JP3288540B2 - Foam wallpaper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamed wallpaper which is used as a building material, especially as an interior material, and which conforms to the quasi-noncombustible (grade 2) and nonflammable (grade 1) of the Building Standards Law.

[0002]

2. Description of the Related Art Conventionally, foamable soft polyvinyl chloride is mainly used as a material for a surface layer of foamed wallpaper. However, polyvinyl chloride generates toxic gas of hydrogen chloride and a large amount of black smoke when incinerated. This is causing environmental problems.

In order to solve this problem, a wallpaper using an ethylene-vinyl acetate copolymer and an emulsion such as an acrylic resin (JP-A-6-143471 and JP-A-6-47875) has been disclosed. In addition, the workability, the embossability, etc. are inferior, and when the composition has a higher hardness, the cold resistance decreases, and when the composition is soft, the composition becomes tacky.

Further, the wallpaper described in the above-mentioned publication has less influence on environmental pollution at the time of incineration than polyvinyl chloride, but does not have physical properties as good as polyvinyl chloride. That is, in the case of the emulsion, when the expansion ratio was increased to 3 times or more, the surface strength was weakened, and the elasticity tended to be lower than that of the emulsion made of polyvinyl chloride.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in order to solve such problems, and it is an object of the present invention to provide a surface material having sufficient strength for practical use even during foaming. Another object of the present invention is to provide a foamed wallpaper that generates less toxic gas and smoke during incineration.

[0006]

In order to solve the above-mentioned problems, the present invention provides: (a) an alkyl acrylate and / or methacrylate having an alkyl group having 1 to 8 carbon atoms and one or more alkyl methacrylates; 3 carbon atoms having a carboxyl group
(B) 50-120 parts by weight of a phthalic acid alkyl ester-based plasticizer having a molecular weight of 360-480. (c) 3 to 15 parts by weight of a microcapsule type foaming agent (d) 50 to 150 parts by weight of aluminum hydroxide A plastisol obtained by mixing as a main component is coated on flame-retardant paper or inorganic paper and foamed. Provide a characteristic foam wallpaper.

Hereinafter, the present invention will be described in detail. In the present invention, the alkyl acrylate and / or methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms used in the component (a) (hereinafter referred to as (meth) acrylate-based monomer) is ethyl acrylate. Propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, and the like. These may be used alone or in combination of two or more.

Also, a monomer of α, β-ethylenically unsaturated carboxylic acid having 3 to 9 carbon atoms and having at least one free carboxyl group (hereinafter referred to as component (a))
Examples of the unsaturated carboxylic acid monomer) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid; maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloro acid. Unsaturated dicarboxylic acids such as maleic acid and anhydrides; unsaturated dicarboxylic acids such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate and monobutyl itaconate And its derivatives.

These may be used alone or in combination of two or more. Among them, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and itaconic acid are particularly preferable in physical properties. It is preferable because it is excellent.

The amount of the unsaturated carboxylic acid monomer based on the total amount of the component (a) is preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight. It is. If it is less than 0.5% by weight, the viscosity stability of the plastisol during storage decreases. If the content is more than 10% by weight, the sheet obtained by heating the plastisol using the plasticizer (b) in the present invention tends to bleed.

Further, together with the (meth) acrylate monomer and the unsaturated carboxylic acid monomer, other monomers copolymerizable as desired can be used. Other copolymerizable monomers used as desired include, for example, aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; cyanidation such as acrylonitrile, methacrylonitrile, and vinylidene cyanide. Vinyl compounds; 2-hydroxyethyl acrylate;
-Hydroxyethyl methacrylate, 3-hydroxybutyl acrylate, 2-hydroxyethyl fumarate,
Examples thereof include hydroxybutyl vinyl ether, monobutyl maleate, glycidyl methacrylate, and butoxyethyl methacrylate. These may be used alone or in combination of two or more, and the amount of use is usually selected in the range of 0 to 40% by weight based on the total weight of the monomers. More preferably, it is used in the range of 0 to 30% by weight. If the amount is more than 40% by weight, the mechanical properties of the molded article tend to decrease.

As a method for preparing the copolymer resin particles of the component (a), a latex obtained by reacting each of the above monomers by emulsion polymerization or fine suspension polymerization is obtained by spray drying or the like. As a result, resin particles having a particle size substantially equal to that of the polyvinyl chloride resin for plastisol can be obtained, and a plastisol having a viscosity equivalent to that of the polyvinyl chloride resin can be obtained. The physical properties of the foamed molded product are the same as those obtained by using the vinyl chloride resin. It also has the advantage of not generating hydrogen chloride during incineration.

The phthalic acid alkyl ester plasticizer having a molecular weight of 360 to 480 used as the component (b) of the present invention includes dipeptyl phthalate (hereinafter referred to as a plasticizer) (molecular weight 363), di-n- Octyl phthalate (390), di-2-ethylhexyl phthalate (390), di-n-nonyl phthalate (419), diisononyl phthalate (419), diisodecyl phthalate (447), di-n-undecyl phthalate (475), but DOP (di-2-ethylhexyl phthalate), which is most widely used in the field of synthetic resin processing and molding, is preferable as the main component. The amount of such a plasticizer is 5 parts per 100 parts by weight of component (a).
The amount is preferably from 0 to 120 parts by weight, more preferably from 60 to 80 parts by weight. If the amount is less than 50 parts by weight, the viscosity is too high, and the component (d) becomes difficult to enter, and the flame retardancy and smoke resistance are reduced.
On the other hand, if the amount is more than 120 parts by weight, the molded article tends to be too soft and sticky.

Further, it is also possible to use the following plasticizers as subcomponents in an amount of 40% by weight or less of the total plasticizer amount. For example, phthalic acid derivatives such as dibutyl phthalate, diisobutyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate and dicyclohexyl phthalate; isophthalic acid derivatives and tetrahydrophthalic acid derivatives corresponding thereto; di-n-butyl adipate, di- ( Adipic acid derivatives such as 2-ethylhexyl) adipate, diisodecyl adipate and diisononyl adipate; azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctyl azelate and di-n-hexyl azelate; di-n-butyl sebacate , Di- (2-ethylhexyl) sebacate and other sebacic acid derivatives; tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl tri Trimellitic acid derivatives such as reitate, triisooctyl trimellitate, tri-n-hexyl trimellitate and triisononyl trimellitate; tetra- (2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate and the like Pyromellitic acid derivative; triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-
Citric acid derivatives such as (2-ethylhexyl) citrate; monomethyl itaconate monobutyl itaconate;
Itaconic acid derivatives such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate and di- (2-ethylhexyl) itaconate; oleic acid derivatives such as butyl oleate, glyceryl monooleate and diethylene glycol monooleate; methyl acetyl ricinolate, butyl acetyl Ricinoleate derivatives such as ricinoleate, glyceryl monoricinoleate and diethylene glycol monoricinoleate; stearic acid derivatives such as n-butyl stearate, glycerin monostearate and diethylene glycol distearate; diethylene glycol monolaurate and diethylene glycol diperargonate; Other fatty acid derivatives such as pentaerythritol fatty acid ester; diethylene glycol dibenzoate, dipropylene glycol Chole dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), dibutylmethylenebisthioglycolate, 2,2,4- Trimethyl-
Glycol derivatives such as 1,3-pentanediol diisobutyrate; glycerin derivatives such as glycerol triacetate and glycerol tributyrate; tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl Phosphoric acid derivatives such as phosphate, tricresyl phosphate, trixylenyl phosphate, and tris (chloroethyl) phosphate; and epoxidized soybean oil and glycol ethers. One of these plasticizers may be used in combination, or two or more of them may be used in combination.

The viscosity stability of the plastisol, the mechanical properties of the heating sheet, the smoke-proof property during burning, the design property and the workability when used as wallpaper can be adjusted by adding a plasticizer composed of these as desired. Can be.

As the microcapsule type foaming agent used as the component (c) of the present invention, organic foaming agents such as polyacrylonitrile, phenol resin, epoxy resin, urea resin and pitch are useful. In particular, polyacrylonitrile-based expanded microcapsules containing low-boiling hydrocarbons are effective.

The foaming start temperature of the microcapsule type foaming agent is preferably in the range of 110 to 150 ° C.
The compounding amount of the microcapsule type foaming agent is preferably 3 to 20 parts by weight, more preferably 7 to 15 parts by weight. If the amount is less than 3 parts by weight, the foaming ratio is low, and the design of the wallpaper is inferior. If the amount is more than 20 parts by weight, the foamed cells are extremely rough.

By using these microcapsule type foaming agents, dense foaming becomes possible and the design of wallpaper can be improved.

The aluminum hydroxide used as the component (d) in the present invention preferably has a particle size of 1 to 10 μm. When it is 1 μm or less, the viscosity of the plastisol tends to increase, and when it is 10 μm or more, sedimentation and separation may occur during storage of the plastisol.

The amount of aluminum hydroxide is preferably in the range of 50 to 150 parts by weight based on 100 parts by weight of the copolymer resin (a). More preferably, it is 60 to 130 parts by weight. In the present invention, since a chlorine-containing material is not used as a flame retardant, about 100 parts by weight of aluminum hydroxide is required to impart flame retardancy, which is an important quality of wallpaper. When the amount is less than 50 parts by weight, the effect of flame retardancy and smoke resistance is reduced. When the amount is more than 150 parts by weight, the viscosity of the plastisol is significantly increased.

Further, 50 parts of the aluminum hydroxide
The amount of not more than% by weight can be replaced by a hydroxide or calcium carbonate of a metal belonging to Groups I to III of the periodic table, if necessary.

Similarly, various pigments can be used, and in particular, a titanium oxide pigment is preferably used. The amount of the pigment is usually 10 to 100 parts by weight of the copolymer resin particles.
20 parts by weight.

In addition, a diluent is usually used for the purpose of improving high-speed coating characteristics. Aliphatic hydrocarbons are particularly effective as diluents. The amount of the diluent is usually 3 to 20 parts by weight per 100 parts by weight of the copolymer resin particles. If it is less than 3 parts by weight, the viscosity reducing effect will be low
If the amount is more than 20 parts by weight, the viscosity of the plastisol tends to be dilatant under high shearing force.

Aromatic and naphthenic hydrocarbons are not desirable because the viscosity of the plastisol using the copolymer resin particles of the component (a) of the present invention increases significantly with time.

For mixing the plastisol of the present invention, a homomixer, a planetary mixer or a Henschel mixer can be used as in the case of the plastisol of polyvinyl chloride.

Examples of the flame-retardant paper or inorganic paper according to the present invention include paper impregnated with a water-soluble flame retardant such as guanazine sulfanilate and guanazine phosphate, and paper mainly containing self-extinguishing aluminum hydroxide. Can be used, and the paper thickness is preferably 100 to 150 μm.

The plastisol of the present invention is coated on the flame-retardant paper or the inorganic paper by the knife coater method, the comma coater method, the gravure printing method, the roll coating method, and the rotary silk printing as in the case of the polyvinyl chloride plastisol. Method, reverse coater method and the like can be used.

The flame-retardant paper or inorganic paper coated in this way is dried with hot air, subjected to gravure printing, heated and foamed, and embossed to obtain the foamed wallpaper of the present invention.

[0029]

According to the present invention, since the resin layer of the wallpaper is mainly composed of an acrylic copolymer, unlike a conventional vinyl chloride wallpaper,
Generation of harmful gases such as hydrochloric acid gas during combustion is eliminated, and the generation of black smoke can be significantly reduced by using a large amount of aluminum hydroxide in combination.

The polymethyl methacrylate homopolymer resin most frequently used as a plastisol resin other than vinyl chloride cannot be used because the bleeding phenomenon occurs remarkably when the plasticizer (b) of the present invention is used. The acrylic copolymer according to the present invention can be converted into a plastisol having a low viscosity equivalent to that of vinyl chloride and excellent storage stability without causing a bleeding phenomenon by using a general-purpose plasticizer (b). Since the present inventors have found that this is possible, it is possible to obtain, on the same production line, wallpaper processing performance equivalent to that of a vinyl chloride paste having excellent processing characteristics.

Further, by using a microcapsule type foaming agent as a foaming agent, a denser and more uniform foam can be obtained, and a wallpaper having an excellent design can be obtained.

The foamed wallpaper of the present invention obtained as described above can be used for general purposes such as ordinary houses and offices as interiors of buildings.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments.

Example 1 70 parts by weight of methyl methacrylate and 27 parts by weight of butyl methacrylate as a (meth) acrylate monomer, 3 parts by weight of methacrylic acid as an unsaturated carboxylic acid monomer, and benzoyl peroxide as a polymerization initiator 1.0 part by weight, 0.5 part by weight of sodium dodecylbenzenesulfonate as an emulsifier, 1.5 parts by weight of a higher alcohol having 18 carbon atoms as a dispersant and 15 parts of water.
0 parts by weight, and then homogenized under high shear with a homomixer to adjust the oil phase to a fine suspension having a particle size of 1 to 5 μm, and then transferred to a polymerization vessel and stirred at 65 ° C. for 5 hours. Polymerization was carried out below. The latex thus obtained was dried by spray drying in a nitrogen stream at 170 ° C. The average particle size of single particles of the polymer resin particles thus obtained is 2.
It was 0 μm.

With respect to 100 parts by weight of the polymer resin particles obtained as described above, 70 parts by weight of di-2-ethylhexyl phthalate as a plasticizer and 1 part of aluminum hydroxide were used.
00 parts by weight, 12 parts by weight of a low-boiling hydrocarbon-encapsulated polyacrylonitrile-based microcapsule as a microcapsule foaming agent, 15 parts by weight of a paraffin-based diluent, and 15 parts by weight of a titanium oxide pigment were blended, and a crusher was used together therewith. To mix for 20 minutes to prepare a plastisol. The following evaluations were performed on the plastisol according to the present invention thus obtained.

<Plasticizer bleeding property> 5 g of a plastisol of each composition was collected in an aluminum dish having a diameter of 50 mm, and 1
What was molded by heating at 40 ° C. for 10 minutes was left at room temperature for one week, and the seepage of the plasticizer on the free surface side was visually observed. A sample without bleeding was rated as “○”, and a sample with no bleeding was rated as “x”.

<Design (Embossing)> Thickness is 120 μm
m of flame retardant paper, apply 250 μm of plastisol,
After foaming four times by heating at 1 ° C. for 1 minute, ten cylindrical embossing pins having a diameter of 1.5 mm and a length of 0.8 mm were embossed. The average embossed depth after embossing was measured from the surface, and the ratio to the pin length was expressed as embossability in%. Consider 80% or more as good.

<Workability>"JISA6921-197"
6 ". When the peeling was not found by visual inspection, it was marked with "O", and when the peeling was found, it was marked with "x".

<Sol viscosity> Using a BM type viscometer,
pm, room temperature 23 ° C., humidity 60%, measured in the unit of measurement poise.

<Change over time of sol viscosity> One week, room temperature 23
The viscosity was measured after the temperature was maintained at 60 ° C. and the humidity was 60%. The viscosity was measured by the ratio of the viscosity excluding the viscosity on the first day. When it is closer to 1, the change with time is small, and when it is larger than 1, the change with time is large.

<Flammability test> According to the Ministry of Construction Public Notice No. 1372 (designating quasi-incombustible materials and flame-retardant materials)
The measurement was performed according to “JIS A1321-1975”. Temperature time area (td
θ), and the smoke emission coefficient per unit area (CA)
And the amount of generated hydrochloric acid gas was measured by the NBS method (mg / g).

<Wallpaper surface strength>"JIS A6921-
1976 ". Dry rubbing and wet rubbing were performed, and both vertical and horizontal grades were grade 4 or higher, and grades 4 and below were rated x.

<Example 2> 75 parts by weight of methyl methacrylate and 22 parts by weight of 2-ethylhexyl acrylate as a (meth) acrylate monomer, and methacryl as an unsaturated carboxylic acid monomer A plastisol was obtained in the same manner as in Example 1 except that the amount of the acid was changed to 3 parts by weight, and the same evaluation as above was performed.

<Comparative Example 1> A plastisol was obtained in the same manner as in Example 1 except that a homopolymer of 100 parts by weight of methyl methacrylate was used instead of the copolymer resin particles, and the same evaluation as above was performed. As a result, the heat-formed product caused a remarkable bleeding phenomenon. Therefore, it was not possible to prepare a test sheet.

Comparative Example 2 A plastisol was prepared in the same manner as in Example 1 except that a vinyl chloride-vinyl acetate copolymer (95 parts by weight of vinyl chloride and 5 parts by weight of vinyl acetate) was used instead of the copolymer resin particles. Then, the same evaluation as above was performed. As a result, chlorine gas was generated in the flammability test, and the calorific value,
The smoke emission rate was also high.

Comparative Example 3 An ethylene-vinyl acetate copolymer (an emulsion of 70 parts by weight of ethylene and 30 parts by weight of vinyl acetate) was used in place of the copolymer resin particles. The emulsion has 100 parts by weight of the polymer component dispersed in 150 parts by weight of water. 5 parts by weight of a thickener (sodium polyacrylate), 50 parts by weight of a filler (aluminum hydroxide) and 1 part by weight of an antifoaming agent (silicone emulsion) are added and mixed, and then applied to a flame-retardant paper. Water was evaporated at a temperature of 40 ° C. or less, and then foaming was carried out by heating. As a result, the workability and the scratching strength of the wallpaper surface were not sufficient.

<Comparative Example 4> A plastisol was obtained in the same manner as in Example 1 except that the plasticizer was changed to 70 parts by weight of phosphate ester tricresyl phosphate, and the same evaluation as described above was performed. As a result, there was a problem in storage stability of the viscosity of plastisol and workability of wallpaper.

Comparative Example 5 A plastisol was obtained in the same manner as in Example 1 except that the plasticizer was replaced with 70 parts by weight of dibutyl phthalate having a molecular weight of less than 360 and 278, and the same evaluation as above was carried out. As a result, there was a problem in storage stability of the viscosity of plastisol.

<Comparative Example 6> A plastisol was obtained in the same manner as in Example 1 except that magnesium hydroxide was used instead of aluminum hydroxide, and the same evaluation as described above was performed. As a result, there was a problem in flammability and coatability of the sol under a high shear rate.

Comparative Example 7 A plastisol was obtained in the same manner as in Example 1 except that calcium hydroxide was used instead of aluminum hydroxide, and the same evaluation as described above was performed. As a result, there was a problem in flammability and coatability of the sol under a high shear rate.

Comparative Example 8 A plastisol was obtained in the same manner as in Example 1, except that the microcapsule type foaming agent was replaced with 3 parts by weight of azodicarbonamide as a general-purpose organic foaming agent, and the same evaluation as above was carried out. . As a result, the embossability was insufficient.

Comparative Example 9 A plastisol was obtained in the same manner as in Example 1 except that the microcapsule-type foaming agent was replaced with 5 parts by weight of sodium bicarbonate, a general-purpose inorganic foaming agent, and evaluated in the same manner as described above. . As a result, the embossability was insufficient.

Comparative Example 10 A plastisol was obtained in the same manner as in Example 1 except that the amount of aluminum hydroxide was changed to 30 parts by weight, and the same evaluation as described above was performed. As a result, the combustion performance decreased.

<Comparative Example 11> A plastisol was obtained in the same manner as in Example 1 except that the amount of the microcapsule type foaming agent was changed to 2 parts by weight, and the same evaluation as above was performed. result,
Embossing performance was greatly reduced.

<Comparative Example 12> A plastisol was obtained in the same manner as in Example 1 except that the amount of the microcapsule type foaming agent was changed to 20 parts by weight, and the same evaluation as above was performed. As a result, an overfoamed state was obtained, and the embossing performance was similarly reduced.

<Comparative Example 13>

Comparative Example 13 A plastisol was obtained in the same manner as in Example 1 except that the amount of the plasticizer was changed to 48 parts by weight, and the same evaluation as described above was performed. As a result, the coating viscosity of the plastisol increased, making it difficult to apply the composition to flame-retardant paper. Even when the amount of the diluent was further increased, the coating speed could not be increased to 50 m / min or more. Therefore, it was not possible to create a test sheet

The results are shown in Table 1.

[0059]

[Table 1]

[0060]

The wallpaper of the present invention uses a special acrylic copolymer resin, so that the amount of smoke generated during combustion is smaller than that of vinyl chloride wallpaper, which is the mainstream of the conventional wallpaper, and
Almost no chlorine gas was generated. Also,
The design is also excellent. Further, a foamed wallpaper which is flexible and has good workability can be obtained by using a predetermined plasticizer. In particular, the surface strength is superior to the wallpaper made of the EVA emulsion in Examples.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI D21H 21/56 D21H 21/56 (72) Inventor Takeo Kobayashi 2-6-1 Marunouchi, Chiyoda-ku, Tokyo Inside Zeon Corporation ( 72) Inventor Atsushi Tsukamoto 1-2-1 Yoko, Kawasaki-shi, Kanagawa Japan Zeon Co., Ltd. Research and Development Center Examiner Hiroaki Hirai (56) References JP-A-6-33399 (JP, A) JP-A-6 −33380 (JP, A) JP-A-6-47875 (JP, A) JP-A-8-100398 (JP, A) JP-A-6-22396 (JP, U) (58) Fields investigated (Int. . ^7, DB name) D21H 11/00 - 27/42

Claims (1)

(57) [Claims] (A) an alkyl acrylate and / or methacrylic acid alkyl ester monomer having an alkyl group having 1 to 8 carbon atoms and an α having 3 to 9 carbon atoms having at least one free carboxyl group; (B) 50-120 parts by weight of an alkyl phthalate plasticizer having a molecular weight of 360 to 480 (c) microcapsules Foaming characterized in that a plastisol obtained by mixing 3 to 15 parts by weight of a mold blowing agent (d) with 50 to 150 parts by weight of aluminum hydroxide as a main component is applied to flame-retardant paper or inorganic paper and foamed. wallpaper.