JP2020070715A - Wall paper - Google Patents

Abstract

To provide a wall paper having an excellent fireproof performance capable of inhibiting an occurence of a crack even if a distortion or a fissure occurs on an inner wall surface over time when the wall paper is affixed to the inner wall of a general house and in addition having an excellent design without an embossment process.SOLUTION: A wall paper has a structure with a substrate layer 1, an under foam layer 2 containing a vinyl chloride resin and a base resin layer 3 containing the vinyl chloride resin laminated in this order, the under foam layer constitutes a resin foam 2a, 2b, a substrate coating rate by the under foam layer is 10% or more and 85% or less in a plain view, the apparent degree of polymerization of the vinyl chloride resin constituting the under foam layer is 700-1500, an apparent degree of polymerization by a base resin layer is 100% in a plain view and the apparent degree of polymerization of the vinyl chloride resin constituting the base resin layer is 1550-4000.SELECTED DRAWING: Figure 1

Description

  The present invention relates to wallpaper having improved crack resistance without impairing fire protection performance.

  On the inner wall of many ordinary houses, a wallpaper in which a resin layer covering the entire surface of the backing paper for wallpaper and a pattern printing layer are further laminated is adhered with an adhesive, but the inner wall changes with time. Since the distortion and cracks are generated, there is a problem that the wallpaper is cracked when the wallpaper cannot follow the distortions and cracks of the inner wall. Therefore, as the resin layer to be laminated on the backing paper, it is possible to use a foamed polyethylene resin layer obtained by foaming a blended product of two types of low-density polyethylene having different densities so that the expansion ratio is 3 to 7 times. It has been proposed (Patent Document 1).

JP, 2009-235635, A

  However, the wallpaper of Patent Document 1 has a problem that the fireproof performance (in other words, flame retardancy) as the wallpaper is insufficient because polyethylene itself has no fireproof ability. In addition, although prevention of cracks during bending such as when wallpaper is attached to a pillar is being studied, when the wallpaper is attached to a flat inner wall, distortion or cracks occur over time on the inner wall surface. Even so, no specific study has been made on how to prevent the wallpaper from cracking. Furthermore, when embossing is applied to improve the design of the wallpaper, the foamed polyethylene resin layer may burst or expand irregularly, impairing the design of the wallpaper. There was a problem.

  An object of the present invention is to solve the above-mentioned problems of the conventional art, and when the wallpaper is attached to a wall surface such as an inner wall of a house, even if distortion or cracks occur over time on the wall surface. It is to prevent cracks from occurring and to be able to exhibit good designability without embossing.

  The present inventors have defined a predetermined amount between a base material layer such as a wallpaper backing paper constituting a wallpaper and a base resin layer that covers the entire surface and contains a vinyl chloride resin that exhibits excellent fireproof performance. An under-foamed layer composed of a resin foam containing a vinyl chloride resin having an apparent degree of polymerization is formed with a predetermined base material coverage, and a predetermined apparent degree of polymerization is obtained as the vinyl chloride resin constituting the base resin layer. It was found that the above-mentioned object can be achieved by using a resin having the following, and has completed the present invention.

That is, the present invention is a wallpaper in which a base material layer, an under-foaming layer containing a vinyl chloride resin, and a base resin layer containing a vinyl chloride resin are laminated in this order,
The under foam layer is made of resin foam,
The substrate coverage by the under foam layer is 10% or more and 85% or less in a plan view, and the apparent degree of polymerization of the vinyl chloride resin constituting the under foam layer is 700 to 1500,
Provided is a wallpaper in which the substrate coverage of the base resin layer is 100% in a plan view and the vinyl chloride resin constituting the base resin layer has an apparent polymerization degree of 1550 to 4000.

  Further, the present invention is the above-mentioned method for producing a wallpaper of the present invention, in which the under-foaming layer-forming composition is applied to one surface of the base material layer by a screen method, and subsequently a base resin layer-forming composition is formed. Provided is a method for producing an under-foamed layer by foaming a composition for forming an under-foamed layer by applying and heat-treating the obtained laminate.

  The wallpaper of the present invention has a structure in which a base material layer, an under-foamed layer made of a resin foam, and a base resin layer which covers 100% of the base material layer in plan view are laminated in this order. The under-foamed layer and the base resin layer contain a vinyl chloride resin-based material exhibiting good fireproof performance. For this reason, the wallpaper itself also exhibits good fire protection performance.

  The under-foamed layer provided between the base material layer and the base resin layer is made of a resin foamed body and has a base material coverage of 10% or more and 85% or less in a plan view. For this reason, the under-foamed layer has cracks and strains that propagate to the base resin layer even if cracks and strains also occur in the base material layer of the wallpaper as a result of cracks and strains in the wall surface to which the wallpaper is attached. It can be mitigated and can impart excellent crack resistance to the wallpaper.

  Further, the base resin layer surface can be formed with an embossed shape which is rich in design and which reflects the concavo-convex shape of the continuous or discontinuous resin foam of the under-foaming layer without embossing. By combining with processing, the degree of freedom of design can be expanded.

  Further, a patterned foam layer may be formed on the base resin layer, whereby the degree of freedom in design can be increased, and further, the visibility of the joints when the wallpaper is stuck can be weakened. Also, the degree of freedom in design can be expanded.

FIG. 1 is a schematic sectional view of the wallpaper of the present invention. FIG. 2 is a schematic sectional view of the wallpaper of the present invention. FIG. 3 is an explanatory view of the method for producing wallpaper according to the present invention.

<Wallpaper>
As shown in FIG. 1, the present invention includes a base material layer 1, an under-foamed layer 2 composed of resin foams 2a, 2b ... Arranged on one surface thereof, and an entire one surface of the base material layer 1. The wallpaper 10 includes the base resin layer 3 that covers the wall 10. As shown in FIG. 2, the wallpaper 10 of the present invention may have a patterned foam layer 4 composed of resin foam bodies 4a, 4b, ... On the surface of the base resin layer 3. It should be noted that these resin foams appear to exist independently when the wallpaper is observed from a certain cross section, but in reality, they may exist independently, for example, a hexagonal lattice or the like. , It may be regularly continuous, or may be irregularly continuous. Further, they may be in a mixed state.

<Base material layer 1>
The base material layer 1 constituting the wallpaper 10 of the present invention is a backing for the wallpaper. The base material layer 1 can be appropriately selected and used from materials known as base materials for foamed wallpaper in consideration of mechanical properties and the like. For example, so-called backing paper using paper can be preferably used.

The thickness of the base material layer 1 is preferably 80 μm or more, more preferably 100 μm or more, from the viewpoint of ease of peeling when the wallpaper is peeled off from the wall surface after the wallpaper is attached, and from the viewpoint of maintaining fire resistance. Is preferably 150 μm or less, more preferably 130 μm or less. Further, the thickness of the base material layer 1 has a positive correlation with the basis weight of the base material layer 1, and therefore can be evaluated by the basis weight. Specifically, the basis weight of the base material layer 1 is preferably 50 g / m ² or more, and preferably 100 g / m ² or less.

<Under foam layer 2>
The under-foamed layer 2 that constitutes the wallpaper 10 of the present invention is a composition that contains a vinyl chloride resin, and is structurally composed of resin foams 2a, 2b, ....

  The under-foamed layer 2 that constitutes the wallpaper 10 of the present invention contains the vinyl chloride resin, as described above. Therefore, good fireproof performance can be imparted to the wallpaper 10. Further, the base material coverage of the under foam layer 2 is 10% or more, preferably 30% or more in plan view from the viewpoint of ensuring the elongation of the base resin layer 3. Accordingly, even if the base material layer 1 of the wallpaper 10 is cracked or distorted as a result of the cracking or distortion of the wall surface to which the wallpaper is pasted, the cracks or distortion propagating to the base resin layer 3 are alleviated. It is possible to impart excellent crack resistance to the wallpaper. Further, the base material coverage of the under foam layer 2 is 85% or less, preferably 80% or less in plan view from the viewpoint of designability. Thus, since the base material coverage of the under-foamed layer 2 is 10% or more and 85% or less, the portion of the base material layer 1 not covered with the under-foamed layer 2 is defined as the concave portion, and the under-foamed layer 2 is defined as the convex portion. As a result, an uneven shape is formed. Therefore, a concavo-convex shape that reflects such a concavo-convex shape can be formed on the surface of the base resin layer 3 without embossing.

  The foaming ratio of the under-foamed layer 2 is preferably 3 times or more, more preferably 5 times or more, preferably 10 times or less, and more preferably 8 times or less from the viewpoint of designability. Further, within this range, even if the base material layer 1 of the wallpaper 10 is cracked or distorted as a result of the cracking or distortion of the wall surface to which the wallpaper is attached, the crack propagating to the base resin layer 3 And the strain can be relaxed, and excellent crack resistance can be imparted to the wallpaper.

The thickness of the under-foamed layer 2 is preferably 200 μm or more, and preferably 400 μm or less, from the viewpoint of ensuring the elongation of the base resin layer 3 and designability. The thickness of the under-foamed layer 2 has a positive correlation with the basis weight of the under-foamed layer 2, and can be evaluated by the basis weight. Specifically, the basis weight of the under foam layer 2 is preferably 10 g / m ² or more, and preferably 100 g / m ² or less.

  The under foam layer 2 compositionally contains at least a vinyl chloride resin, a plasticizer, a stabilizer, and a filler.

(Vinyl chloride resin)
The vinyl chloride resin is the main resin forming the under foam layer 2. As the vinyl chloride resin, one or more known vinyl chloride resins used in conventional wallpaper can be used. Even vinyl chloride homopolymers, vinyl chloride and modifying monomers (olefins such as ethylene and propylene) can be used. Copolymers with monomers, vinyl esters such as vinyl acetate, etc.). From the viewpoint of designability, the apparent polymerization degree of such vinyl chloride resin is 700 or more, preferably 900 or more, and 1500 or less, preferably 1300 or less. The apparent degree of polymerization when a plurality of vinyl chloride resins having different degrees of polymerization are used together can be calculated from the degree of polymerization and the resin mass of the degree of polymerization. For example, when the mass of the vinyl chloride resin having the degree of polymerization A is X part and the mass of the vinyl chloride resin having the degree of polymerization B is Y part, the apparent polymerization degree F of the mixed vinyl chloride resin is F = {(A × X ) + (B × Y)} / (X + Y).

(Plasticizer)
The plasticizer is a component for plasticizing the vinyl chloride resin and improving processability such as screen coatability. As such a plasticizer, those known as plasticizers for vinyl chloride resins can be used, and adipic acid plasticizers, phosphoric acid plasticizers, polyester plasticizers, phthalic acid plasticizers and the like can be used. Can be mentioned. Among them, phthalic acid esters such as bis (2-ethylhexyl) phthalate and diisononyl phthalate can be preferably used.

  The content of such a plasticizer in the under-foamed layer 2 is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, from the viewpoint of workability and designability, with respect to 100 parts by mass of the vinyl chloride resin. It is preferably 70 parts by mass or less, more preferably 60 parts by mass or less.

(Stabilizer)
The stabilizer is a component for suppressing deterioration of the vinyl chloride resin due to heat, ultraviolet rays or oxygen. As such a stabilizer, it is possible to appropriately select and use from among known stabilizers for vinyl chloride resins. For example, a barium-zinc stabilizer, a calcium-zinc stabilizer and the like can be mentioned. In the case of barium-zinc stabilizers and calcium-zinc stabilizers, they are used in the form of salts of higher fatty acids such as stearic acid.

  The content of such a stabilizer in the under-foamed layer 2 is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the vinyl chloride resin, from the viewpoint of heating stability. From the viewpoint, it is preferably 7 parts by mass or less, more preferably 4 parts by mass or less.

(filler)
The filler is a component for improving the mechanical strength, heat resistance, workability and the like of the under foam layer 2. Such a filler can be appropriately selected and used from known fillers for vinyl chloride resins. Specific examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide and zinc borate. Among them, calcium carbonate can be preferably mentioned from the viewpoint of availability cost.

  The content of such a filler in the under-foamed layer 2 is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, from the viewpoint of fire protection performance, based on 100 parts by mass of the vinyl chloride resin, and coating stability From the viewpoint, it is preferably 100 parts by mass or less, more preferably 70 parts by mass or less.

(Other additives)
The under-foamed layer 2 further contains known additives for vinyl chloride resins, for example, pigments such as zinc oxide and titanium oxide, lubricants such as metal soap (eg zinc stearate), antioxidants, fungicides and the like. Can be included.

<Base resin layer 3>
The vinyl chloride resin-based base resin layer 3 constituting the wallpaper 10 of the present invention is laminated so as to cover the entire one surface of the base material layer 1 via the under foam layer 2. By forming the base resin layer 3 from a vinyl chloride resin-based material, it is possible to impart good fireproof performance to the wallpaper 10. Also. Since it is laminated on the entire one surface of the base material layer 1 via the under-foaming layer 2, even if the base material layer 1 is distorted or cracked, it is less likely to be affected by the distortion and crack resistance of the wallpaper 10. Can be improved.

  The base resin layer 3 may be a resin layer that does not contain bubbles (in other words, a resin layer that is not foamed), but may also contain fine bubbles for adjusting the gloss of the wallpaper surface. Such fine bubbles may be communicated with each other or may be independent. The expansion ratio when the base resin layer 3 contains air bubbles is preferably more than 1 time and less than 2 times from the viewpoint of maintaining crack resistance, but in the relative relationship with the under foam layer 2, The foaming ratio of the resin layer is smaller than that of the under-foaming layer. Preferably, the expansion ratio of the base resin layer 3 is 0.1 to 0.7 times the expansion ratio of the under foam layer 2.

The thickness of the base resin layer 3 is preferably 90 μm or more, more preferably 120 μm or more from the viewpoint of extensibility and crack resistance of the coating film, and preferably 170 μm or less, more preferably 150 μm or less from the viewpoint of fire prevention performance. is there. In addition, the thickness of the base resin layer 3 has a positive correlation with the basis weight of the base resin layer 3, and thus can be evaluated by the basis weight. Specifically, the basis weight of the base resin layer 3 is preferably 100 g / m ² or more, and preferably 150 g / m ² or less, from the viewpoint of fire protection performance.

  The base resin layer 3 is formed by layering a vinyl chloride resin-based material, and in terms of composition, contains at least a vinyl chloride resin, a plasticizer, a stabilizer, and optionally a filler. be able to.

(Vinyl chloride resin)
The vinyl chloride resin is a main resin forming the base resin layer 3, and the same resin as the vinyl chloride resin forming the under foam layer 2 can be used. The apparent polymerization degree is preferably 1550 or more, more preferably 2000 or more, from the viewpoint of ensuring the elongation at which the base resin layer can maintain crack resistance, and preferably 4000 or less from the viewpoint of workability. It is preferably 3000 or less.

(Plasticizer)
As the plasticizer, the same plasticizer as the plasticizer constituting the under foam layer 2 can be used, and adipic acid plasticizer, phosphoric acid plasticizer, polyester plasticizer, phthalic acid plasticizer, etc. can be used. Can be mentioned. Among them, phthalic acid esters such as bis (2-ethylhexyl) phthalate and diisononyl phthalate can be preferably used.

  The content of such a plasticizer in the base resin layer 3 is preferably 40 parts by mass or more, more preferably 50 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of processability and designability. It is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.

(Stabilizer)
As the stabilizer, the same stabilizer as the stabilizer forming the under foam layer 2 can be used. For example, a barium-zinc stabilizer, a calcium-zinc stabilizer and the like can be mentioned.

  The content of such a stabilizer in the base resin layer 3 is preferably 1 part by mass or more, more preferably 2 parts by mass or more, from the viewpoint of heating stability, with respect to 100 parts by mass of the vinyl chloride resin, and the foamed appearance. From the viewpoint, it is preferably 7 parts by mass or less, more preferably 4 parts by mass or less.

(filler)
When the filler is used in the base resin layer 3, the same filler as the filler forming the under foam layer 2 can be used. Specific examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate and the like. Among them, calcium carbonate can be preferably mentioned from the viewpoint of cost of acquisition.

  When a filler is used in the base resin layer 3, the content of the filler in the base resin layer 3 is preferably 10 parts by mass or more based on 100 parts by mass of the vinyl chloride resin from the viewpoint of fireproof performance. The amount is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, from the viewpoint of ensuring elongation such that the layer can maintain crack resistance.

(Other additives)
The base resin layer 3 further includes known additives for vinyl chloride resins, for example, pigments such as zinc oxide and titanium oxide, lubricants such as metal soap (eg, zinc stearate), antioxidants and fungicides. Can be included.

<Pattern foam layer 4>
In the wallpaper 10 of the present invention, it is preferable that the patterned foam layer 4 is further laminated on the surface of the base resin layer 3 opposite to the under foam layer 2 in order to improve the design and the like. The patterned foam layer 4 is disposed on the surface of the base resin layer 3, and contains vinyl chloride resin in terms of composition, and is structurally composed of resin foam bodies 4a, 4b ... There is. As described above, by constructing the patterned foam layer 4 from the vinyl chloride resin-based material, it is possible to impart good fireproof performance to the wallpaper 10. Also. By partially providing the pattern foam layer 4 on the base resin layer 3, the wallpaper 10 can be provided with irregularities rich in designability without performing embossing. Further, by providing the pattern foam layer 4, it is possible to impart a complicated nuance due to the unevenness of the wallpaper surface, and it is possible to expand the degree of freedom in design. Further, the visibility of the boundary between the wallpapers when the wallpaper is applied to the wall surface can be effectively weakened. In addition, the range of gloss adjustment of the entire wallpaper can be expanded.

  The handle foam layer 4 may be a single layer, or may be a handle foam unit layer having two or more layers. In the case of multiple layers, the plurality of pattern foaming unit layers can have different foaming ratios and different patterns (planar shape, for example, continuous pattern, discontinuous pattern, or a combination of these patterns), and design freedom It can be expanded even more.

  As for the base material coverage of the handle foam layer 4 in plan view, the coverage necessary for realizing the intended design appearance may be appropriately selected. Regardless of whether it is a single layer or a multi-layer, the base material coverage of the patterned foam layer 4 is preferably 20% or more and 85% or less, more preferably 30% or more and 80% or less.

  The expansion ratio of the patterned foam layer 4 is preferably greater than 1 times, more preferably 2 times or more from the viewpoint of designability, etc., and is preferably 7 times or less, more preferably 4 times from the viewpoint of surface strength. It is below.

  The thickness of the handle foam layer 4 is not particularly limited, and may be appropriately selected to achieve the intended design appearance.

  The handle foam layer 4 is formed by forming a vinyl chloride resin material into a layer and subjecting it to foaming, and contains at least a vinyl chloride resin, a plasticizer, a stabilizer, and a filler.

(Vinyl chloride resin)
The vinyl chloride resin is the main resin that constitutes the patterned foam layer 4, and the same resin as the vinyl chloride resin that constitutes the under-foamed layer 2 can be used. The apparent polymerization degree is preferably 500 or more, more preferably 600 or more from the viewpoint of handleability, and preferably 1500 or less, more preferably 1300 or less from the viewpoint of foaming stability.

(Plasticizer)
As the plasticizer, the same plasticizer as the plasticizer constituting the under foam layer 2 can be used, and adipic acid plasticizer, phosphoric acid plasticizer, polyester plasticizer, phthalic acid plasticizer, etc. can be used. Can be mentioned. Among them, phthalic acid esters such as bis (2-ethylhexyl) phthalate and diisononyl phthalate can be preferably used.

  The content of such a plasticizer in the handle foam layer 4 is preferably 40 parts by mass or more, and more preferably 50 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of processability and designability. , Preferably 80 parts by mass or less, more preferably 70 parts by mass or less.

(Stabilizer)
As the stabilizer, the same stabilizer as the stabilizer forming the under foam layer 2 can be used. For example, a barium-zinc stabilizer, a calcium-zinc stabilizer and the like can be mentioned.

  The content of such a stabilizer in the foamed foam layer 4 is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 7 parts by mass or less, based on 100 parts by mass of the vinyl chloride resin. It is preferably 6 parts by mass or less.

(filler)
As the filler, the same stabilizer as the filler forming the under foam layer 2 can be used. Specific examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate and the like. Among them, calcium carbonate can be preferably mentioned from the viewpoint of availability cost.

  The content of such a filler in the handle foam layer 4 is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and preferably 80 parts by mass or less, based on 100 parts by mass of the vinyl chloride resin. It is preferably 70 parts by mass or less.

(Other additives)
The patterned foam layer 4 further includes known additives for vinyl chloride resins, for example, pigments such as zinc oxide and titanium oxide, lubricants such as metal soap (eg, zinc stearate), antioxidants and fungicides. Can be included.

(surface treatment)
In the wallpaper of the present invention, after the base resin layer and the pattern foam layer are provided, embossing or pattern printing may be appropriately performed on the surface, if necessary.

<Wallpaper manufacturing method>
In the wallpaper of the present invention, a composition for forming an under foam layer is applied to one surface of a base material layer by a known coating method such as a screen method (for example, a silk screen method, preferably a rotary screen method), and subsequently, a base resin. It can be produced by applying the layer forming composition and heat-treating the obtained laminate to foam the under foamed layer forming composition to form the under foamed layer. More specifically, it can be manufactured using a rotary screen printing apparatus as shown in FIG. 3, which is an example of a screen printing apparatus. The details will be described below.

(A) Step of forming composition layer for forming under-foamed layer First, the base material layer 31 unwound from the unwinding roll 30 in the arrow direction is passed between the rotary screen 32a and the backup roll 33a. At that time, the composition for forming an under foam layer (not shown) filled in the rotary screen 32a is applied to one surface of the base material layer 31 by a squeegee (not shown) arranged in the rotary screen 32a, An under-foamed layer forming composition layer (not shown) is formed by passing through the drying oven 34a. In addition, in FIG. 3, application was performed using a rotary screen, but a knife coater or the like may be used to form the composition layer for forming the base resin layer.

  Here, the composition of the under-foamed layer forming composition is one in which a foaming agent and, if necessary, a solvent are added to the components constituting the under-foamed layer 2. As the foaming agent, a known pyrolytic foaming agent used for forming a vinyl chloride foam layer of a vinyl chloride resin-based wallpaper can be used. As such a thermal decomposition type foaming agent, an azodicarbonamide type foaming agent or an oxybisbenzenesulfonyl hydrazide type foaming agent can be preferably used. The content of the foaming agent in the composition for forming an under-foamed layer is preferably 1 part by mass or more, and more preferably 3 parts with respect to 100 parts by mass of the vinyl chloride resin, from the viewpoint of ensuring the elongation of the base resin layer 3 and designability. The amount is at least 10 parts by mass, preferably 10 parts by mass or less, and more preferably 9 parts by mass or less, from the viewpoint of uniformity of foam appearance and design.

(B) Forming Step of Composition Layer for Forming Base Resin Layer Next, after cooling the laminate having passed through the drying oven 34a by the cooling cylinder 35a, while passing between the rotary screen 32b and the backup roll 33b, The base resin layer forming composition (not shown) filled in the rotary screen 32b is applied to the under foaming layer forming composition layer by a squeegee (not shown) arranged in the rotary screen 32b and dried. A composition layer (not shown) for forming a base resin layer is formed by passing through the furnace 34b. In FIG. 3, the base resin layer-forming composition was applied using a rotary screen, but it may be applied using another application method, for example, a knife coater. If the base resin layer-forming composition does not contain a foaming agent, the base resin layer 3 will be formed in this step.

  Here, the composition of the composition for forming the base resin layer is a composition in which a foaming agent or a solvent is added to the components constituting the base resin layer 3 as necessary. As the foaming agent, a known pyrolytic foaming agent used for forming a vinyl chloride foam layer of a vinyl chloride resin-based wallpaper can be used, but a microcapsule type foaming agent that generates relatively small bubbles. Can be preferably used. The content of the foaming agent in the base resin layer-forming composition is preferably 0.1 part by mass or more from the viewpoint of designability with respect to 100 parts by mass of the vinyl chloride resin, and preferably from the viewpoint of processability and acquisition cost. It is 0.8 parts by mass or less, more preferably 1.0 parts by mass or less.

(C) Under-foaming layer forming step After the laminate that has passed through the drying oven 34b is cooled by the cooling cylinder 35b, the laminate passes through the foaming oven 36, thereby foaming the under-foaming layer-forming composition layer to under-deposit. A foam layer is formed and cooled by the cooling cylinder 35c. Further, when the composition for forming a base resin layer contains a foaming agent, it is foamed in this step to form a base resin layer. Thereby, the wallpaper 10 is obtained.

(D) Pattern Foam Layer-Forming Composition Layer Forming Step After the formation of the base resin layer-forming composition layer, before use of the laminate in a foaming furnace, a pattern foam layer-forming composition is optionally used. To form a pattern foam layer-forming composition layer by performing the same step as the under foam layer-forming composition layer forming step one or more times, and further foaming similarly to the under foam layer-forming step. The pattern foam layer can be formed by passing through the furnace 36.

  Here, the composition of the pattern foam layer-forming composition is a composition in which a foaming agent or a solvent is added to the components constituting the pattern foam layer 4, if necessary. As the foaming agent, a known pyrolytic foaming agent used for forming a vinyl chloride foam layer of a vinyl chloride resin-based wallpaper can be used. As such a thermal decomposition type foaming agent, an azodicarbonamide type foaming agent or an oxybisbenzenesulfonyl hydrazide type foaming agent can be preferably used. When a foaming agent is used in the composition for forming a pattern foam layer, the content thereof is preferably 1 part by mass or more from the viewpoint of designability with respect to 100 parts by mass of the vinyl chloride resin, and preferably from the viewpoint of processability. It is 6 parts by mass or less, and more preferably 5 parts by mass or less.

  Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto. Comparative Example 1 relates to a wallpaper having a three-layer structure of base material / base resin layer / patterned foam layer, and Comparative Example 8 and Example 8 have three layers of base material / under-foamed layer / base resin layer. The wallpapers of Examples 1 to 7 and Comparative Examples 2 to 7 relate to a wallpaper having a four-layer structure including a substrate / under foam layer / base resin layer / pattern foam layer. Moreover, the same base material was used in all the Examples and Comparative Examples. Further, the same patterned foam layer was adopted in the wallpapers of Examples 1 to 7 and Comparative Examples 1 to 7. The compounds and raw materials used in Examples and Comparative Examples are shown in Table 1 below.

Example 1
(1) Formation of composition layer for forming under-foamed layer A composition for forming under-foamed layer is prepared by uniformly mixing the following components of the composition for forming under-foamed layer, and the prepared composition for forming under-foamed layer is formed. The composition was applied to one side of a 110 μm thick wallpaper base material by a screen method at a rate of 15 g / m ² so that the base material coverage of the under-foamed layer was 15.2% in a top view, and at 130 ° C. The composition layer for forming an under foam layer was formed on the substrate by heating and drying for 60 seconds.

(Composition for forming under foam layer)
Vinyl chloride resin (Kanevinyl (registered trademark) paste PSM-271R (polymerization degree 1150), Kaneka Corporation) 100 parts by mass;
60 parts by mass of plasticizer (DOP);
Blowing agent (Uniform (registered trademark) AZH, Otsuka Chemical Co., Ltd.) 4 parts by mass;
Stabilizer (Adeka Stub (registered trademark) FL44, ADEKA Co., Ltd.) 3 parts by mass;
50 parts by mass of a filler (Whiten (registered trademark) H, Toyo Fine Chemical Co., Ltd.); and 20 parts by mass of a colorant (JR-401, Teika Co., Ltd.).

(2) Formation of Base Resin Layer-Forming Composition Layer A base resin layer-forming composition is prepared by uniformly mixing the following components of the base resin layer-forming composition, and the prepared base resin layer-forming composition is prepared. The composition was applied onto the composition layer for forming an under-foamed layer by a screen method at a rate of 140 g / m ² so that the base material coverage of the base resin layer was 100% in a top view, and the composition was applied at 60 ° C. at 130 ° C. The base resin layer-forming composition layer was formed on the under foam layer-forming composition layer by heating and drying for seconds.

(Base resin layer forming composition)
Vinyl chloride resin (Kanevinyl (registered trademark) paste PSH-24 (polymerization degree 2800), Kaneka Corporation) 100 parts by mass;
60 parts by mass of plasticizer (DOP);
0.5 part by mass of foaming agent (EHM302, Sekisui Chemical Co., Ltd.);
Stabilizer (Adeka Stub (registered trademark) FL 44, ADEKA Co., Ltd.) 3 parts by mass;
30 parts by mass of filler (Whiten (registered trademark) H, Toyo Fine Chemical Co., Ltd.);
20 parts by mass of colorant (JR-401, Teika Co., Ltd.).

(3) Formation of Pattern Foam Layer-Forming Composition Layer A pattern foam layer-forming composition was prepared by uniformly mixing the following composition components of the pattern foam layer-forming composition, and the prepared pattern foam layer-forming composition was prepared. The composition was applied on the composition layer for forming a base resin layer by a screen method at a rate of 40 g / m ² so that the base material coverage of the patterned foam layer was 40% in a top view, and the composition was applied at 60 ° C. at 130 ° C. A pattern foam layer-forming composition layer was formed on the base resin layer-forming composition layer by heating and drying for seconds.

(Pattern for forming foam layer)
Vinyl chloride resin (Kanevinyl (registered trademark) paste PSM-271R (polymerization degree 1150), Kaneka Corporation) 100 parts by mass;
60 parts by mass of plasticizer (DOP);
Blowing agent (Uniform (registered trademark) AZH, Otsuka Chemical Co., Ltd.) 4 parts by mass;
Stabilizer (Adeka Stab (registered trademark) FL44, ADEKA Co., Ltd.) 3 parts by mass;
50 parts by mass of a filler (Whiten (registered trademark) H, Toyo Fine Chemical Co., Ltd.); and 20 parts by mass of a colorant (JR-401, Teika Co., Ltd.).

(4) Manufacture of wallpaper A laminate obtained from the substrate / under-foam layer-forming composition layer / base resin layer-forming composition layer / patterned foam layer-forming composition layer obtained as described above is used in a foaming furnace. And heated at 190 ° C. for 75 seconds. Thereby, the foaming agent in each layer of the composition layer for forming an under foam layer, the composition layer for forming a base resin layer and the composition layer for forming a pattern foam layer is foamed, and an under foam layer having a foaming ratio of 6 times and a foaming ratio of 1 A wallpaper of Example 1 was obtained by forming a base resin layer of 0.5 times and a patterned foam layer having an expansion ratio of 3 times.

Comparative Example 1
A wallpaper of Comparative Example 1 was obtained in the same manner as in Example 1 except that the under foam layer was not formed.

Comparative example 2
The same procedure as in Example 1 was carried out except that the composition for forming an under-foamed layer was applied on a base material at a rate of 8 g / m ² so that the base material coverage of the under-foamed layer was 8.7% in a top view. A wallpaper of Comparative Example 2 was obtained.

Examples 2-5, Comparative Example 3
The composition for forming an under foam layer has a base material coverage of 31.2%, 54.7%, 78.6%, 83.1%, or 100% of the under foam layer in a top view. Thus, a wallpaper was obtained in the same manner as in Example 1 except that the coating was applied at a rate of 30 g / m ² , 50 g / m ² , 75 g / m ² , 80 g / m ² , or 100 g / m ² , respectively.

Comparative Example 4, Example 6, Comparative Example 5
As the vinyl chloride resin used in the composition for forming a base resin layer, instead of the vinyl chloride resin having a polymerization degree of 2800, in Comparative Example 4, a vinyl chloride resin having a polymerization degree of 700 (Kanevinyl (registered trademark) paste PSL-675, ( Kaneka Co., Ltd.), in Example 6 a vinyl chloride resin having a degree of polymerization of 1550 (ZEST PQHP, Shin Daiichi Vinyl Co., Ltd.) was used, and in Comparative Example 5, a vinyl chloride resin having a degree of polymerization of 4500 (Leuron) was used. Wallpapers of Comparative Example 4, Example 6 and Comparative Example 5 were obtained in the same manner as in Example 3 except that Paste (registered trademark) 960 and Tosoh Corporation were used.

Comparative Example 6, Example 7, Comparative Example 7
As the vinyl chloride resin used in the composition for forming the under foam layer, instead of the vinyl chloride resin having a polymerization degree of 1150, in Comparative Example 6, a vinyl chloride resin having a polymerization degree of 480 (Kanevinyl (registered trademark) paste S-400, ( Kaneka Co., Ltd.), a vinyl chloride resin having a polymerization degree of 700 (Kanevinyl (registered trademark) paste PSL-675, Kaneka Co., Ltd.) was used in Example 7, and a chloride having a polymerization degree of 3000 was used in Comparative Example 7. Vinyl resin blend (vinyl chloride resin having a degree of polymerization of 700 (Kanevinyl (registered trademark) paste PSL-675, Kaneka Co., Ltd.)) and vinyl chloride resin having a degree of polymerization of 4,500 (Luron paste (registered trademark) 960, Tosoh Corporation) )) Was blended in a mass ratio of 3: 2), and wallpaper of Comparative Example 6, Example 7, and Comparative Example 7 was obtained in the same manner as in Example 3.

Comparative Example 8, Example 8
Wallpapers of Comparative Example 8 and Example 8 were obtained in the same manner as Comparative Example 2 and Example 3, except that the patterned foam layer was not formed.

<Evaluation>
For the under-foaming layer forming composition and the base resin layer forming composition obtained in Examples and Comparative Examples, "coating workability" was evaluated as an evaluation item, and for wallpaper, "folding property", “Elongation”, “flame retardancy” and “design” were evaluated, and the evaluation results are shown in Table 2. In Table 2, “◯” indicates good, “Δ” indicates that there is no problem in practical use, and “x” indicates failure.

(A) Coating workability With respect to the composition for forming an under-foamed layer and the composition for forming a base resin layer, the coating workability when applied by the screen method was evaluated according to the following evaluation criteria, and Table 2 shows the evaluation results. ..

(Coating processability evaluation criteria)
◯: When it can be applied without problems x: When the composition for forming the under-foamed layer or the composition for forming the base resin layer cannot be properly transferred from the screen to the coated surface

(B) Folding property The wallpaper obtained in each of the examples and comparative examples was attached to a cardboard having a basis weight of 2000 g / m ² with a paste for wallpaper, and the cardboard was bent 90 degrees so that the inside was formed. The bent state of the surface was visually observed and evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.
(Bending bendability evaluation standard)
◯: When the resin coating film covers the entire surface and no cracks are observed by bending. Δ: The resin coating film covers the entire surface, but cracks are likely to be formed on a part of the resin coating film by bending. Is observed, but there is no problem in practical use x: When the resin coating film disappears in the bent portion and cracks are observed

(C) Elongation The wallpaper obtained in each of the examples and comparative examples was cut into a piece having a width of 15 mm and a length of 50 mm to obtain an elongation evaluation sample. Separately, two sheets of cardboard having a width of 20 mm and a length of 50 mm and a basis weight of 300 g / m ² were prepared, and a double-sided tape having a width of 20 mm and a length of 25 mm was attached to each of them. Next, place the thick paper with the double-sided tape attached so that the width of the thick paper touches it, and then stick the double-sided tape on the base material surface of the wallpaper so as to straddle the two thick papers. After leaving it at constant temperature and humidity for 1 day, Shimadzu A tensile test was conducted using a universal testing machine manufactured by Seisakusho Co., Ltd. so that the wallpaper would stretch, and the elongation (mm) was measured when the width of the wallpaper sample became 7.5 mm, which was half the original width of 15 mm. The measurement results obtained are shown in Table 2. The average value of 5 points of the sample is shown in Table 2 as a displacement value. The displacement value is desired to be 6 mm or more.

(Coating processability evaluation criteria)
◯: When it can be applied without problems x: When the composition for forming the under-foamed layer or the composition for forming the base resin layer cannot be properly transferred from the screen to the coated surface

(D) Flame Retardancy The wallpaper obtained in each of the examples and comparative examples was heated for 10 minutes by a method in accordance with the exothermic test method of ISO 5660 (corn calorimeter method), and the following evaluation indices (a) to ( The flame retardancy was rated as "good" when all of the conditions c) were satisfied, and the flame retardancy was rated as "poor" when none of them was satisfied. The obtained results are shown in Table 2.

(Flame retardancy evaluation index)
(A) The total calorific value for 10 minutes after the start of heating is 8 MJ / m ² or less (b) For 10 minutes after the start of heating, there are no cracks or holes penetrating to the back surface harmful to fire prevention (c) Start of heating For the next 10 minutes, the maximum heat release rate should not exceed 200 Kw / m ² for 10 seconds.

(E) Designability The surface of the wallpaper obtained in each Example and Comparative Example was visually observed and evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.

(Design evaluation criteria)
○: When the unevenness due to the foaming of the under-foaming layer or the pattern foaming layer can be clearly confirmed and is rich in three-dimensional effect. When there is no ×: When the foaming state of the foamed under layer is insufficient and there is almost no foaming, or an abnormal bulge is observed on the foamed surface.

<Discussion of evaluation results>
The wallpaper of Examples 1 to 8 has a base material coverage of the under-foamed layer in the range of 10% to 85% in plan view, and shows good or practically no problem in any evaluation item. It was In addition, in the case of Example 1, since the base material coverage of the under-foamed layer was relatively low at 15.2%, the bending bendability was evaluated as “Δ”, but there was no problem in practical use. In the case of Example 5, since the base material coverage of the under-foamed layer was relatively high at 83.1%, the designability was evaluated as “Δ”, but there was no problem in practical use. From these, it is understood that it is particularly preferable that the substrate coverage of the under-foamed layer is in the range of 30% to 80% in plan view (Examples 2 to 4).

  In addition, in the case of Example 6, since the degree of polymerization of the vinyl chloride resin of the base resin layer was relatively low at 1550, the bending bendability was evaluated as “Δ”, but there was no problem in practical use. In the case of Example 7, the degree of polymerization of the vinyl chloride resin in the under-foamed layer was 700, which was relatively low, and therefore the designability was evaluated as “Δ”, but there was no problem in practical use. In the case of Example 8, since the pattern foam layer was not present, the designability was evaluated as “Δ”, but there was no problem in practical use.

  On the other hand, since the wallpaper of Comparative Example 1 was not provided with the under-foamed layer, not only the bending property but also the design property was evaluated as “x”. Moreover, the extensibility was less than 6 mm. In the wallpaper of Comparative Example 2, since the base material coverage of the under-foamed layer was less than 10% in a plan view, similarly to Comparative Example 1, the bendability was evaluated as “x” and the extensibility was 6 mm. Was less than. The wallpaper of Comparative Example 8 has the same configuration as that of Comparative Example 2 except that it does not have a patterned foam layer. Therefore, the wallpaper is the same as that of Comparative Example 2 except that the design property is evaluated as “Δ”. It was an evaluation.

  In the wallpaper of Comparative Example 3, the base material coverage of the under foam layer was 100%, which was too high. In the wallpaper of Comparative Example 4, the degree of polymerization of the vinyl chloride resin constituting the base resin layer was 700, which is much lower than 1500, and thus the bending property was also evaluated as “x” and the extensibility was also less than 6 mm. It was In the case of Comparative Example 5, the degree of polymerization of the vinyl chloride resin constituting the base resin layer was 4500, which was much higher than 4000, so the coating processability of the composition for forming a base resin layer was evaluated as “x”, and the wallpaper Could not be created.

  In the wallpaper of Comparative Example 6, the degree of polymerization of the vinyl chloride resin forming the under-foamed layer was 480, which was much lower than 700, so the degree of unevenness was too small and the designability was evaluated as “x”. In the wallpaper of Comparative Example 7, the degree of polymerization of the vinyl chloride resin constituting the under-foamed layer was 3000, which was much higher than 1500, so the degree of unevenness was too large and the designability was evaluated as “x”.

  The wallpaper of the present invention has a structure in which a base material layer, an under-foamed layer made of a resin foam, and a base resin layer that covers 100% of the base material layer in plan view are laminated in this order, and As described above, it is possible to have an uneven shape that exhibits good fireproof performance, excellent crack resistance, and is highly designable without embossing. Therefore, it is particularly useful as a wallpaper for ordinary houses.

1, 31 Base material layer 2 Under foam layer 2a, 2b, 4a, 4b Resin foam 3 Base resin layer 4 Pattern foam layer 10 Wallpaper 30 Unwinding roll 32a, 32b Rotary screen 33a, 33b Backup roll 34a, 34b Drying oven 35a , 35b, 35c Cooling cylinder 36 Foaming furnace

Claims (12)

A wallpaper in which a base material layer, an under-foaming layer containing a vinyl chloride resin, and a base resin layer containing a vinyl chloride resin are laminated in this order,
The under foam layer is made of resin foam,
The substrate coverage by the under foam layer is 10% or more and 85% or less in a plan view, and the apparent degree of polymerization of the vinyl chloride resin constituting the under foam layer is 700 to 1500,
A wallpaper in which the base material coverage of the base resin layer is 100% in a plan view, and the apparent degree of polymerization of the vinyl chloride resin forming the base resin layer is 1550 to 4000.   The wallpaper according to claim 1, wherein the coverage of the base layer with the under-foamed layer is 30% or more and 80% or less in plan view.   The wallpaper according to claim 1 or 2, wherein a foaming ratio of the under-foaming layer is larger than that of the base resin layer when the base resin layer is foamed.   The wallpaper according to claim 3, wherein the under-foaming layer has a foaming ratio of 3 to 10 times, and the base resin layer has a foaming ratio of 1 to 2 times.   The wallpaper according to any one of claims 1 to 4, wherein the base material layer has a thickness of 80 to 150 µm, the under-foamed layer has a thickness of 200 to 400 µm, and the base resin layer has a thickness of 90 to 170 µm. The basis weight of the base material layer is 50 to 100 g / m ² , the basis weight of the under-foamed layer is 10 to 100 g / m ² , and the basis weight of the base resin layer is 100 to 150 g / m ^2. The wallpaper according to any one of to 5.   The under foaming layer contains 40 to 70 parts by mass of a plasticizer, 1 to 7 parts by mass of a stabilizer, and 5 to 100 parts by mass of a filler with respect to 100 parts by mass of a vinyl chloride resin. wallpaper.   The wallpaper according to any one of claims 1 to 7, wherein the base resin layer contains 40 to 80 parts by mass of a plasticizer and 1 to 7 parts by mass of a stabilizer with respect to 100 parts by mass of a vinyl chloride resin.   The wallpaper according to claim 8, wherein the base resin layer further contains 10 to 50 parts by mass of the filler with respect to 100 parts by mass of the vinyl chloride resin.   The wallpaper according to any one of claims 1 to 9, wherein a patterned foam layer is further laminated on the surface of the base resin layer opposite to the under foam layer.   The method for producing a wallpaper according to claim 1, wherein the underfoaming layer-forming composition is applied to one surface of the base material layer by a screen method, and subsequently, the base resin layer-forming composition is applied to obtain one. A method for producing, wherein the under-foamed layer-forming composition is foamed to form an under-foamed layer by heat-treating the laminate.   The method for producing a wallpaper according to claim 10, wherein the underfoaming layer forming composition is applied to one surface of the base material layer by a screen method, and subsequently, the base resin layer forming composition is applied, and further, pattern foaming. By applying the layer-forming composition and heat-treating the obtained laminate, the under-foamed layer-forming composition and the pattern-foamed layer-forming composition are foamed to form the under-foamed layer and the patterned foam layer. Production method.

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