JP2003055898A - Foamed wall paper and multi-layered sheet for foamed wall paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide foamed wall paper which can easily be cut with a cutter and has an excellent emboss-transferring property, and to provide a multi- layered sheet for the foamed wall paper, which is used as a raw material for the foamed wall paper. SOLUTION: This foamed wall paper is composed by laminating an un-foamed resin sheet containing foamable microcapsules in a dispersed state obtained by sealing an evaporable liquid in shells comprising acrylonitrile- methacrylonitrile-vinyl acetate terpolymer, on a back sheet, and if necessary, is heated to obtain multi-layered sheet for the foamed wall paper disposing a printed layer on the surface of the un-foamed resin sheet.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a foam wallpaper and a multilayer sheet for foam wallpaper.

[0002]

2. Description of the Related Art Wallpapers are first temporarily adhered to a wall base material such as a gypsum board in a state in which the ends of one of the wallpapers that are adhered to each other are superposed on the ends of the other wallpaper. The overlapping portion of the wallpaper is cut in the longitudinal direction by a cutter, the separated edges of both wallpapers are removed, and the wallpaper is constructed so that there are no gaps or steps at the joints between the wallpapers.

[0003] In addition, in order to enhance the design of the wall surface in the room, the wallpaper is provided on a back sheet of paper, woven cloth, non-woven cloth, etc.
As disclosed in JP-A-8-246397, a foamed resin layer foamed using a microcapsule type foaming agent is laminated, and a printing layer is provided on the surface of the foamed resin layer as necessary, and A wallpaper called a foamed wallpaper in which a foamed resin layer is embossed has already been proposed.

However, the conventional foamed wallpaper as described above is
The emboss transfer is poor, and when cutting wallpaper by stacking it as described above, it is hard and difficult to cut, so you need to cut it with force.In some cases, too much force is applied to the wall base material. May be cut off. That is, in the case of the conventional microcapsule type foaming agent, about 90
Since foaming occurs at a relatively low temperature of up to 130 ° C., if exposed to a high temperature state during heat foaming for a long period of time, the foam is broken or the expanded particles shrink.

Therefore, in order to obtain a sufficient foaming state, the addition amount of the microcapsule type foaming agent must be increased. However, when the addition amount of the foaming agent is increased, the amount of foamed particles scattered inside the foamed resin layer is increased. It is considered that the expanded particles adversely affect the embossing and impair the passage of the cutter.

[0006]

In view of the above circumstances, the present invention provides a foamed wallpaper which is easily cut by a cutter and has excellent emboss transferability, and a multilayered foamed wallpaper which is a raw material of the foamed wallpaper. The purpose is to provide a seat.

[0007]

In order to achieve such an object, the foamed wallpaper according to claim 1 of the present invention (hereinafter,
The "foamed wallpaper of claim 1") is a foamed microcapsule obtained by encapsulating a volatile liquid in an outer shell made of acrylonitrile-methacrylonitrile-vinyl acetate terpolymer in a dispersed state on a back sheet. The composition was obtained by stacking the unfoamed resin sheets contained therein, and heating the multilayered sheet for foamed wallpaper in which a printing layer was provided on the surface of the unfoamed resin sheet as needed.

The foamed wallpaper according to claim 2 of the present invention (hereinafter referred to as "foamed wallpaper according to claim 2") is defined by claim 1.
In the foam wallpaper of, further embossed,
The structure is such that an uneven pattern is formed on the surface.

The multi-layer sheet for foamed wallpaper according to claim 3 of the present invention is a foam sheet in which a volatile liquid is enclosed in an outer shell made of acrylonitrile-methacrylonitrile-vinyl acetate terpolymer on a back sheet. An unfoamed resin sheet containing microcapsules in a dispersed state was laminated, and a printing layer was provided on the surface of the unfoamed resin sheet as needed.

In the present invention, a printing primer layer may be provided on the surface of the unfoamed resin sheet or the resin sheet after foaming in order to facilitate printing. Also,
A printing protection layer may be provided on the printing ink layer to protect the printing ink.

Back Sheet The back sheet used in the present invention is a sheet that supports an unfoamed resin sheet, and is a sheet that becomes an adhesive surface to a wall when a wallpaper is applied, and is, for example, paper or nonwoven fabric. However, a flame-retardant material is preferable, and, for example, a flame-retardant paper or a glass nonwoven fabric containing an inorganic material is particularly preferable. Although the thickness of the back sheet is not particularly limited, it may be 0.
It is preferably 1 mm to 0.2 mm.

Unfoamed Resin Sheet In the present invention, the unfoamed resin sheet means a thermoplastic resin composition containing expandable microcapsules in a dispersed state,
Alternatively, it is a resin sheet obtained from an aqueous resin emulsion containing expandable microcapsules in a dispersed state.

The thermoplastic resin (binder resin) constituting the thermoplastic resin composition is not particularly limited, but examples thereof include polyethylene resin, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene. -EPD with (meth) acrylate copolymer, synthetic rubber, polypropylene or polyethylene as the hard segment
Polyolefin thermoplastic elastomer having a rubber component such as M and NBR as a soft segment, polystyrene thermoplastic elastomer having a polystyrene as a hard segment and polydiene such as polybutadiene and polyisoprene as a soft segment, and hydrogenated products thereof, random SBR Of hydrogenated polymer (HSBR) and polypropylene, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-vinyl stearate copolymer, vinyl chloride -Acrylic ester copolymer, vinyl chloride-vinyl ether copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-vinylidene chloride copolymer, polyacrylic resin, polyvinyl acetate resin, polyurethane Fat, polystyrene resins, polyvinyl alcohol resins.

In the above thermoplastic resin composition, if necessary, a plasticizer, a flame retardant, a lubricant, a colorant, a filler,
Antioxidants, fillers, surfactants, pigments, ultraviolet absorbers, light stabilizers, antistatic agents, deodorants, fungicides, antibacterial agents, insect repellents, and reinforcing agents may be added. As the reinforcing agent, inorganic powder such as chrome yellow, carbon black, talc, mica is suitable.

The thermoplastic resin is polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-vinyl stearate copolymer, vinyl chloride-acrylic acid ester. If it is a copolymer, vinyl chloride-vinyl ether copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-vinylidene chloride copolymer, polyacrylic resin, it may be a plastisol to which a plasticizer is added. preferable.

As the plasticizer, dioctyl phthalate,
Phthalates such as dibutyl phthalate, butyl benzyl phthalate and diisononyl phthalate, phosphates such as alkyldiphenyl phosphate, chlorinated aliphatic esters, chlorinated paraffins, low molecular weight epoxies,
Examples thereof include low molecular weight polyesters, adipic acid esters such as dioctyl adipate, and long chain alkyl alcohols such as n-octyl alcohol. As the flame retardant, aluminum hydroxide, metal hydroxide such as magnesium hydroxide, alumina, hydrotalcite, antimony trioxide, nickel oxide, zinc borate, magnesium borate, organic phosphate ester, ammonium monophosphate. ,
Examples thereof include kaolin clay, ferrocene, molybdenum compounds and the like. Of these, aluminum hydroxide and magnesium hydroxide are preferable in terms of cost and safety.

When a binder resin containing halogen is used, a metal salt of boric acid is preferably used as the flame retardant, and examples thereof include zinc borate, aluminum borate, iron boride, sodium borate and the like. . Examples of the lubricant include paraffin, low molecular weight polyolefin, stearic acid, stearic acid ester, stearyl alcohol, petrolatum, and polyglycol ester of fatty acid. The workability of embossing can be improved by adding a lubricant.

Examples of the colorant include pigments such as calcium carbonate, zinc oxide and magnesium oxide. Texture and whiteness can be improved by adding a colorant. As the antifungal agent, silica gel silver, silver zeolite, zirconium phosphate silver salt, calcium phosphate silver salt, 10,10′-oxybisphenoxyarsine, 8-oxyquinoline copper, 2- (4-thiazolyl) -benzimidazole, 2 -Methyl benzimidazole carbamate, 2-n-octyl-4-isothiazolyl-3-one, bis (pyridine-2-thiol-
1-oxide) zinc salt, 2-peridithiol-1-oxide sodium salt, N, N ′, N ″ -triazine and the like.

The aqueous resin emulsion is not particularly limited, and examples thereof include acrylic resin emulsion, acrylic-vinyl chloride emulsion, urethane emulsion, ethylene-vinyl acetate emulsion and the like. The solid content of the emulsion is preferably 10 to 80% by weight, more preferably 20 to 70% by weight. A flame retardant, a colorant, a defoaming agent, a fluidity improver, a filler, and a reinforcing material are added as needed. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compounds and the like. Of these, aluminum hydroxide and magnesium hydroxide are preferable in terms of cost and safety.

The expandable microcapsules used in the present invention have an outer shell made of an acrylonitrile-methacrylonitrile-vinyl acetate terpolymer filled with a volatile liquid, and contain 55 to 75% by weight of acrylonitrile.
Methacrylonitrile 20-40% by weight, vinyl acetate 1-
A monomer component containing 10% by weight and 0.1 to 1% by weight of a tetrafunctional or more cross-linking agent and a volatile liquid which becomes a gas at a temperature above the softening point of the polymer are subjected to suspension polymerization under nitrogen pressure. It is obtained by

That is, by adding a small amount (1 to 10% by weight) of vinyl acetate monomer having a high radical reactivity,
It is possible to promote the reactivity of methacrylonitrile, which has a significantly low growth radical reactivity. As a result, the polymerization rate of methacrylonitrile having high heat resistance can be increased, and the particle stability of the expanded particles themselves at high temperature for a long time can be maintained. As a measure for promoting the reaction of methacrylonitrile, which has low growth reactivity, it is possible to increase the pressure in addition to the addition of vinyl acetate. That is, it is considered that methacrylonitrile, which is a monomer in which the hydrogen at the α-position of acrylonitrile is replaced with a methyl group, has steric hindrance at least. By increasing the pressure, the steric hindrance is overcome, and the settling (particle shrinkage / foaming) at high temperature / long time is suppressed.

Examples of the volatile liquid include butane, pentane, hexane, cyclohexane, toluene,
Xylene and the like can be mentioned, and butane, pentane, hexane, and cyclohexane, which have high volatility, are more preferable.

Manufacturing Method The foamed wallpaper of the present invention is not particularly limited, but can be manufactured by the following method, for example. (Aspect of Producing Wallpaper Main Body Layer on Back Sheet) 1. The plastisol in which the expandable microcapsules are dispersed is applied to the back sheet, then dried and gelled to form a coating film of about 0.3 mm, which is sufficiently foamed by heating at 130 to 250 ° C. for several tens of seconds to several minutes. Method. 2. The acrylic resin emulsion in which the expandable microcapsules were dispersed was applied on the back sheet using a knife coating device, and then dried to form a coating film.
A method of sufficiently foaming by heating at 50 ° C. for several tens of seconds to several minutes.

(Aspect in which Separately Forming Foamed Resin Sheet as Wallpaper Main Body Layer) While supplying the thermoplastic resin composition to the extruder, the expandable microcapsules are supplied from another supply port of the extruder and kneaded, and the foamed resin sheet is directly drawn from the die, or the molding temperature and pressure conditions are equal to or less than the foaming conditions. To form an unfoamed resin sheet, and then the unfoamed resin sheet is heated to foam to obtain a foamed resin sheet. Then, the foamed resin sheet obtained as described above is stacked on the back sheet,
A method of bonding both layers with an adhesive.

A method in which a molten polyethylene resin is extruded and pressure-bonded between the foamed resin sheet and the back sheet obtained as in 2.1. In such a case, since a strong adhesive force can be obtained, it is desirable to previously subject the adhesive surface of the foamed resin sheet to corona discharge treatment.

3. A method in which a pre-formed non-foamed sheet is laminated and adhered on the back sheet, or fusion-laminated, and then this laminated body is heated to foam.

On the other hand, the method of forming the printing layer is not particularly limited, but examples thereof include a printing method such as gravure printing, screen printing, flexo printing, rotary screen printing, and a printing method such as inkjet coating. The printing ink may be either dye ink or pigment ink. The printing process may be performed after foaming and embossing and before foaming and embossing. If you want to print before foaming and embossing,
Since the printing ink is heated to a high temperature during embossing,
It is preferable to use a pigment ink resistant to heat as the printing ink.

Embossing The embossing is not particularly limited, but it can be done by a method using an embossing roll or an embossing plate. Since it is possible to accurately form a concavo-convex pattern having an appropriate depth during embossing, the total thickness after foaming is preferably about 0.5 to 1.5 mm.

The foaming step and the embossing step may be carried out separately, but it is also possible to use the heating state of the embossing step and also serve as the foaming step. Generally, the unfoamed resin sheet can be foamed by holding the foaming microcapsules at a temperature not lower than the foaming temperature for several tens of seconds.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the present invention will be described below.

(Example 1) A foamed wallpaper was manufactured as follows. Production of effervescent microcapsules [oil mixture] -Acrylonitrile 2220 parts-methacrylonitrile 990 parts-vinyl acetate 100 parts-dipentaerythritol hexaacrylate 5 parts-n-pentane 640 parts-azobisisobutyro Nitrile 17 parts by weight [aqueous mixture] Deionized water 7300 parts by weight Silica dispersion (solid content 20%) 1260 parts by weight Potassium dichromate (2.5% solution) 45 parts by weight Polyvinylpyrrolidone 8 parts by weight Sodium chloride 2200 parts by weight, hydrochloric acid 8.5 parts by weight

The above oily mixture and aqueous mixture were mixed by stirring with a homogenizer, then charged into a pressure polymerization vessel (20 L) which was replaced with nitrogen and pressurized to 1.0 MPa,
The reaction was carried out at 0 ° C for 16 hours. Then, filtration and washing with water of the obtained reaction product were repeated and then dried to obtain expandable microcapsules having an average particle size of 22 μm. Using the expandable microcapsules thus obtained, a microcapsule-containing acrylic resin emulsion having the following formulation was obtained.

[0033]   [Microcapsule-containing acrylic resin emulsion] ・ Acrylic ester emulsion (Brand name AD-46, manufactured by NSC Japan) 100 parts by weight ・ Dispersant (Poise 520, manufactured by Kao Corporation) 1 part by weight ・ Antifoaming agent (Deformer 154, San Nobuco) 0.5 parts by weight ・ Titanium oxide (PVW-7T, manufactured by Sumika Color Co., Ltd.) 15 parts by weight -Aluminum hydroxide (H-32, Showa Denko KK) 80 parts by weight -Thickener (FX-928, manufactured by Nippon Carbide Industry Co., Ltd.) 1.5 parts by weight ・ Thickener (Aron A201, manufactured by Toagosei Kagaku) 0.12 parts by weight ・ Effervescent microcapsule 15 parts by weight

The above-mentioned acrylic resin emulsion containing microcapsules was coated on a paper backsheet with a knife coater so that the coating amount was 60 g / m ^{2 in} terms of dry weight. Then, the acrylic resin emulsion is heated and dried at about 100 ° C. to form a coating film, and then 180
The foamable microcapsules were foamed by heating at ℃ for 5 minutes to obtain a foamed wallpaper.

Comparative Example 1 A foamed wallpaper was obtained in the same manner as in Example 1 except that the foaming microcapsules were obtained by using the following mixture as the oily mixture. [Oil-based mixture] Acrylonitrile 2220 parts by weight Methacrylonitrile 990 parts by weight Vinyl acetate 100 parts by weight Dipentaerythritol hexaacrylate 5 parts by weight n-Pentane 640 parts by weight Azobisisobutyronitrile 17 parts by weight

The expansion ratios of the expandable microcapsules obtained in Example 1 and Comparative Example 1 were examined according to the heating temperature and the heating time, and the results are shown in Table 1 below. The expansion ratio is such that 1.0 g of the expandable microcapsules is placed in a gear-type oven and heated at a predetermined temperature (foaming temperature) for 5 minutes for foaming, and the resulting foam is put in a graduated cylinder to adjust the volume. It was measured and divided by the volume before unfoaming to obtain the foaming ratio.

[0037]

[Table 1]

From Table 1 above, it is understood that the expandable microcapsules obtained in Example 1 have a larger expansion ratio than the expandable microcapsules obtained in Comparative Example 1 when expanded at 170 to 180 ° C. Next, the foamed wallpaper obtained in Example 1 and Comparative Example 1 was evaluated for embossing evaluation and ease of cutting in the following manner.

[Embossing Evaluation] The foamed wallpaper obtained in Example 1 and Comparative Example 1 was coated with a maximum depth of 340 μm.
The wallpaper surface was embossed by hot pressing using an embossing roll having a sharp concavo-convex pattern of m and a pitch width of 2.4 mm. Then, a visual evaluation was made as to whether or not the embossed pattern was clearly transferred.

[Easy to cut wallpaper] Two foamed wallpapers are attached to a wall surface made of gypsum board with an overlapping portion,
The overlapping portion of the two foamed wallpapers was cut with a cutter knife. At this time, it was tested whether or not the problem that the overlapping part was difficult to separate and the blade of the cutter knife was strongly cut into the underlying gypsum board and the blade of the cutter knife spilled out.

As a result of the evaluation of the embossing of the foamed wallpaper and the evaluation of the ease of cutting, the foamed wallpaper of Example 1 was very clearly transferred with the concavo-convex pattern, and scratches on the gypsum board due to the cutter knife were hardly seen. On the other hand, in the case of the foamed wallpaper of Comparative Example 1, the uneven portion of the unevenness was partially seen, the blade was deeply inserted into the ground gypsum board, and the blade of the cutter knife was spilled. .

That is, since the expandable microcapsules used in the present invention can be expanded at a higher temperature than conventional ones, they have a larger expansion ratio than conventional capsules. This reduces the amount of capsules required for foaming,
The foamed wallpaper contains less foamed microcapsules than conventional foamed wallpaper. Therefore, in the foamed wallpaper of the present invention, when the surface is embossed, the uneven pattern can be transferred very clearly, and the wallpaper can be easily cut. Probably, too many expanded microcapsules contained in the expanded wallpaper will hinder transfer during embossing. In addition, it is considered that the foamed microcapsules will be an obstacle to the cutting of the wallpaper.

[0043]

Since the foamed wallpaper according to the present invention is constructed as described above, the wallpaper can be easily cut and the workability is improved. Further, the transferability by embossing is excellent, the concavo-convex pattern can be transferred very clearly, and the design can be made excellent. And, it is considered that the performance of the present invention is improved as compared with the conventional art by the foamed wallpaper of claim 2.

The multilayer sheet for foamed wallpaper according to the present invention comprises
Since it is configured as described above, it can be foamed by heat during embossing and at the same time embossed. Therefore, it is possible to manufacture a foamed wallpaper in which the embossed pattern is more beautifully transferred.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasushi Nakata             2-4-4 Nishitenma, Kita-ku, Osaka City, Osaka Prefecture Sekisui             Chemical Industry Co., Ltd. (72) Inventor Yasuhiro Kawaguchi             4560 Kaisei-cho, Shinnanyo-shi, Yamaguchi Prefecture Tokuyama Sekisui Industry Co., Ltd.             Within the corporation F-term (reference) 4F055 AA17 BA12 CA06 DA02 DA11                       EA26 FA07 HA06                 4F100 AA01B AA05B AA19B AA20B                       AA21B AH01B AH02B AH03B                       AK01B AK22B AK25B AK27B                       AL01B AS00B AT00A BA03                       BA07 BA10C DE04B DG10A                       EJ39 GB08 HB31C JL01                       JM01B                 4L055 AG64 AG74 AG89 AH50 AJ01                       AJ02 AJ07 AJ08 BE08 BE14                       BE15 FA30 GA23

Claims (3)

[Claims] 1. Acrylonitrile-on a back sheet
Methacrylonitrile-a non-foamed resin sheet containing a foamable microcapsule containing a volatile liquid in a dispersed state in an outer shell made of a terpolymer of vinyl acetate is laminated,
A foamed wallpaper, which is obtained by heating a multilayered sheet for foamed wallpaper in which a printing layer is provided on the surface of the unfoamed resin sheet as necessary. 2. The foamed wallpaper according to claim 1, which is further embossed and has an uneven pattern on its surface. 3. Acrylonitrile-on the back sheet
Methacrylonitrile-a non-foamed resin sheet containing a foamable microcapsule containing a volatile liquid in a dispersed state in an outer shell made of a terpolymer of vinyl acetate is laminated,
A multi-layered sheet for foamed wallpaper, wherein a printing layer is provided on the surface of the unfoamed resin sheet, if necessary.