerizable polymer which can be copolymerized with the vinyl acetate monomer. The monomer is, for example, an aqueous solution of polyvinyl alcohol (hereinafter referred to as “PVA”) or the like as a protective colloid, for example, a peroxide such as hydrogen peroxide solution as a polymerization catalyst, in water at about 60 to 80 ° C. It can be obtained by emulsion (co) polymerization at a temperature for about 1 to 2 hours. Here, “(co) polymerization” means “polymerization” or “copolymerization”.

The polymerizable monomer copolymerizable with the vinyl acetate monomer is not particularly limited. Examples thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. ) Ethylenically unsaturated monomers such as acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, glycidyl (meth) acrylate;
Examples include hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate, and one or more of these are preferably used. Here, “(meth) acryl” means “acryl” or “methacryl”.

The protective colloid is not particularly limited, but includes PVA;
A modified PVA such as VA; a copolymer of α-olefin and unsaturated carboxylic acid such as a copolymer of isobutylene and maleic anhydride or a water-soluble product of a derivative thereof with a basic substance; carboxymethyl cellulose; One or two or more of the above are preferably used, and among them, PVA is more preferably used in that the initial adhesive strength of the obtained adhesive composition is improved.

Examples of the polymerization initiator include, but are not particularly limited to, aqueous hydrogen peroxide; persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; reduction of tartaric acid, formic acid, oxalic acid, and the like. Agents and the like, and one or more of these are suitably used.

In the adhesive composition according to the first or second invention, it is necessary that 6 to 12 parts by weight of titanium oxide is contained with respect to 100 parts by weight of the resin component of the vinyl acetate resin emulsion. .

When the adhesive composition obtained by adding titanium oxide to a vinyl acetate resin emulsion is used for bonding a wall covering for construction such as wallpaper, for example, the concealing property of the wall covering, etc. The effect as a white pigment to improve the design surface of the resin and the effect as an inorganic filler that raises the ignition point and lowers the combustion energy because the content of the resin component in the adhesive composition is reduced. Can be done.

The type of the titanium oxide is not particularly limited, and any crystal form of titanium oxide such as rutile-type titanium oxide, anatase-type titanium oxide and brookite-type titanium oxide is preferably used. It is preferable to use rutile-type titanium oxide when importance is attached to improvement of weather resistance, and it is preferable to use anatase-type titanium oxide when importance is attached to improvement of whiteness. If necessary, two or more kinds of titanium oxides may be used in combination. The average particle size of the titanium oxide is not particularly limited, but is preferably 0.5 μm or less.

Resin content of vinyl acetate resin emulsion 1
When the content of the titanium oxide is less than 6 parts by weight with respect to 00 parts by weight, the effect as a white pigment and the effect as an inorganic filler described above cannot be sufficiently obtained. Storage stability and adhesive properties of the resulting adhesive composition are reduced.

The method of adding the above-mentioned titanium oxide to the vinyl acetate resin emulsion is not particularly limited, and may be directly added. Min 50-7
It is preferable to add in a state of a water slurry of about 0% by weight.

In the adhesive composition according to the first or second invention, it is necessary that 6 to 18 parts by weight of aluminum hydroxide is contained with respect to 100 parts by weight of the resin component of the vinyl acetate resin emulsion. is there.

The above-mentioned aluminum hydroxide functions as a main flame retardant, and when used in combination with a heat-expandable graphite or a silicone-based powder as a flame-retardant aid described later, the resulting adhesive composition has excellent flame retardancy. Can be given.

The shape of the aluminum hydroxide is not particularly limited, and may be any of powder, granules, granules and the like. The average particle size of the aluminum hydroxide is not particularly limited, but is preferably 100 μm or less for secondary particles, and more preferably 1 μm or less.
The following fine particle product is more preferable.

Resin content of vinyl acetate resin emulsion 1
When the content of the aluminum hydroxide is less than 6 parts by weight with respect to 00 parts by weight, the flame retardancy of the obtained adhesive composition is not sufficiently improved, and when it exceeds 18 parts by weight, the obtained adhesive is The storage stability and adhesive properties of the composition are reduced.

The method of adding the aluminum hydroxide to the vinyl acetate resin emulsion is not particularly limited, and it may be added directly. It is preferable to add aluminum in the form of a water slurry having a nonvolatile content of about 50 to 70% by weight.

In the adhesive composition according to the first invention,
It is necessary that 10 to 20 parts by weight of thermally expandable graphite is contained with respect to 100 parts by weight of the resin component of the vinyl acetate resin emulsion.

The thermally expandable graphite functions as a flame-retardant auxiliary, and when used in combination with the aluminum hydroxide as the main flame-retardant, excellent flame retardancy can be imparted to the resulting adhesive composition. .

The heat-expandable graphite is obtained by mixing powders such as natural phosphorous graphite, pyrolytic graphite, and Kish graphite with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, and concentrated nitric acid.
This is a crystallized product which has been treated with a strong oxidizing agent such as hydrogen peroxide to produce a graphite intercalation compound while maintaining a layered structure of carbon.

The thermally expandable graphite obtained by the acid treatment as described above is preferably further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

The aliphatic lower amine is not particularly restricted but includes, for example, monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like, and are preferably used. The alkali metal compound and alkaline earth metal compound are not particularly limited, but include, for example, potassium, sodium, calcium, barium,
Hydroxides, oxides, carbonates, sulfates such as magnesium,
Organic acid salts and the like can be mentioned, and are preferably used.

The particle size of the heat-expandable graphite is not particularly limited, but is preferably 20 to 200 mesh. If the particle size is smaller than 200 mesh, the degree of expansion of graphite becomes small, and sufficient flame retardancy cannot be obtained,
Conversely, if it is larger than 20 mesh, the dispersibility in the vinyl acetate resin emulsion becomes poor, and the storage stability of the obtained adhesive composition decreases.

The degree of expansion of the heat-expandable graphite is not particularly limited. However, in order to obtain excellent flame retardancy, the degree of expansion when heated at 1000 ° C. for 10 seconds is 50%.
It is preferably ~ 250 cc / g. The term "degree of expansion" used herein means that a quartz beaker having a capacity of 150 cc, which was heated for 10 minutes or more and held in an electric furnace maintained at 1000 ° C., was taken out of the furnace, and 0.5 g of thermally expandable graphite was obtained. , Immediately put into a furnace also kept at 1000 ° C., and kept as it is for 10 seconds, taken out of the furnace, and naturally cooled, and the volume / weight ratio of expanded graphite (unit: cc / g) Means

Resin content of vinyl acetate resin emulsion 1
If the content of the heat-expandable graphite relative to 00 parts by weight is less than 10 parts by weight, the flame retardancy of the obtained adhesive composition will not be sufficiently improved. Storage stability and adhesive properties of the agent composition are reduced.

The method of adding the heat-expandable graphite to the vinyl acetate resin emulsion is not particularly limited, and may be directly added. However, in order to uniformly disperse and mix the heat-expandable graphite, Non-volatile content of thermally expandable graphite 5
It is preferable to add in a state of a water slurry of about 0 to 70% by weight.

In the adhesive composition according to the second invention,
It is necessary that 10 to 20 parts by weight of silicone powder is contained with respect to 100 parts by weight of the resin component of the vinyl acetate resin emulsion.

The silicone-based powder functions as a flame-retardant auxiliary agent and a hiding agent, and when used in combination with the aluminum hydroxide as the main flame-retardant, the resulting adhesive composition has excellent flame retardancy. Along with imparting, for example, by using in combination with titanium oxide as a white pigment for improving the design surface such as the concealing property of a wall covering material such as wallpaper, the design surface such as the concealing property of the obtained adhesive composition is significantly improved. Let it.

The silicone-based powder is a spherical fine particle of an organopolysiloxane having a white appearance, and in some cases, functional groups such as an epoxy group, a methacryl group, and an amino group are introduced. The silicone-based powder is commercially available, for example, from Dow Corning Toray Silicone Co., Ltd. or Toshiba Silicone Co., Ltd.

Resin content of vinyl acetate resin emulsion 1
The content of the silicone-based powder is 1 to 100 parts by weight.
If the amount is less than 0 parts by weight, the flame retardancy and concealing properties of the obtained adhesive composition will not be sufficiently improved, and if it exceeds 20 parts by weight, the storage stability and adhesion of the obtained adhesive composition will be reduced. The characteristics and the like deteriorate.

The method of adding the silicone-based powder to the vinyl acetate-based resin emulsion is not particularly limited, and may be directly added. However, in order to uniformly disperse and mix the silicone-based powder, It is preferable to add the silicone-based powder in a state of a water slurry having a nonvolatile content of about 50 to 70% by weight.

The adhesive composition according to the first invention comprises a vinyl acetate resin emulsion, titanium oxide,
In addition to aluminum hydroxide and heat-expandable graphite, if necessary within a range that does not hinder achievement of the object of the present invention, silicone-based powder, tackifier resin, surfactant, softener, plasticizer,
One or more of various additives such as fillers, pigments, dyes, stabilizers, antioxidants, ultraviolet absorbers, preservatives, fungicides, defoamers, and organic solvents may be contained. .

The adhesive composition according to the second invention comprises, in addition to the essential components, a vinyl acetate resin emulsion, titanium oxide, aluminum hydroxide and silicone powder,
If necessary, the thermal expansion graphite, tackifying resin, surfactant, softener, plasticizer, filler, pigment, dye, stabilizer, antioxidant, and ultraviolet absorption as long as the object of the present invention is not hindered. One or more of various additives such as an agent, a preservative, a fungicide, an antifoaming agent, and an organic solvent may be contained.

The method for producing the adhesive composition according to the first invention or the second invention is not particularly limited, and a conventionally known stirring mixer such as a Satake-type stirrer, a universal mixer, a kneader or a colloid mill is used. A predetermined amount of each of titanium oxide, aluminum hydroxide, and heat-expandable graphite (first invention) or silicone-based powder (second invention), and various additives to be contained as required, based on the resin emulsion. A desired adhesive composition can be obtained by adding one or more kinds and uniformly dispersing and mixing.

The adhesive composition according to the first or second invention is preferably used mainly for bonding wall coverings for buildings, but is not limited to the above-mentioned applications, and is not limited to the above-mentioned applications. It may be used for woodworking, general use, and the like.

Next, the textile wallpaper according to the third invention is characterized in that the raw fabric and the backing material are adhered by the adhesive composition according to the first or second invention.

The type of raw fabric used for the textile wallpaper according to the third aspect of the present invention is not particularly limited.
Raw materials of natural fabrics such as silk, wool, hemp, and plain paper, twill, and other various weaves, such as paper cloth, kuzubu, and nonwoven cloth; viscose, rayon, cupra, etc. Semi-synthetic fiber cloth such as cellulose-based regenerated fiber cloth, acetate, triacetate, etc .; synthetic fiber cloth such as polyethylene fiber, polyvinyl chloride fiber, acrylic fiber, polyclar fiber, etc .; And any of them is preferably used.

The above-mentioned raw fabric was subjected to a flame-retarding treatment using, for example, an organic phosphoric acid-based flame retardant under conditions such that the effective adhesion amount was 25% by weight or more of the weight of the raw fabric. Preferably, it is

Further, the above-mentioned raw fabric material may be provided with a decorative layer by printing, flocking, applying a decorative material or the like on the surface which is not bonded to the backing material.

The type of backing material used for the textile wallpaper according to the third invention is not particularly limited,
Various papers, various cloths, etc. are mentioned, and all are suitably used.

The above-mentioned backing material may have been subjected to a flame-retardant treatment using, for example, an organic phosphoric acid-based flame retardant under the condition that the total weight is 80 g / m ² or less. preferable.

The method for producing a woven fabric wallpaper according to the third invention is not special, and a conventionally known device such as a laminator or a roll coater is used, and the adhesive composition according to the first or second invention is used as a backing adhesive. A desired fabric wallpaper can be obtained by bonding and laminating the back surface (non-decorative surface) of the above-described fabric raw material and one surface of the backing material by an ordinary method.

The coating amount of the adhesive composition at the time of the production is not particularly limited, but is 2% by weight after drying.
It is preferably about 0 g / m ² .

[0058]

The adhesive composition according to the first or second aspect of the present invention
For vinyl acetate resin emulsion which is the main component,
As the flame retardant (auxiliary) agent contains specific amounts of titanium oxide, aluminum hydroxide, and heat-expandable graphite (first invention) or silicone-based powder (second invention), excellent flame retardancy Since it does not contain halogen-containing compounds, it does not generate toxic gases or substances that pollute the work environment.

The adhesive composition according to the first or second aspect of the present invention comprises titanium oxide, aluminum hydroxide and thermally expandable graphite (100 parts by weight) based on 100 parts by weight of the resin component of the vinyl acetate resin emulsion as the main component. Since the total content of the (1 invention) or the silicone-based powder (2nd invention) is as small as 50 parts by weight or less, storage stability and adhesive properties are not impaired.

Further, the adhesive composition according to the second invention comprises:
Since it contains the titanium oxide and the specific amount of the silicone-based powder, it is possible to obtain a white dried film having excellent concealing properties, and it is widely used without limiting the color of an adherend such as a wall covering material.

The woven fabric wallpaper according to the third aspect of the invention has excellent fire protection performance since the raw fabric sheet and the backing material are adhered by the adhesive composition according to the first or second aspect of the invention.
In particular, by using the fire retardant-treated textile wallpaper and the fire-retardant-treated backing material, the fire retardancy of the obtained textile wallpaper becomes even more excellent. It passes the second rank of the fire protection performance of textile wallpaper set by the association.

[0062]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”, and “%” means “% by weight” unless otherwise specified.

[0063]

【Example】

(Example 1)

( 1) Weight of vinyl acetate resin emulsion
In a reactor equipped with a mixing stirrer, a reflux condenser, a thermometer and a dropping funnel, 100 parts of water and polyvinyl alcohol (trade name "Kuraray PVA-CST", saponification degree 96 mol%, average polymerization degree 1700, manufactured by Kuraray Co., Ltd.) 10 parts were charged and stirred at 95 ° C. for 1 hour to obtain an aqueous solution of polyvinyl alcohol (hereinafter referred to as “PVA”). Next, this PVA aqueous solution was added to 70
After cooling to ℃, 20 parts of a vinyl acetate monomer and 0.08 parts of ammonium persulfate (polymerization catalyst) were added thereto to carry out initial polymerization. Next, 80 parts of vinyl acetate monomer was added to 3 parts.
The polymerization catalyst aqueous solution was added dropwise over a period of time.
Parts (hydrogen peroxide 0.24 parts, tartaric acid 0.15 parts and water 10 parts) were added dropwise over 3.5 hours, and emulsion polymerization was carried out at 70 ° C. Furthermore, after the end of the dropping of the vinyl acetate monomer,
After aging at 70 ° C. for 1 hour and cooling, a vinyl acetate resin emulsion having a nonvolatile content of 50% was obtained.

( 2) Preparation of Adhesive Composition To 100 parts by weight of the resin component of the vinyl acetate resin emulsion obtained above, an aqueous slurry of rutile-type titanium oxide (trade name “PSM-3272W”, non-volatile content) 57%,
After adding and mixing 11 parts of Okunikoshi Co., Ltd. and 6 parts of aluminum hydroxide (average particle diameter of secondary particles 0.6 μm), heat-expandable graphite (trade name “Expandable Graphite 8099”, 1000 ° C.) Expansion degree of 160-2
(00 cc / g, manufactured by Chuo Kasei Co., Ltd.) and uniformly dispersed and mixed to obtain an adhesive composition.

( 3) Evaluation The performance (viscosity, film forming property, storage stability, combustion test) of the adhesive composition obtained above was evaluated by the following methods. The results were as shown in Table 1. The evaluation was performed in an atmosphere of 20 ° C. and 65% RH unless otherwise specified.

[0068] Using the viscosity BH type rotational viscometer, rotor # 4, the rotational speed 10r
pm, the viscosity of the adhesive composition at 30 ° C. (m
pa · s) was measured.

The film forming property of the adhesive composition at 2 ° C. was visually observed in accordance with JIS 5-6828 “Testing method for vinyl acetate resin emulsion”, and the film forming property was evaluated according to the following criteria. .

[Judgment criteria]

○ ‥‥ The dried film was a transparent and uniform continuous film × ‥‥ The dried film was cloudy or did not form a continuous film

Storage stability The adhesive composition was placed in a closed container, allowed to stand at 20 ° C. for 90 days, opened, and the state of the adhesive composition was visually observed. Was evaluated.

[Judgment criteria]

○ ‥‥ No precipitate or phase separation was observed, and the adhesive composition was in a uniform state. × ‥‥ Precipitation or phase separation was observed.

Combustion test The adhesive composition was applied on a polyethylene plate and dried to obtain a dry film having a thickness of 2 mm. Next, a certain weight (A) of the obtained dried film was sampled, one end thereof was ignited and burned, and the remaining weight (B) of the dried film after a certain period of time was measured. %). Number is 10
It can be said that the closer to 0%, the better the flame retardancy. Film remaining rate (%) = (B / A) × 100 Further, the smoke emission state during combustion was visually observed, and the smoke emission was evaluated according to the following criteria.

[Judgment criteria]

 ○ ‥‥ Smoke was hardly observed △ ‥‥ Moderate smoke was observed × ‥‥ A large amount of smoke was observed

Example 2 In the preparation of the adhesive composition, the addition amount of aluminum hydroxide was 10 parts based on 100 parts of the resin component of the vinyl acetate resin emulsion, and the addition of expandable graphite “expandable graphite 8099” was added. An adhesive composition was obtained in the same manner as in Example 1 except that the amount was changed to 16 parts.

Example 3 In the preparation of the adhesive composition, 100 parts by weight of the vinyl acetate resin emulsion was added to the heat-expandable graphite “Expandable Graphite 8”.
[099] In the same manner as in Example 1, except that 20 parts of silicone powder (trade name "DC-7105", manufactured by Dow Corning Toray Silicone Co., Ltd.) was added instead of 20 parts, the adhesive composition was used. I got

Example 4 In the preparation of the adhesive composition, 100 parts of the resin component of the vinyl acetate resin emulsion was added to the heat-expandable graphite “Expandable Graphite 8”.
099 ”instead of 16 parts, silicone-based powder“ DC-
An adhesive composition was obtained in the same manner as in Example 2 except that 16 parts of “7105” was added.

Comparative Example 1 An adhesive composition was prepared in the same manner as in Example 1 except that none of titanium oxide, aluminum hydroxide, thermally expandable graphite and silicone powder was added. An adhesive composition was obtained.

(Comparative Example 2) An adhesive composition was prepared in the same manner as in Example 1 except that aluminum hydroxide, thermally expandable graphite and silicone-based powder were not added in the preparation of the adhesive composition. Obtained.

(Comparative Example 3) In the preparation of the adhesive composition, the addition amount of aluminum hydroxide was 10 parts based on 100 parts by weight of the resin component of the vinyl acetate resin emulsion.
An adhesive composition was obtained in the same manner as in Example 1, except that the heat-expandable graphite and the silicone-based powder were not added.

(Comparative Example 4) In the preparation of the adhesive composition, the addition amount of aluminum hydroxide was 20 parts with respect to 100 parts by weight of the resin component of the vinyl acetate resin emulsion.
An adhesive composition was obtained in the same manner as in Example 1, except that the heat-expandable graphite and the silicone-based powder were not added.

The performance of the seven types of adhesive compositions obtained in Examples 2 to 4 and Comparative Examples 1 to 4 was evaluated in the same manner as in Example 1. The results were as shown in Table 1.

[0080]

[Table 1]

As shown in Table 1, the adhesive composition of Example 1 or Example 2 according to the first invention and the adhesive composition of Example 3 or Example 4 according to the second invention were excellent. In addition to exhibiting flame retardancy, it also has excellent film forming properties and storage stability.

On the other hand, the adhesive composition of Comparative Example 1 containing none of titanium oxide, aluminum hydroxide, heat-expandable graphite and silicone-based powder, aluminum hydroxide, heat-expandable graphite and silicone-based powder The adhesive composition of Comparative Example 2, which does not contain, has extremely poor flame retardancy and poor smoke emission. Also, the adhesive composition of Comparative Example 3 or Comparative Example 4, which does not contain the heat-expandable graphite and silicone-based powder, is inferior in flame retardancy as compared with the adhesive compositions of Examples 1 to 4.

[0083]

As described above, the adhesive composition according to the first or second aspect of the present invention does not contain a halogen-containing compound, so that it does not generate toxic gases or substances that pollute the working environment, and is excellent in difficulty. Since it exhibits flammability and also has excellent storage stability and adhesive properties, it is suitably used mainly for adhesion of building wall coverings.

The adhesive composition according to the second aspect of the present invention forms a white dried film having excellent concealing properties, so that it is widely and suitably used without being affected by the color of an adherend such as a wall covering. .

Further, the textile wallpaper according to the third invention produced using the adhesive composition according to the first invention or the second invention has an excellent fire protection performance, and is a textile wallpaper specified by the Wall Materials Association. It is suitable for use mainly as a wall covering for buildings, etc., because it passes the second rank of fire safety performance.

Claims (3)

[Claims] 1. A resin composition containing 100 parts by weight of a vinyl acetate resin emulsion, 6 to 12 parts by weight of titanium oxide, 6 to 18 parts by weight of aluminum hydroxide, and 1 part of thermally expandable graphite.
An adhesive composition comprising 0 to 20 parts by weight. 2. A vinyl acetate-based resin emulsion containing 6 to 12 parts by weight of titanium oxide, 6 to 18 parts by weight of aluminum hydroxide, and 10 to 20 parts by weight of a silicone-based powder based on 100 parts by weight of a resin component. An adhesive composition comprising: 3. A woven wallpaper, wherein the woven fabric and a backing material are adhered by the adhesive composition according to claim 1 or 2.