JP2010046974A - Multilayer paper for wallpaper and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide multilayer paper for wallpaper in which a plurality of base wallpaper sheets are made into multilayers and in which, if the upper layer of the base wallpaper sheets is peeled and renewed, a protective layer of synthetic resin is formed in the upper layer of the renewed base wallpaper layers. <P>SOLUTION: The multilayer paper for wallpaper is composed of a plurality of base wallpaper layers by alternately laminating the base wallpaper and the synthetic resin layer. The synthetic resin layer is composed of a plurality of thermoplastic synthetic resin layers, wherein one interface between the thermoplastic synthetic resin layers constituting the synthetic resin layers is a peelable interface. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to paper wallpaper. In particular, the present invention relates to a multilayer paper wallpaper that includes a plurality of wallpaper base paper layers, and can be used after being pasted on a wall and then peeled off from the outermost layer and updated.

Paper wallpaper is an interior material that is affixed to a wall in order to beautify the room in general houses, offices, rental rooms, restaurants, hotels, hospitals, etc., and is very commonly used.
The wallpaper is renewed and renewed by moving or redesigning. In particular, the frequency is high for business use such as rental properties, restaurants, and guest rooms.
The present applicant has continuously proposed paper wallpaper suitable for renewal work in which old paper wallpaper is temporarily removed and new paper wallpaper is pasted.

In Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-124270), a multilayer paper composed of a bulky pulp layer and a support layer mainly composed of natural pulp is used as an upper layer paper, and a backing paper is bonded to the support layer side. This paper wallpaper is not only easy to peel at the time of re-stripping, but also has a wall surface after peeling, by providing peelability at the interface between the support layer of the upper paper layer and the bulky pulp layer or between the bulky pulp layers. The paper layer remaining on the paper is uniform, and can be easily applied from the top without any background treatment, and paper wallpaper is disclosed.
Patent Document 2 (Japanese Patent Application Laid-Open No. 2005-314861) discloses a quaternary ammonium salt of a condensate of a higher fatty acid, a polyalkylene polyamine and epichlorohydrin, and a quaternary ammonium salt of a higher fatty acid, a polyaminopolyamide and an epichlorohydrin condensate in paper. Fatty acid-based derivatives such as, preferably, a steecht sizing degree of 10 seconds or more, a paper interlayer strength of 20 N / m to 40 N / m, and a water-soluble resin binder and / or a water-dispersible resin binder as a main component A wallpaper backing paper coated with at least one side of the coating liquid, which has a long open time required during wallpaper construction, is easy to peel off when the wallpaper is replaced, and the backing paper layer remaining on the wall is uniform after the replacement. A wallpaper backing paper is disclosed.
In addition, there has been proposed a wallpaper that can be renewed by sequentially removing the multilayered wallpaper. Patent Document 3 (Japanese Utility Model Publication No. 59-9036) discloses an idea of pasting together a plurality of wallpaper having an adhesive layer on the back surface so as to be sequentially separated from the front surface. In Patent Document 4 (Japanese Patent Laid-Open No. 2006-144143), a mixed paper made of polyethylene synthetic fiber and wood pulp fiber and a mixed paper made of polypropylene synthetic fiber and wood fiber are alternately laminated and then hot pressed. The resulting multilayer wallpaper is disclosed.

JP 2004-124270 A Japanese Patent Laid-Open No. 2005-314861 Japanese Utility Model Publication No.59-9036 JP 2006-144143 A

  In the multi-layer wallpaper described in Patent Document 3 and Patent Document 4, there is a problem that the new wallpaper surface that appears on the surface after peeling the surface wallpaper is exposed to paper, so that the stain resistance and water resistance are poor. . Therefore, the present invention is a multilayer paper wallpaper in which a plurality of wallpaper base papers are provided in multiple layers, and when the upper wallpaper base paper is peeled off and updated, a protective layer of synthetic resin is formed on the upper layer of the updated wallpaper base paper layer. An object of the present invention is to provide a multi-layered wallpaper.

  The present invention is a multilayer paper wallpaper in which a paper layer and a synthetic resin layer are alternately laminated, wherein a synthetic resin layer provided between the paper layer and the paper layer is formed from a plurality of thermoplastic synthetic resin layers, and the thermoplastic synthesis The interface between the resin layers is detachable so that the thermoplastic synthetic resin layer appears on the new surface that is renewed when the upper layer (which becomes the surface layer when bonded to the wall) is peeled off. Propose multi-layer paper wallpaper. The main configuration of the present invention is as follows.

(1) A multilayer paper wallpaper comprising a plurality of wallpaper base paper layers by alternately laminating wallpaper base paper and synthetic resin layers, wherein the synthetic resin layer is composed of a plurality of thermoplastic synthetic resin layers, and the synthetic resin layer A multilayer paper wallpaper characterized in that one interface between the thermoplastic synthetic resin layers constituting the layer is a peelable interface.
(2) The multi-layered paper wallpaper according to (1), wherein the peelable interface is formed of two thermoplastic resin layers made of different types of thermoplastic resins having low compatibility with each other.
(3) The peelable interface is formed of two thermoplastic synthetic resin layers having different thicknesses, and the difference between the thickness of the upper thermoplastic resin layer and the thickness of the lower thermoplastic resin layer is 5 μm or more. The multilayer paper wallpaper as described in (1) or (2).
(4) Any one of (1) to (3), wherein any one of the thermoplastic synthetic resin layers forming the peelable interface contains an additive for adjusting the peel strength of the peelable interface. Multi-layer paper wallpaper as described in Crab.
(5) The multilayer paper wallpaper according to any one of (1) to (4), wherein the thickness of the synthetic resin layer is 40 μm or less.
(6) The peel strength of the peelable interface in the synthetic resin layer provided on the upper layer side is smaller than the peel strength of the peelable interface in the synthetic paper layer provided on the lower layer side (1) The multilayer paper wallpaper in any one of-(5).
(7) The multilayer paper wallpaper according to any one of (1) to (6), which is embossed.
(8) The multilayer paper wallpaper according to any one of (1) to (7), wherein a coating layer is provided on the surface of the uppermost wallpaper base paper.
(9) A method for producing a multilayer paper wallpaper having a plurality of wallpaper base paper layers by alternately laminating a wallpaper base paper and a synthetic resin layer by using a sand lamination means, wherein the synthetic resin layer includes a plurality of different thermoplastic resins. A method for producing a multilayer paper wallpaper, which is provided by extruding and forming a single peelable interface between the plurality of thermoplastic synthetic resin layers.
(10) The renewable multilayer paper according to any one of (1) to (8), wherein the peelable interface formed at the interface between the thermoplastic synthetic resin layers has a peel strength of 3 to 30 N / m wallpaper.
(11) The updatable multilayer paper wallpaper according to any one of (1) to (8), wherein a pattern is formed on the paper wallpaper of each layer.

1. A new wallpaper surface can be easily exposed by peeling the upper paper layer out of the multiple layers of the wallpaper base paper layer provided. And since an update surface becomes a synthetic resin layer, the update surface which has antifouling property and water resistance is obtained, without exposing a paper surface.
2. It can peel from the interface of a thermoplastic synthetic resin layer by adjusting the adhesive strength of the interface in the provided thermoplastic synthetic resin layer. Thereby, when the paper layer of the upper layer (which becomes the surface layer when bonded to the wall) is peeled off, it can be peeled from the synthetic resin layer.
3. By adjusting the adhesive strength at the interface between the thermoplastic synthetic resin layers in each synthetic resin layer provided between the paper layer and the paper layer that constitutes the multilayer paper wallpaper, peeling is performed in order from the wallpaper base paper on the upper layer side. It can be configured to be easy. It can be realized by adopting a combination of different types of thermoplastic resins with low compatibility, providing resin layers with different layer thicknesses, using additives, etc. as means for forming the peeling interface. . On the other hand, by applying corona treatment or plasma treatment to the paper side, the adhesive strength between the paper and the resin can be improved, and the thermoplastic synthetic resin layer can be reliably left on the renewal surface side.
4). As a means for joining the paper layer and the synthetic resin layer, the paper layer and the synthetic resin layer can be laminated without using an adhesive separately, and a peeling surface can be formed at the interface of the synthetic resin layer.
5). A pattern can be printed on a paper surface, and a new pattern surface can be expressed when updated. Seasonal feeling can also be given, and it is easy to change the appearance according to the atmosphere such as customer service space. Since the paper layer is multi-layered, the embossed pattern can be provided up to the lower layer, and the embossed pattern can be exposed even if updated.
6). A multilayer paper wallpaper having a difference in adhesive force can be easily produced only by the sand lamination process. There is no need to increase the number of steps, and productivity can be improved.

  The present application is designed so that a paper layer and a plurality of synthetic resin layers are alternately laminated and can be peeled off from the intermediate interface of the plurality of synthetic resin layers, and the synthetic resin layer appears on the updated new surface. We propose an invention related to multi-layer paper wallpaper. The present invention is a multilayer paper wallpaper in which the lower layer exposed by peeling can be used as a renewal surface, and a synthetic resin layer serving as a protective layer is formed on the surface side of the wallpaper base paper serving as a base material layer. A multilayer paper wallpaper with controlled peelability. The multilayer paper wallpaper according to the present invention is obtained by alternately bonding and laminating a paper layer as a wallpaper base paper and a synthetic resin having a plurality of layers, and the bonding function can be sequentially peeled without requiring an adhesive. A multilayer paper wallpaper with controlled interfacial adhesion.

<Layer structure of multilayer paper wallpaper>
A schematic diagram of an example of the multilayer wallpaper of the present invention is shown in FIG. From the surface side, the coating layer, wallpaper base paper a layer, synthetic resin layer a1 / synthetic resin layer a2, wallpaper base paper b layer, synthetic resin layer b1, synthetic resin layer b2, wallpaper base paper c layer,. This is a multilayer paper wallpaper in which a plurality of synthetic resin layers are alternately laminated. The wall surface shown in the figure is displayed to indicate the direction of lamination, and is not an element constituting the multilayer paper wallpaper of the present invention. This multilayer paper wallpaper is peeled off from the peelable interfaces 1, 2,... Formed between the plurality of synthetic resin layers provided between the upper and lower wallpaper base papers, and is applied to the surfaces of the wallpaper base papers b and c. The provided synthetic resin layers a2, b2,... Can be updated as new surfaces.

  As a means of forming a peelable interface between synthetic resin layers, a method in which the synthetic resin layer is made of a plurality of thermoplastic synthetic resin layers is adopted, a method in which thermoplastic resins having low compatibility are combined, and a paper layer is synthesized. The peelability of the peelable interface can be adjusted by a method of increasing the adhesive strength between the resin layers or a method of blending an additive for adjusting the peel strength into the thermoplastic resin layer. Further, when there are a plurality of synthetic resin layers, a design is applied by applying a method in which the peel strength of the peelable interface on the upper side (which becomes the outermost layer when attached to the wall) is larger than that on the lower side.

The multilayer paper wallpaper of the present invention can create a laminated state by a sand lamination method in which a thermoplastic synthetic resin is coextruded between two wallpaper base papers and the two wallpaper base papers are joined.
FIG. 2 shows a schematic diagram of lamination by the sand lamination method. While supplying the wallpaper base papers 2 and 5 from the left and right, the thermoplastic resins 3 and 4 are supplied from the T die 6 provided in the center, and the crimping can be completed by the cooling roll 8 and the nip roll 7 disposed below. The wallpaper base paper 5 supplied from the right side is the lower layer side. Alternatively, the coating layer 1 can be formed by performing a coating process in advance on the surface side of the wallpaper base paper 2 supplied from the left side. Multi-layering is possible by performing this sand lamination in two stages and three stages. When the layer structure shown in FIG. 2 is applied to FIG. 1, the wallpaper base papers 2 and 5 correspond to the wallpaper base papers a and b, the thermoplastic resins 3 and 4 correspond to the thermoplastic resins a1 and a2, and the coating layer 1 corresponds to the coating layer. To do. Further, the corona treatment 11 can be applied as necessary.

<Wallpaper base paper>
Paper base materials used for the base paper for wallpaper of the present invention are bleached kraft pulp (NBKP) of coniferous wood, bleached kraft pulp (LBKP) of hardwood, groundwood pulp (GP), thermomechanical pulp (TMP), chemithermomechanical pulp. (CTMP) and deinked pulp (DIP) are used alone or mixed at an arbitrary mixing ratio to make paper.
In order to improve the opacity, the paper base material used for the base paper for wallpaper of the present invention preferably contains 1 to 30% by weight of filler per paper base material. As the filler, at least one selected from baked clay, kaolin, and illite that can suppress the occurrence of blisters (blowing between the backing paper and the vinyl chloride layer) at the time of vinyl paste coating is used. It is preferable to contain. In addition to these, clay, delaminated clay, heavy calcium carbonate, light calcium carbonate, light calcium carbonate-silica composite, magnesium carbonate, barium carbonate, titanium dioxide, zinc oxide, silicon oxide, amorphous silica, Inorganic fillers such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and zinc hydroxide, and organic fillers such as urea-formalin resin, polystyrene resin, and phenol resin may be used.
When the surface of the base paper for wallpaper is subjected to corona treatment, plasma treatment, or frame treatment, the adhesive strength between the treated surface and the thermoplastic synthetic resin surface can be improved. Therefore, it is possible to make a difference in the peel strength at the interface depending on the presence or absence of such surface treatment. Further, it is possible to make a difference in the peeling force depending on the degree of treatment. By combining such a paper surface treatment with the composition and surface treatment of a thermoplastic resin, it becomes possible to rank the base paper for wallpaper arranged in multiple layers so that it can be peeled off from the surface.

<Corona treatment and frame treatment>
The corona treatment is a treatment for corona discharge on the surface of the base paper, and the corona discharge treatment density calculated by voltage × current / (electrode width × film running speed) (W · min / m ² ) is 1 to 200 W · is preferably min / m ^2, more preferably 5~150W · min / m ^2, further preferably 10~100W · min / m ^2. The higher the corona discharge treatment density, the better the bond strength between the treated surface and the thermoplastic resin surface. By applying the corona treatment described above to any surface that adheres to the thermoplastic resin layer, the adhesive strength between the synthetic resin layer and the paper layer can be adjusted.

  The flame treatment is performed by bringing the film surface into contact with a flame generated when natural gas, propane, or the like is burned. Plasma treatment is an excited inert gas that is electrically neutral after removing charged particles by electronically exciting a single or mixed gas such as argon, helium, neon, hydrogen, oxygen, and air with a plasma jet. Is sprayed onto the film surface.

<Thermoplastic synthetic resin>
In the present invention, a synthetic resin layer is provided as an intermediate layer between at least upper and lower wallpaper base papers, and the layer is composed of two or more thermoplastic resin layers.
Of the three layers of the wallpaper base paper / synthetic resin layer (= plurality of thermoplastic resin layers) / wall paper base paper, it can be peeled off (pseudo-adhesion) from the thermoplastic resin layer interface between the synthetic resin layers. . The next wallpaper base paper coated with the thermoplastic synthetic resin layer appears when the upper wallpaper base paper is peeled off from the pseudo-adhered thermoplastic resin layer interface.

As the thermoplastic resin layer used in the present invention, both a crystalline resin and an amorphous resin can be used as long as extrusion lamination is possible. Examples of the crystalline resin include polyolefin resins such as high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, and polymethylpentene, polyester resins, polyamide, polyacetal, and PPS resins. Examples of the amorphous resin include polystyrene, polyvinyl chloride, ABS resin, acrylic resin, modified PPE, polycarbonate, polyurethane, polyvinyl acetate, and amorphous polyethylene terephthalate (PET).
Moreover, as a thermoplastic resin used for a thermoplastic resin layer, since adhesiveness with wallpaper base paper is favorable, polyethylene is used preferably. Polyethylene is roughly classified into linear low density polyethylene, low density polyethylene, medium density polyethylene, and high density polyethylene. The density, linear low density polyethylene 888~910kg / ^{m 3,} low density polyethylene 910~925kg / ^{m 3,} medium density polyethylene 925~940kg / ^{m 3,} higher density polyethylene has 940~970kg / m ^{About three} . The density of the other thermoplastic resin is not particularly limited, and a known material may be used.

Among the above-described thermoplastic resins, polymethylpentene is also suitable as the thermoplastic resin used for the thermoplastic resin layer. Polymethylpentene has a relatively weak adhesion to other thermoplastic resins, and it has been a drawback that it has been easy to peel off between the interfaces when co-extrusion is used in the past. It is a thing.
Polystyrene and polycarbonate are preferably used because of their excellent processability for extrusion lamination. In particular, polystyrene is available at low cost and is industrially advantageous, and is generally classified into two types, general-purpose polystyrene (hereinafter referred to as GPPS) and high-impact polystyrene with impact resistance (hereinafter referred to as HISP). Any of these can be used.

<Example of a combination of thermoplastic resins forming a peeling interface>
As a combination of the thermoplastic resins forming the synthetic resin layer of the present invention, it is preferable to adjust the adhesiveness by using resins having low compatibility with each other. In addition, resin compatibility is low when the resin is mixed in a molten state and is not completely mixed and becomes cloudy.
Examples include polyethylene and polymethylpentene, polyethylene and polystyrene, polyethylene and polyester, polyethylene and polycarbonate, polypropylene and polycarbonate, polypropylene and polymethylpentene, polypropylene and polystyrene, polypropylene and polyester, high density polyethylene and polypropylene, and the like. In addition, even if it is the same resin, an interface can be made peelable by using suitably the means of adhesiveness adjustment mentioned later.

<Peel strength adjustment additive>
The peel strength can be adjusted by adding an inorganic filler to one of the thermoplastic resin layers.
As the kind of inorganic filler, one or more kinds such as calcium carbonate, clay, talm, silica and the like can be used. When the content of the inorganic filler is large, the peeling becomes light, so the content may be appropriately determined according to the desired adhesiveness, but it is 1 to 10% by weight, preferably about 3 to 6% by weight with respect to the thermoplastic resin. Is appropriate.

Also, an α-olefin copolymer, a copolymer of a vinyl aromatic compound and a conjugated diene, a hydrogenated derivative of a copolymer of a vinyl aromatic compound and a conjugated diene, or a modified polyolefin described later is mixed with the thermoplastic resin. You can also. The α-olefin copolymer has good compatibility with the polyolefin resin, and examples thereof include an ethylene-propylene copolymer, a propylene-butene-1 copolymer, an ethylene-propylene-butene-1 copolymer, and a propylene-hexene. Examples include -1-octene-1 copolymer, butene-1-hexene-1-octene-1 copolymer, and propylene-hexene-1--4-methylpentene-1 copolymer.
Copolymers of vinyl aromatic compounds and conjugated dienes or hydrogenated derivatives thereof include hydrogenated styrene-butadiene rubber, styrene-isoprene-styrene block copolymers or hydrogenated derivatives thereof, styrene-butadiene-styrene block copolymers. Examples thereof include a polymer or a hydrogenated derivative thereof. Among these, hydrogenated styrene butadiene rubber (for example, trade name Dynalon 1320P manufactured by JSR Corporation) is preferable.

(Modified polyolefin)
As the modified polyolefin, modified products obtained by graft-modifying a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms with a monomer having a polar group and an ethylenic double bond can be used. It is not limited to. In the present invention, an ethylene methacrylic acid copolymer is preferably used because it is particularly excellent in adhesiveness with a paper substrate at a low temperature.
Examples of homopolymers or copolymers include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density linear polyethylene, polypropylene, ethylene / pentene-1 copolymer, ethylene Examples include 4-methylpentene-1 copolymer and ethylene-butene-1 copolymer. Examples of monomers having polar groups and ethylenic double bonds used as homopolymer or copolymer modifiers include (meth) acrylic acid, tetrahydrophthalic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid. Acids, crotonic acid, norbornene dicarboxylic acid, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid TM) and endo-cis-bicyclo [2,2,1 ] Carboxylic acids such as hept-5-ene-2-methyl-2,3-dicarboxylic acid (methylnadic acid TM); maleic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, crotonic anhydride, norbornene Dicarboxylic acid anhydride, acid anhydride of endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid TM) and endo-cis-bicyclo [2,2,1 ] Hept-5-ene-2-methyl-2,3-dicarbo Carboxylic anhydrides such as acid anhydrides of acids (methylnadic acid ™); alkyl esters of (meth) acrylic acid, (mono or di) alkyl esters of tetrahydrophthalic acid, (mono or di) alkyl esters of maleic acid, (Mono or di) alkyl esters of itaconic acid, (mono or di) alkyl esters of citraconic acid, (mono or di) alkyl esters of fumaric acid, (mono or di) alkyl esters of crotonic acid, (mono) of norbornene dicarboxylic acid Or di) alkyl esters, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid TM) alkyl esters and endo-cis-bicyclo [2,2,1 ] Esters such as alkyl esters of hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid TM); hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, penta Erythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and 2- (6-hydroxyhexanoyloxy) ) Hydroxy (meth) acrylic esters such as ethyl acrylate; 10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N- Hydroxyl-containing compounds such as tyrolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol and glycerol monoalcohol; glycidyl ( (Meth) acrylate, (mono or di) glycidyl ester of itaconic acid, (mono or di) glycidyl ester of butenetricarboxylic acid, (mono or di) glycidyl ester of citraconic acid, endo-cis-bicyclo [2,2,1] (Mono or di) glycidyl ester of hept-5-ene-2,3-dicarboxylic acid (nadic acid TM), endo-cis-bicyclo [2,2,1] hept-5-en-2-methyl-2, (Mono or di) glycidyl ester of 3-dicarboxylic acid (methyl nadic acid TM), (mono or di) glycidyl ester of allyl succinic acid, p-styre Glycidyl ester of carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3, Epoxy compounds having ethylenically unsaturated bonds such as 4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene and vinylcyclohexene monoxide; acrylic (Meth) such as aminoethyl acid, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate and methacryloyloxyethyl acid phosphate monomethanol amino half sol Alkylamino ester of acrylic acid; N-vinyldiethyl Vinylamines such as amines and N-acetylvinylamine; allylamines such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide and N-methyl Mention may be made of acrylamides such as acrylamide; aminostyrene compounds such as p-aminostyrene; and aminoalkyl succinimides such as 6-aminohexyl succinimide and 2-aminoethyl succinimide. These modifiers can be used alone or in combination as long as the properties of the modifier are not impaired. Of these modifiers, (meth) acrylic acid, maleic acid, fumaric acid, and maleic anhydride are preferred.

<Ozone treatment>
The ozone treatment is performed by spraying ozone-containing air on one surface of the molten thermoplastic synthetic resin film extruded from the T-die, and the adhesion strength between the ozone-treated surface and the wallpaper base paper surface can be improved. The conditions of the ozone treatment can be performed, for example, at a resin film deposition rate of 100 m / min, an air gap of 130 mm, an ozone concentration of 40 g / m ³ , and an ozone flow rate of 2 m ³ / hour.

<Generation of peelable interface>
By laminating (sand lamination) two or more layers of thermoplastic resin on upper and lower wallpaper base paper, and laminating a resin layer having a two-layer structure combining polyethylene and polymethylpentene, the resin layer can be peeled off. it can. Further, the laminate resin adheres strongly to the paper surface-treated, and the adhesiveness with the thermoplastic resin surface becomes relatively weak on the side opposite to the surface-treated surface (that is, the back surface), and peeling becomes possible.
For example, in the case of wallpaper base paper a / TPXa1 and LDPEa2 / wallpaper base paper b, a peelable portion is formed at the interface between the TPX layer a1 and the LDPE layer a2. In this case, the fact that the compatibility between TPX and LDPE is small was used for the generation of a peeling interface. Further, by applying corona treatment or the like to the b surface side of the wallpaper base paper a, the adhesive strength between the thermoplastic resin and the wallpaper base paper can be increased. Therefore, the peelability of the interface between the resins can be relatively improved. Further, since the peelability tends to be worse as the synthetic resin layer is thickened, when the synthetic resin layer is thickened in the lower layer, the interfacial peeling can be ranked.

Further, in the case of wallpaper base paper a / thermoplastic resin a1, thermoplastic resin a2 / wallpaper base paper b / thermoplastic resin b1, thermoplastic resin b2 / wallpaper base paper c, as it goes from the base paper base paper to the lower layer (that is, the wall side). It is necessary to increase the peel strength. As this method, in addition to combining the above-mentioned corona treatment and ozone treatment, the adhesive strength can be improved by increasing the thickness of the thermoplastic resin layer. For example, by setting the thermoplastic resins a1 and a2 to 6 μm and the thermoplastic resins b1 and b2 to 8 μm, the adhesive strength on the side of the thermoplastic resins b1 and b2 can be increased. Further, when an inorganic filler such as calcium carbonate is added to the thermoplastic synthetic resin layer, the adhesive strength can be reduced, and when a modified polyolefin is added to the low density polyethylene resin, the adhesive strength can be increased.
Therefore, factors for adjusting the adhesive strength between the layers include the type of thermoplastic resin, the layer thickness, whether or not to include an additive in the thermoplastic resin layer, the type and amount used, and the corona treatment on the surface of the paper substrate layer. Strength of ozone treatment on the surface of the thermoplastic resin layer, preheating temperature of wallpaper base paper, resin extrusion temperature, and the like. Among the adhesive strength adjustment factors, corona treatment and ozone treatment are methods developed to obtain a large adhesive strength, but in the present invention, by appropriately using these treatments for each intermediate layer, A laminate sheet that can be easily peeled can be produced.
By using such a combination of means, the layer peeling of the multilayer paper wallpaper is controlled so that it can be peeled sequentially from the interface on the back side of the wallpaper base paper of the surface layer.

<Decoration>
The wallpaper is required to have not only a design property but also a stain resistance which is difficult to get dirty, and is given an embossing or a pattern pattern. Even if the paper wallpaper of the present invention is renewed, the resin layer is exposed on the surface, so that it can satisfy water resistance and antifouling property.
By using a wallpaper base paper on which a pattern has been printed in advance as the paper wall base paper, the pattern can be displayed on the updated new surface. Multi-layer paper wallpaper according to the user's preference and usage environment can be supplied. For example, it is easy to produce in accordance with the seasons such as restaurants and hotels.
Embossing can be provided on the entire surface after being laminated in multiple layers, thereby providing embossed irregularities up to the lower layer.
Furthermore, the outermost surface can be provided with a pattern or a surface protective layer by using wallpaper base paper provided with a coating layer, and can be reprocessed on the surface after shipment. And the back surface directly affixed to a wall performs the process which attaches rehumidification adhesive glue etc., The process currently performed can be applied according to the kind etc. of wall.

<Multi-stage sand lamination>
Fig. 2 shows the three-layer structure of wallpaper base paper / thermoplastic synthetic resin / wall paper base paper by the basic sand lamination method. This is to supply the wallpaper base paper a on the front side from the left side and the base paper b of the next layer from the left side, and extrude the thermoplastic synthetic resin placed in the center with two T dies and two types of thermoplastic synthetic resin melt films. Then, they are pressed and laminated with a nip roll and a cooling roll disposed below. If necessary, the surface of the wallpaper base paper b supplied from the left side can be subjected to corona treatment in order to increase the adhesive strength.
FIG. 3 shows a multi-stage lamination showing an example in which this is continuously arranged in multi-stages. Although the corona treatment is described in each step as a means for changing the adhesive strength, it does not mean that the adhesive strength is changed significantly only by the corona treatment, and is schematically shown. As described above, it is performed in combination with ozone treatment or additive blending of a thermoplastic synthetic resin. It is preferable to form the upper layer by laminating from the lower layer side and applying the required number of sand laminations. FIG. 3 shows that the surface of the lowermost wallpaper base paper e is corona-treated from the left side, and the synthetic resins d1 and d2 supplied from the center and the wallpaper base paper d supplied from the right side are first sand-laminated and joined. In the next stage, the synthetic resin c1 and c2 and the wallpaper base paper c supplied from the right side are joined by sand lamination to the surface of the base paper d supplied from the left side. By repeating this operation one after another, a multilayer paper wallpaper having 5 layers of wallpaper base papers a, b, c, d, and e can be manufactured.

<Update process>
The multilayer paper wallpaper of the present invention can be renewed by peeling off the paper layer from the surface layer side. Since the synthetic resin layer is provided on the renewed surface, water resistance and contamination resistance are maintained.

<Application location>
The application location is not particularly limited. When planning to change the pattern periodically every four seasons, colors and patterns can be set in advance, which is suitable for business purposes such as sightseeing spots, hotels, restaurants, and restaurants. It is also suitable for businesses that require renovation in a short period of time, such as apartments, rental condominiums, and weekly apartments that have many relocations.

  First, as a base material, a thermoplastic resin layer composed of two layers of polymethylpentene (TPX) 20 μm and low-density polyethylene (LDPE) 15 μm is laminated together with the upper wallpaper base paper (sand) while corona treatment is applied to the lower wallpaper base paper. A two-layer paper wallpaper was made by laminating. The configuration is shown in FIG. The upper-layer wallpaper base paper has not been subjected to corona treatment. The resin temperature for laminating was 300 ° C. “← P” shown in FIG. 4 indicates that the film can be peeled from the bonding interface between TPX (polymethylpentene) and LDPE (low density polyethylene) (hereinafter, the same applies to FIGS. 5 to 10). The peelable interface is schematically indicated by a double line. In addition, the “wall” shown in FIG. 4 is shown for convenience in order to represent the top and bottom, and is not the configuration of the multi-paper wallpaper of Example 1 (the same applies to FIGS. 5 to 10 below).

  This was carried out in the same manner as in Example 1 and in the same manner as in Example 1 except that polymethylpentene was changed to polycarbonate. The configuration is shown in FIG.

  This was carried out in the same manner as in Example 1, and was carried out in the same manner as in Example 1 except that polymethylpentene was changed to polystyrene. The processing temperature was 250 ° C., and the configuration was polystyrene / LDPE / ethylene methacrylic acid copolymer /. The configuration is shown in FIG.

  The same procedure as in Example 1 was performed, except that 8% by weight of maleic anhydride-modified polyolefin was added to the low density polyethylene. The configuration is shown in FIG.

  This was carried out in the same manner as in Example 1, and the resin composition of the thermoplastic resin of the intermediate layer was a 40 μm polypropylene and 40 μm multilayer simultaneous laminate of high density polyethylene. The peel strength was adjusted by adding 8% by weight of charcoal to high density polyethylene. The configuration is shown in FIG.

  The multi-layer wallpaper obtained in Example 1 was provided with a coating layer. The configuration is shown in FIG.

  The same procedure as in Example 1 was performed except that the resin temperature was 285 ° C. The configuration is shown in FIG.

[Reference Example 1]
This was carried out in the same manner as in Example 1, except that the laminate thickness of the two-layer thermoplastic resin was 23 μm. The configuration is shown in FIG.
In Reference Example 1, two layers of thermoplastic resin were used for the intermediate layer. However, the thickness of each layer was large, the peel strength was increased, and peeling was difficult with the paper layer of the wallpaper base paper, making peeling difficult.

[Reference Example 2]
This was carried out in the same manner as in Example 1 except that the two-layer thermoplastic resin was laminated and the thickness was changed to 30 μm for polymethylpentene and 10 μm for low density polyethylene. The configuration is shown in FIG. In Reference Example 2, two layers of thermoplastic resin were used for the intermediate layer. However, since the polymethylpentene layer was thick and the resin itself was hard, the embossing suitability deteriorated and it was difficult to use as a multilayer wallpaper base paper.

[About delamination strength and embossing]
1. Measuring method of delamination strength For a sample having a width of 10 mm, which had been previously triggered for delamination, the force required for delamination at 90 degrees between the thermoplastic resin layers in a pseudo-adhesion state was measured according to JIS Z 0237.
2. Embossing method A sample (10 × 20 cm) that had been sanded was nipped between a heated metal roll with an embossed groove and a rubber roll (no groove) and embossed. Processing conditions are shown below. The evaluation was performed by visual evaluation.
Machining conditions Machining speed: 5m / min
Nip pressure: 10 kg / cm ²
Metal roll surface temperature: 85 ° C
Evaluation
A: The surface embossing depth and the state of the embossing depth after peeling were uniform and good.
○: Although the surface emboss depth and the emboss depth after peeling are somewhat uneven, it can be used as a multilayer wallpaper.
(Triangle | delta): Although the state of the embossing depth of a surface layer and the embossing depth after peeling is a little uneven, it can be used as a multilayer wallpaper.
X: The surface emboss depth and the emboss depth after peeling are non-uniform and cannot be used as a multilayer wallpaper.

Table 1 shows data regarding each example and each reference example regarding delamination strength and embossing suitability.
In each Example, it was peelable between resin layers. In Example 1 and Reference Example 1, the type of synthetic resin forming the layer is the same, but in Reference Example 1, compared with Example 1, the thickness of each layer is thick, so the adhesive strength between the thermoplastic resin layers is strong, It is thought that peeling became difficult because it peeled between the paper layer of the wallpaper base paper and the thermoplastic resin layer. In Reference Example 2, the type of resin is the same as in Example 1, and it is considered that interfacial peeling can be achieved by thinning the low-density polyethylene compared to Reference Example 1, but the polymethylpentene layer is thick, Since the resin itself is hard, the embossing suitability deteriorated, so the suitability as wallpaper base paper is reduced.
Examples 1 to 7 are examples in which wallpaper base paper is made into two layers. As shown in each example, the resin delamination strength is 3.9 to 30 N / m and shows various values. As described above, the peel strength can be adjusted by changing the thickness, corona treatment, additives, and the like. Therefore, by taking these measures, it is possible to realize an updatable multi-layer paper wallpaper that includes the multi-layer wallpaper base paper shown in FIG.

It is the schematic 1 which shows the layer structure of a multilayer paper wallpaper. It is a lamination | stacking schematic diagram by a sand lamination. It is a multi-stage sand lamination schematic diagram. 2 is a schematic diagram illustrating a layer configuration of Example 1. FIG. 6 is a schematic diagram showing a layer configuration of Example 2. FIG. 6 is a schematic diagram showing a layer configuration of Example 3. FIG. 6 is a schematic diagram showing a layer configuration of Example 4. FIG. 6 is a schematic diagram showing a layer configuration of Example 5. FIG. 6 is a schematic diagram showing a layer configuration of Example 6. FIG. 10 is a schematic diagram showing a layer configuration of Example 7. FIG. 4 is a schematic diagram showing a layer configuration of Reference Example 1. FIG. 6 is a schematic diagram showing a layer configuration of Reference Example 2. FIG.

Explanation of symbols

1 Coating layer 2 Wallpaper base paper a
3 thermoplastic synthetic resin layer a1
4 thermoplastic synthetic resin layer a2
5 wallpaper base paper b
6 T-die 7 Nip roll 8 Cooling roll 9 Extruder 10 Extruder 11 Corona treatment

Claims (9)

A multilayer paper wallpaper comprising a plurality of layers of wallpaper base paper by alternately laminating wallpaper base paper and synthetic resin layers,
The multilayer paper wallpaper, wherein the synthetic resin layer comprises a plurality of thermoplastic synthetic resin layers, and one interface between the thermoplastic synthetic resin layers constituting the synthetic resin layer is a peelable interface.   The multilayer paper wallpaper according to claim 1, wherein the peelable interface is formed of two thermoplastic resin layers made of different types of thermoplastic resins having low compatibility with each other.   The peelable interface is formed of two thermoplastic synthetic resin layers having different thicknesses, and the difference between the thickness of the upper thermoplastic resin layer and the lower thermoplastic resin layer is 5 μm or more. The multilayer paper wallpaper according to claim 1 or 2.   The multilayer according to any one of claims 1 to 3, wherein an additive for adjusting the peel strength of the peelable interface is contained in any one of the thermoplastic synthetic resin layers forming the peelable interface. Paper wallpaper.   The multilayer paper wallpaper according to any one of claims 1 to 4, wherein the synthetic resin layer has a thickness of 40 µm or less.   The peel strength of the peelable interface in the synthetic resin layer provided on the upper layer side is smaller than the peel strength of the peelable interface in the synthetic resin paper layer provided on the lower layer side. The multilayer paper wallpaper as described in any one.   The multilayer paper wallpaper according to any one of claims 1 to 6, which has been embossed.   The multilayer paper wallpaper according to any one of claims 1 to 7, wherein a coating layer is provided on the surface of the uppermost wallpaper base paper.   A method of producing a multilayer paper wallpaper having a plurality of wallpaper base paper layers by alternately laminating a wallpaper base paper and a synthetic resin layer by sand lamination means, wherein the synthetic resin layer is provided by coextrusion of a plurality of different thermoplastic resins. And the manufacturing method of the multilayer paper wallpaper characterized by forming one peelable interface between several said thermoplastic synthetic resin layers.

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