JPH08246397A - Foamed wall paper - Google Patents

Abstract

PURPOSE: To obtain foamed wall paper capable of suppressing a gas emitting in sheeting by low-temperature treatment (<=150 deg.C), printing and blowing without using a compounding agent having low-temperature volatility (<=300 deg.C) in production of the foamed wall paper by a gravure printing machine. CONSTITUTION: This foamed wall paper is obtained by blending 100 pts.wt. of copolymer resin particles comprising an acrylic acid alkyl ester and/or a methacrylic acid alkyl ester containing a 1-8C alkyl group and a monomer of an α, β-ethylenic unsaturated carboxylic acid containing one or more free carboxyl groups and 3-8 carbons with 50-120 pts.wt. of a phthalic acid alkyl ester-based plasticizer having 360-480 molecular weight, 3-15 pts.wt. of a blowing agent and 50-150 pts.wt. of aluminum hydroxide to give a plastisol, coating a paper base with the plastisol, drying and blowing.

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 satisfies the standards of quasi-incombustible (class 2) and noncombustible (class 1) of the Wallpaper Association.

[0002]

2. Description of the Related Art Soft vinyl chloride is mainly used as a plastisol used for the foamed wallpaper used for the above-mentioned purposes. However, polyvinyl chloride causes environmental problems because hydrogen chloride, which is a toxic gas, and a large amount of black smoke are generated when incinerated. Further, even at the time of production, even if a copolymer is used, a high temperature treatment of 180 ° C. or higher is required, so a gas containing a plasticizer is generated, and a large amount of equipment is required for the production environment and exhaust gas treatment. In addition, problems such as the generation of tars are also occurring in production machines. Especially in the gravure printing machine, since the solvent is used at the same time,
High temperature heating devices are very dangerous.

To solve this problem, it is considered to use ethylene / vinyl acetate copolymer.
Even if the coating suitability and the gravure suitability are satisfied by the treatment at 0 ° C. or lower, the sheet strength, the viscosity, the foaming suitability and the like are not satisfied.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its object is to have low temperature volatility (300 ° C.) during production in a gravure printing machine. It is an object of the present invention to provide a foamed wallpaper that can suppress generated gas as much as possible when performing sheeting, printing and foaming at low temperature treatment (150 ° C or less) without using the compounding material of the following).

[0005]

In order to solve the above-mentioned problems, the present invention provides (1) an alkyl acrylate and / or methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and one or more free carboxyl groups. And carbon number 3 to
100 parts by weight of copolymer resin particles consisting of 8 monomers of α, β-ethylenically unsaturated carboxylic acid (2) 50 to 120 parts by weight of phthalic acid alkyl ester plasticizer having a molecular weight of 360 to 480 (3) 3 to 15 parts by weight of a foaming agent (4) A plastisol obtained by mixing 50 to 150 parts by weight of aluminum hydroxide is coated on a paper base material,
A foamed wallpaper characterized by being dried and foamed.

The present invention will be described in detail below. Examples of the (1) acrylic acid alkyl ester and / or methacrylic acid alkyl ester whose alkyl group has 1 to 8 carbon atoms include ethyl acrylate, propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate. , Ethyl methacrylate, n-butyl methacrylate, and the like, and these may be used alone or in combination of two or more.

Further, α, which has one or more free carboxyl groups and 3 to 8 carbon atoms, used as the same component,
Examples of the β-ethylenically 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, and citraconic acid. Unsaturated dicarboxylic acids such as chloromaleic acid and its anhydrides, monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconic acid, etc. Examples thereof include acid monoesters and their derivatives.

These may be used alone or in combination of two or more, and among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and itaconic acid are particularly preferable. The amount used is preferably in the range of 0.5 to 10% by weight, based on the total amount of monomers, and 1 to 5% by weight.
Is a more preferable range. When it is less than 0.5% by weight, the viscosity stability of plastisol during storage is lowered. 10% by weight
In the above, the sheet obtained by heating the plastisol containing the component (b) plasticizer in the present invention has a bleed tendency.

In addition to the (meth) acrylate-based monomer and the radical-polymerizable unsaturated carboxylic acid monomer, other copolymerizable monomers may be used if desired.
As the other copolymerizable monomer used as desired, for example, styrene, vinyltoluene, aromatic vinyl compounds such as α-methylstyrene, acrylonitrile, methacrylonitrile, and cyanide such as vinylidene cyanide. Vinyl compounds, further, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Examples thereof include 3-hydroxybutyl acrylate, 2-hydroxyethyl fumarate, hydroxybutyl vinyl ether, monobutyl maleate, glycidyl methacrylate, butoxyethyl methacrylate and the like.

These may be used alone or in combination of two or more, and the amount used is usually selected in the range of 0 to 40% by weight based on the total weight of the monomers. It is more preferably used in the range of 0 to 30% by weight. When it is used in an amount of 40% by weight or more, the mechanical properties of the sheet obtained by heating the plastisol containing the resin having the same composition tend to be deteriorated.

The copolymer resin particles as the component (1) are obtained by spray-drying a latex obtained by reacting the above-mentioned monomer by emulsion polymerization or fine suspension polymerization. The resin has a single average diameter of 1 to 5 μm, and the viscosity when made into plastisol is almost the same as that of plastisol using polyvinyl chloride resin particles having the same particle size as that obtained by fine suspension polymerization. Became.

The molecular weight used as the component (2) is 36.
As the phthalic acid alkyl ester plasticizer of 0 to 480, di-2 ethylhexyl phthalate (hereinafter referred to as DOP), which is most commonly used, is desirable as a main component. By using this, it is possible to obtain the one having excellent viscosity stability of plastisol, mechanical properties of the heating sheet, smoke generation at the time of combustion, designability and workability when used as wallpaper. The compounding amount of the plasticizer is 50 to 120 with respect to 100 parts by weight of the copolymer resin.
Weight part is preferable, and the range of 60-80 weight part is more preferable. Furthermore, the following plasticizers are used as subcomponents and the total amount of plasticizers is 4
It is also possible to use it at 0% by weight or less. For example, phthalic acid derivatives such as dibutyl phthalate, diisobutyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate and dicyclohexyl phthalate, corresponding isophthalic acid derivatives and tetrahydrophthalic acid derivatives, di-n-butyl adipate, di- ( Adipic acid derivatives such as 2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctyl azelate, di-n-hexyl azelate, di-n-butyl sebacate , Sebacic acid derivatives such as di- (2-ethylhexyl) sebacate, tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl tri Riteto, tri isooctyl trimellitate,
Trimellitic acid derivatives such as tri-n-hexyl trimellitate and triisononyl trimellitate, tetra-
(2-ethylhexyl) pyromellitate, tetra-n-
Pyromellitic acid derivatives such as octylpyromellitate,
Triethyl citrate, tri-n-butyl citrate,
Acetyl triethyl citrate, acetyl tri- (2-
Citric acid derivatives such as ethylhexyl) citrate, monomethyl itaconate monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate, etc. itaconic acid derivatives, butyl oleate, greceryl monooleate , Oleic acid derivatives such as diethylene glycol monooleate, methyl acetyl ricinoleate, butyl acetyl ricinoleate, glycer mono ricinoleate,
Ricinoleic acid derivatives such as diethylene glycol monoricinolate, stearic acid derivatives such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, and other fatty acids such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid ester. Derivatives, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-
(2-ethylbutyrate), triethyleneglycol di- (2-ethylhexoate), dibutylmethylenebisthioglycolate, 2,2,4-trimethyl-1,3-
Glycol derivatives such as pentanediol diisobutyrate, glycerol triacetate, glycerin derivatives such as glycerol tributyrate, tributyl phosphate, tri- (2-ethylhexyl) phosphate,
Phosphoric acid derivatives such as tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate, and further epoxidized soybean oil, glycol ethers and the like. . These plasticizers may be used alone or in combination of two or more.

As the foaming agent used as the component (3), polyacrylonitrile-based, phenol resin-based, polyvinylidene chloride-based, epoxy resin-based, urea resin-based, pitch-based microcapsule type organic foaming agent-based agents are useful, In particular, polyacrylonitrile-based expandable microcapsules containing low-boiling hydrocarbons are effective, and by using the microcapsule-type foaming agent, it is possible to obtain a dense foam or a wallpaper excellent in design. The microcapsule type foaming agent preferably has a foaming initiation temperature in the range of 90 to 130 ° C. The compounding amount of the microcapsule type foaming agent is preferably 3 to 20 parts by weight. When the amount is 3 parts by weight or less, the expansion ratio is low and the design of the wallpaper is poor, and when the amount is 20 parts by weight or more, the foamed cells are remarkably rough. In addition to the above foaming agents, organic foaming agents such as azodicarbonamide, ρ-toluenesulfonyl hydrazide, dinitrosopentamethylenetetramine, and 4,4′-oxybisbenzenesulfonyl hydrazide, and inorganic materials such as sodium hydrogen carbonate and sodium borohydride. It is also possible to partly use a foaming agent.

The aluminum hydroxide used as the component (4) preferably has a particle size of 1 to 10 μm. When it is 1 μm or less, the viscosity of plastisol tends to increase, and when it is 10 μm or more, sedimentation and separation may occur during storage of plastisol. The blending amount of aluminum hydroxide is 50 to 1 with respect to 100 parts by weight of the copolymer resin.
A range of 50 parts by weight is preferred. More preferably 60-1
If the amount is 30 parts by weight or less and 50 parts by weight or less, the effects of flame retardancy and smoke emission are reduced, and if it is 150 parts by weight or more, the viscosity of plastisol is significantly increased. It is also possible to replace a part of aluminum hydroxide with a hydroxide of a metal belonging to Groups I to III of the periodic table. In addition to this, a filler such as calcium carbonate can also be used if necessary.

Similarly, various pigments can be used, and in particular, the pigment used in the present invention is a titanium oxide pigment. The pigment content is preferably 10 to 20 parts by weight with respect to 100 parts by weight of the copolymer resin.

In addition to the above, a viscosity reducing agent is used for the purpose of adjusting the viscosity. Aliphatic hydrocarbons having 11 to 18 carbon atoms are particularly effective as the viscosity reducing agent. The compounding amount of the lower viscous agent is 3 to 15 parts by weight per 100 parts by weight of the above copolymer and resin particles. When it is less than 3 parts by weight, the effect of reducing the viscosity becomes low,
When it is 20 parts by weight or more, the viscosity of plastisol tends to be dilanthanum under high shearing force.

As the paper base material in the present invention, flame-retardant paper,
Inorganic paper or the like is used, and particularly flame-retardant paper of 100 to 140 g / m ² is preferably used.

Regarding the mixing of the above (1) to (4) and other additives, the mixture is mixed by using a homomixer, a planetary mixer or a Henschel mixer as in the case of plastisol of polyvinyl chloride. Can be made.

Regarding the production of the foamed wallpaper of the present invention, the knife coater method, the comma coater method, the gravure printing method, the roll coating method, the rotary silk printing method, which is used in the same manner as in the case of plastisol of polyvinyl chloride,
Although a reverse coater method or the like is used, the gravure printing method is preferable in terms of cost. The thus coated sheet is dried, subjected to gravure printing with a water-based ink and the above-mentioned plastisol, and heat-foamed to obtain the wallpaper of the present invention.

[0020]

As described above, according to the present invention, since the acrylic copolymer is the main component as the plastisol of the foamed wallpaper, unlike conventional vinyl chloride wallpaper, generation of harmful gas 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 together. In addition, since the gravure printing machine produces very little gas during production, it is possible to reduce pollution during production, suppress generation of tars in the production machine, and reduce the cost of exhaust gas equipment. The polymethylmethacrylate homopolymer resin, which is most often used as a resin for plastisols other than vinyl chloride, cannot be used because it causes a remarkable bleeding phenomenon in the sheet using the plasticizer of the component (4) of the present invention. The acrylic copolymer of the present invention can be used as a plastisol having a low viscosity comparable to that of vinyl chloride and excellent storage stability without causing a bleeding phenomenon by using a general-purpose (2) component plasticizer. Therefore, it is possible to obtain wallpaper processing performance equivalent to that of the vinyl chloride paste having excellent processing characteristics on the same production line.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention shown in FIG. 1 will be described below. Flame-retardant paper 1 is used as a paper base material, and 70 parts by weight of methyl methacrylate, 27 parts by weight of butyl methacrylate, 3 parts by weight of methacrylic acid, and dioctyl phthalate (hereinafter referred to as DOP) are used as a base paste for the foamed base layer 3. 60 parts by weight, 100 parts by weight of aluminum hydroxide, capsule foaming agent (Ekulpancell Co., Ltd.)
(Manufactured by: “DU # 642”) 8 parts by weight, titanium oxide pigment (manufactured by Hihiro Vix Co., Ltd .: “1017”) 18 parts by weight, viscosity reducing agent (manufactured by BYK Chem KK: “Disperplast-115”).
0 ") 10 parts by weight were mixed in a mixer,
Printing was performed using a solid plate having a plate depth of 210 μm. After drying
80% by weight of methyl methacrylate, 17 parts by weight of butyl methacrylate, 3 parts by weight of methacrylic acid, 55 parts by weight of DOP, and 80 parts by weight of aluminum hydroxide are used as a gravure printing paste for performing pattern printing with the water-based ink 5 and forming the foamed printing layer 4. Capsule foaming agent (Expancel Co., Ltd.)
Manufactured by: "DU # 551") 12 parts by weight, titanium oxide pigment (manufactured by Nikko Vix Co., Ltd .: "1017") 18 parts by weight,
Thickener (manufactured by BYK Chem Co., Ltd .: “Disperplast-115
0 ") 12 parts by weight were mixed in a mixer,
After printing the synchronous pattern, foaming was performed to obtain a foamed wallpaper of the present invention. In addition,
The waterproof resin layer 2 may be optionally provided between the paper base material and the base foam layer.

[0022]

As described above, by using a special acrylic copolymer resin in the foamed wallpaper of the present invention, compared to the vinyl chloride wallpaper, which is the mainstream of conventional wallpaper, it is possible to reduce The amount of smoke emitted is small, and it is possible to almost eliminate the generation of toxic gas. In addition, the design is excellent, and because the amount of gas generated during production by the gravure printing machine is extremely small, low pollution during production, suppression of tar in the production machine, and cost reduction of exhaust gas equipment And so on.

[0023]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a cross-sectional structure of a foamed wallpaper according to an embodiment of the present invention.

[Explanation of symbols]

1 ... Flame-retardant paper 2 ... Water-resistant resin layer 3 ... Foaming base layer 4 ...
Foam printing layer 5 ... Water-based ink

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area D21H 19/20 D21H 1/34 E // C08L 33:06

Claims (1)

[Claims] (1) Acrylic acid alkyl ester and / or methacrylic acid alkyl ester whose alkyl group has 1 to 8 carbon atoms, and α, β- having one or more free carboxyl groups and 3 to 8 carbon atoms. 100 parts by weight of copolymer resin particles consisting of an ethylenically unsaturated carboxylic acid monomer (2) 50 to 120 parts by weight of a phthalic acid alkyl ester plasticizer having a molecular weight of 360 to 480 (3) a foaming agent 3 to 15 parts by weight (4) A foamed wallpaper comprising a paper base material coated with a plastisol obtained by mixing 50 to 150 parts by weight of aluminum hydroxide, dried and foamed.