JP7154062B2 - wallpaper - Google Patents

Description

TECHNICAL FIELD The present invention relates to wallpaper used for building interior materials such as floors, walls and ceilings, and a method for producing the wallpaper.

Wallpaper is relatively inexpensive, can be mass-produced, and has a wide variety of designs, so it is widely used as an interior decoration material both in Japan and overseas.

Polyvinyl chloride-based resins and olefin-based resins are often used for wallpaper. In particular, polyvinyl chloride-based resins are used exclusively because they are inexpensive, have excellent physical properties, and can be embossed to form fine unevenness on the surface to further impart designability. However, there is a problem that it is susceptible to contamination from food, cigarettes, fingerprints, graffiti, etc., and damage from pet or accidental contact.

Therefore, conventionally, a method of laminating a film for the purpose of imparting stain resistance and scratch resistance to wallpaper has been known. ing. A wallpaper using a polypropylene film is disclosed, for example, in Patent Document 2.

JP 2006-282834 A JP 2006-096021 A

In embossing, which is performed for the purpose of imparting design to wallpaper, a foaming agent is often used in the resin layer, etc., since increasing the thickness difference between the recesses and protrusions improves the three-dimensional effect. Among them, azodicarbonamide foaming agents are widely used because they are inexpensive and generate a large amount of gas. However, this foaming agent is yellow, and although it is decolorized by thermal decomposition, the undecomposed residue imparts a yellow tint to the product. That is, there is a problem that the degree of yellowness becomes high and pale color tone cannot be expressed.

That is, an object of the present invention is to provide a wallpaper which is excellent in stain resistance and scratch resistance and has a low degree of yellowness.

As a result of intensive verification of the above problems, the means used in the present invention is a base material, a resin layer containing a polyvinyl chloride resin laminated on the base material, and a film layer laminated on the upper side of the resin layer. wherein an oxybisbenzenesulfonyl hydrazide-based foaming agent is added to the resin layer, substantially no azodicarbonamide-based foaming agent is added , and the width of the substrate and the width of the film layer are equal to the width of the resin layer The wallpaper is wider than the above, and the base material and the film layer are directly bonded at both ends . In addition, it comprises a substrate, a resin layer containing a polyvinyl chloride resin laminated on the substrate, and a film layer laminated on the upper side of the resin layer, and an oxybisbenzenesulfonyl hydrazide foaming agent is added to the resin layer. and substantially no azodicarbonamide-based foaming agent is added, and the width (R) of the resin layer and the width (F) of the film layer are expressed as "film layer width (F) - resin layer width (R) ≤ 4 mm", comprising a base material, a resin layer containing a polyvinyl chloride resin laminated on the base material, and a film layer laminated on the upper side of the resin layer, and oxybisbenzenesulfonyl A hydrazide-based foaming agent is added, and substantially no azodicarbonamide-based foaming agent is added, and the width (P) of the substrate is set to "substrate width (P) - film layer width (F) > 0 mm". is a wallpaper that satisfies.
Furthermore, a step of laminating a resin layer containing a polyvinyl chloride resin on the upper side of the base material, and a film laminating step of laminating a film layer on the upper side of the resin layer, wherein the width of the film layer is the width of the resin layer More broadly, it is possible to use a wallpaper manufacturing method in which both ends of a substrate and a film layer are directly adhered in the film lamination process.

INDUSTRIAL APPLICABILITY The present invention can provide a wallpaper having a low yellowness index and excellent stain resistance and scratch resistance.

It is a sectional view concerning one embodiment of wallpaper of the present invention. It is a sectional view concerning one embodiment of wallpaper of the present invention.

The gist of the present invention is to provide a substrate, a resin layer containing a polyvinyl chloride resin laminated on the substrate, and a film layer laminated on the upper side of the resin layer, wherein the resin layer contains an oxybisbenzenesulfonyl hydrazide-based It is a wallpaper to which a foaming agent is added and substantially no azodicarbonamide foaming agent is added. Here, substantially no azodicarbonamide foaming agent is added means that the azodicarbonamide foaming agent is not added to the extent that the foaming property of the oxybisbenzenesulfonylhydrazide foaming agent is affected. This makes it possible to obtain wallpaper with a low degree of yellowness.

"resin layer"
As the oxybisbenzenesulfonylhydrazide foaming agent used in the resin layer, p,p'-oxybisbenzenesulfonylhydrazide is preferable. Additives may be used as long as they do not affect the foamability.

Here, it is preferable to use only the oxybisbenzenesulfonyl hydrazide foaming agent. The use of an azodicarbonamide-based blowing agent is not preferable because yellowing is increased. The azodicarbonamide-based foaming agent is a foaming agent composed of azodicarbonamide, and includes a single foaming agent and a foaming agent containing an additive for improving physical properties. In the present invention, the azodicarbonamide foaming agent is not added in an amount effective as a foaming agent. That is, wallpaper with a low degree of yellowness can be obtained by using an oxybisbenzenesulfonylhydrazide-based foaming agent without substantially adding an azodicarbonamide-based foaming agent.

The polyvinyl chloride-based resin used for the resin layer may contain vinyl chloride as a main component, but may contain a copolymer component other than vinyl chloride. Specifically, polyvinyl chloride, ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer, vinyl chloride-acrylic resin copolymer, vinyl chloride-urethane copolymer, vinyl chloride-vinylidene chloride copolymer , vinyl chloride-vinyl acetate copolymer, and the like. As the vinyl chloride resin, polyvinyl chloride resin for paste processing and suspension polyvinyl chloride resin can be used. Further, these polyvinyl chloride resins may be used singly or in combination of two or more. In particular, the use of a polyvinyl chloride resin for paste processing enables paste coating, enabling various foamed products to be produced by blending a large amount of various compounding agents with inexpensive equipment, and is suitable for small-lot, high-variety products. In terms of scratch resistance, calendering using a suspension polyvinyl chloride resin is easier to achieve, but in the present invention, even if a polyvinyl chloride resin for paste processing, which is disadvantageous in scratch resistance, is used. They have found that by firmly adhering the resin layer and the film layer, it is possible to provide a wallpaper having excellent scratch resistance and excellent adhesiveness between the resin layer and the film layer.

Polyvinyl chloride resin for paste processing is fine polymer particles having an average primary particle size of, for example, 0.02 to 20.0 μm, which is obtained mainly by emulsion polymerization or microsuspension polymerization. It is a general feature that it becomes paste-like with the addition of a plasticizer. The suspension polyvinyl chloride-based resin is a porous, amorphous vinyl chloride-based resin having an average primary particle size of, for example, 50 to 200 μm, which is obtained mainly by a suspension polymerization method. Due to its porous shape, it can absorb liquids such as plasticizers, so it is characterized by not becoming a paste, and is mainly used in extrusion and calendering.

By using a metal perchlorate for the resin layer, a foamed wallpaper with a lower yellowness can be obtained. This is presumed that the metal perchlorate acts as a stabilizer for the polyvinyl chloride resin in the foamed polyvinyl chloride resin layer and suppresses the yellowing caused by the oxybisbenzenesulfonylhydrazide foaming agent. . Oxybisbenzenesulfonylhydrazide-based blowing agents themselves are white, but they become colored at high temperatures, and the decomposition residue is acidic and generates a large amount of heat when decomposed, which may cause discoloration of polyvinyl chloride resins. be. Metal perchlorate is thought to suppress yellowing caused by oxybisbenzenesulfonylhydrazide foaming agents.

Furthermore, by using a stabilizer other than metal perchlorate in the foamed polyvinyl chloride resin layer, it is possible to further reduce the yellowness. Examples of stabilizers include barium-based stabilizers, calcium-based stabilizers, tin-based stabilizers, zinc-based stabilizers, potassium-based stabilizers, and the like, and two or more of these may be used in combination. In particular, it is preferable to use a barium-based stabilizer, a calcium-based stabilizer, a potassium-based stabilizer, and a zinc-based stabilizer in combination to obtain sufficient workability while reducing yellowness.

Examples of perchlorate metal salts include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, magnesium perchlorate, calcium perchlorate, barium perchlorate, and ammonium perchlorate. be done. Among them, sodium perchlorate and potassium perchlorate are preferably used. These perchlorates may be either anhydrides or hydrates, and may be dissolved in an alcoholic or ester solvent such as butyldiglycol or butyldiglycol adipate, or dehydrated products thereof. Perchloric acid-containing hydrotalcite obtained by treating hydrotalcite with perchloric acid may also be used.

The oxybisbenzenesulfonylhydrazide foaming agent used in the resin layer is preferably contained in an amount of 0.01 to 4 parts by weight per 100 parts by weight of the polyvinyl chloride resin. If it is less than 0.01 part by weight, the foaming property may not be sufficient, and if it exceeds 4 parts by weight, the foaming ratio becomes too high and sufficient scratch resistance may not be obtained. The use of a perchloric acid metal salt as a stabilizer can suppress yellowing, and is suitable because it is easy to maintain a low degree of yellowness even when the amount of foaming agent added is increased.
Although it is preferable not to add an azodicarbonamide foaming agent, if it is less than 0.1 parts by weight, the effect on yellowing is relatively small, and if it is less than 0.01 parts by weight, the effect on yellowing is less. It is preferable.

It is preferable that the resin layer contains 1 to 50 parts by weight of titanium oxide per 100 parts by weight of the polyvinyl chloride-based resin because the concealability and the weather resistance are improved. If the amount is less than 1 part by weight, it is difficult to obtain the effect of improving the hiding property or weather resistance.

The basis weight of the resin layer used in the present invention is preferably 100 g/m ² to 220 g/m ² from the viewpoint of concealability and fire resistance. If it is less than 100 g/m ² , the hiding power may be insufficient. If it exceeds 220 g/m ² , the fire resistance may deteriorate. Furthermore, by limiting the basis weight of the resin layer, the scratch resistance is improved, and is preferably 220 g/m ² or less, more preferably 160 g/m ² or less.
Therefore, from the viewpoints of hiding power and scratch resistance, it is preferably 100 g/m ² to 220 g/m ² , more preferably 120 g/m ² to 160 g/m ² .

Stabilizers, plasticizers, fillers, foaming agents, coloring agents, processing aids, antibacterial agents, antifungal agents, flame retardants, flame retardants, and defoaming agents are added to the resin layer as long as they do not interfere with problem solving. Various additives such as agents may be added as appropriate.

The plasticizer is not particularly limited, but examples include di-2-ethylhexyl phthalate, dioctyl terephthalate, diisononyl phthalate, dibutyl phthalate, dihexyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, trioctyl phthalate, dioctyl adipate, chlorinated fatty acid esters, and chlorinated paraffins. , epoxidized soybean oil, epoxidized fatty acid ester, polyester, etc., and two or more of them may be used in combination.

"Base material"
Substrates used in the present invention include plain paper (mainly pulp treated with a known sizing agent), flame-retardant paper (mainly pulp treated with a flame retardant such as guanidine sulfamate and guanidine phosphate), and inorganic materials. Examples include paper (containing inorganic additives such as magnesium hydroxide and aluminum hydroxide) and fleece paper (made by mixing pulp and synthetic fibers such as polyester). In particular, use of plain paper is preferable because it improves scratch resistance and workability.

Although the basis weight of the substrate is not particularly limited, it is preferably from 50 g/m ² to 170 g/m ² from the viewpoint of concealability and workability. If it is less than 50 g/m ² , the hiding property may be lacking or the workability may be deteriorated. If it exceeds 170 g/m ² , the fire resistance may deteriorate.

"film layer"
The resin used for the film layer of the present invention is not particularly limited, but polyolefins such as polyethylene and polypropylene, polybutylene, ethylene-vinyl alcohol copolymer, methacrylic, thermoplastic polyester, polyvinyl alcohol, and polyethylene. Examples include terephthalate-based, polylactic acid-based, polyvinyl chloride-based, polytetrafluoroethylene-based, ethylene-tetrafluoroethylene-based copolymers, polycarbonate-based, and silicone-based. In particular, polyolefin-based and ethylene-vinyl alcohol-based copolymer resins are suitable from the viewpoints of stain resistance, scratch resistance, curl resistance, and economy.

Although the thickness of the film layer is not particularly limited, it is preferably 10 μm to 25 μm. If it is less than 10 µm, the scratch resistance may be lacking. If it exceeds 25 µm, the workability and fire resistance may deteriorate.

In the present invention, it is preferable that the width of the film layer is larger than that of the resin layer. This will be described with reference to FIGS. 1 and 2, which are cross-sectional views of wallpaper in the width direction. The wallpaper 4 is formed by laminating a resin layer 2 and a film layer 3 on a substrate 1 . The width of the film layer 3 is wider than that of the resin layer 2 and the width of the film layer 3 is narrower than that of the substrate 1 . Also, the film layer 3 is adhered to the base material 1 at the ends 5-1 and 5-2 of the wallpaper 4. As shown in FIG. That is, the film layer 3 and the base material 1 are adhered at both ends 5 .
As a result, the film layer 3 is laminated up to the end of the resin layer 2 and the film layer 3 is sufficiently bonded to the resin layer 2 even at the end of the resin layer 2 . Therefore, the film layer 3 is less likely to peel off from the resin layer 2 at the edges 5-1 and 5-2 of the wallpaper, which is preferable.
Furthermore, by adhering the film layer 3 and the base material 1 at both ends 5 of the wallpaper 4 , the film layer 3 and the resin layer 2 are strongly adhered over the entire width of the wallpaper 4 . As a result, the adhesiveness between the resin layer as the wallpaper 4 and the film layer laminated thereon is excellent. In addition, such excellent adhesiveness between the resin layer and the film layer makes it difficult for the film layer to peel off, so that the wallpaper 4 having excellent scratch resistance can be obtained, which is preferable.

It is preferable not to make the difference in width between the resin layer 2 and the film layer 3 too large. If this difference is not made too large, it is economically preferable because the portion to be removed during construction can be reduced. Specifically, the difference between the width (R) of the resin layer 2 and the width (F) of the film layer 3 should be 4 mm or less (“width (F) of film layer” - “width (R) of resin layer”). ≦“4 mm”) is preferred.

Moreover, it is preferable that the width (P) of the base material is larger than the film layer (F). As a result, the film layer is placed inside the substrate, and the problem of the film layer being caught and peeled off can be reduced.

Furthermore, an adhesive layer may be provided between the film layer and the resin layer in order to increase the adhesion between the two layers. Means for providing an adhesive layer are not particularly limited, and known methods can be used. For example, as a method of obtaining an adhesive layer by coating with a solvent coating method or the like, an adhesive dissolved in an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, or the like can be used. A method of applying the agent to the film layer or the resin layer by using a gravure printing machine, a dry laminating machine, or the like can be mentioned.

The foamed wallpaper of the present invention has a yellowness index of less than 3.0, more preferably less than 2.5, as defined by "JIS K 7373".

In the wallpaper of the present invention, a printed layer may be provided on the resin layer as long as it does not hinder the solution of the problem. A known method can be used as a method for providing the printed layer, and examples thereof include gravure printing, flexographic printing, offset printing, and silk screen printing. Various surface treatment agents may also be used in combination for the purpose of improving the coating properties of the printed layer and reducing the gloss. Known pigments and binder resins can be used.
Further, when the print layer is provided between the resin layer and the film layer, the film layer should be sufficiently bonded to the resin layer and the print layer. When a printed layer is provided, it is often printed on the handle rather than printed on the front surface so as to completely cover the resin layer, in which case the film layer is sufficiently bonded to both the resin layer and the printed layer. is more preferable. In addition, even when printing is performed on the front surface so as to cover the resin layer, for example, in gravure printing, printing is performed along the mesh shape of the gravure printing roll, so the printing layer completely covers the surface of the resin layer. It is rarely provided, and even in such a case, it is a more preferable aspect that the film layer is sufficiently bonded to the resin layer and the printed layer. Furthermore, an adhesive layer may be provided between the film layer and the resin layer or the print layer in order to improve the adhesion between the film layer and the resin layer or the print layer.

In the wallpaper of the present invention, a functional-imparting treatment layer may be provided on the resin layer as long as it does not hinder the solution of the problem. The function added by the function-imparting layer is not particularly limited, but examples thereof include deodorant properties, antistatic properties, negative ionic properties, and relaxation effects, and two or more of them may be used in combination. When a printed layer is provided in addition to the functionality-imparting layer, it is preferable to provide the functionality-imparting layer on top of the printed layer.

As a method for producing the wallpaper of the present invention, a known method can be used. It is only necessary to have a film lamination step. For example, after laminating a resin layer on a base material by a paste coating method or a calendar method, the resin layer is foamed by a heater embossing machine or a foaming embossing machine to obtain mechanical embossing, and then a film layer is laminated. . Especially when performing mechanical embossing, it is preferable to use a heater embossing machine because it is easy to suppress an increase in yellowness. The three steps may be performed continuously, divided into two or three steps and performed sequentially, or a plurality of steps may be performed simultaneously. In addition, if there is no need to perform foaming, the foaming step may not be used.
Moreover, it is desirable to use paste coating when laminating the resin layer on the base material, because it can be applied to a large amount of various compounding agents. Gravure printing, flexographic printing, offset printing, silk screen printing, or the like can be used to provide a printed layer on the resin layer.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

"Yellowness evaluation"
The yellowness of the resulting foamed wallpaper was measured according to "JIS K 7373" using an SM color computer manufactured by Suga Test Instruments Co., Ltd.

"Stain resistance"
The test was carried out in accordance with the standard "Anti-fouling wallpaper performance standard" stipulated by the Wallpaper Industry Association. Contaminants were coffee, soy sauce, water-based pen (black), and crayon (red). For coffee and soy sauce, a test sample (A4 size) was attached to a test table inclined at 45 degrees, and 100 mL of the contaminant was sprinkled thereon so that the contaminant was about 10 cm wide. Five straight lines each having a length of 10 cm were drawn in parallel on the specimen (30 mm×220 mm) with an aqueous pen at intervals of about 2 mm. The crayon was attached to a friction element of a friction tester type II specified in JIS L 0849, and rubbed 5 times at a speed of 30 times per minute with a load of 200 g over a distance of 120 mm on the test piece (30 mm x 220 mm). After standing at room temperature for 24 hours, it was wiped off with a cloth soaked with water. The water-based pen and crayon were removed by wiping with a cloth soaked with water and then wiping with a cloth soaked with a neutral detergent. Regarding the removal of each contaminant, JIS L 0805 contamination gray scale was used, and if the contaminant was about No. 4 to 5, it was acceptable, and if it was about No. 1 to 3, it was not acceptable.

"Scratch resistance"
Although it conforms to the standard "Surface Reinforced Wallpaper Performance Standards" stipulated by the Wallpaper Industry Association, the friction tester type II specified in JIS L 0849 is equipped with a friction element with a load of 400 gf on the surface of a 30 mm x 250 mm test piece. Scratching at a reciprocating speed of 30 times should be 100 times or more until the resin layer is broken and the base material is clearly visible. It was evaluated as acceptable if no relatively large cracks or the like were observed in the surface layer after scratching 5 times, and as unacceptable if the tear in the surface layer was clearly visible.

"Adhesiveness"
The specimen was made into A4 size, and water was applied to the back surface of the base material with a brush. After curing for 5 minutes with the back surfaces facing each other, it was folded in half with respect to the longitudinal direction and the back surface was inside or outside. A load of 1.74 kg was evenly applied with a glass plate, and left at room temperature for 1 hour. After that, the surface condition of the folded portion of both the inner and outer sides of the back surface was visually observed. There was no peeling, but if there were any wrinkles, it was accepted, and if there was peeling, it was accepted.

In Example 1, plain paper was used as the substrate, and polyvinyl chloride resin for paste processing, p,p'-oxybisbenzenesulfonyl hydrazide, di-2-ethylhexyl phthalate, and barium-zinc-based resin were added in predetermined amounts as shown in Table 1. A paste sol obtained by mixing a stabilizer, a sodium perchlorate-based stabilizer, calcium carbonate and titanium dioxide was applied by a paste coater to provide a resin layer on the substrate. Thereafter, a film layer composed of an ethylene-vinyl alcohol copolymer was laminated using a heater embossing machine, and mechanical embossing was applied. The width of the substrate and the width of the film layer were made wider than the width of the resin layer, and the substrate and the film layer were adhered at both ends.

Example 2 conformed to Example 1, except that the sodium perchlorate-based stabilizer was not used.

Example 3 was the same as Example 1, except that the amount of p,p'-oxybisbenzenesulfonyl hydrazide was changed.

Example 4 conformed to Example 1 except that the blending amount and basis weight of titanium dioxide were changed.

Example 5 conformed to Example 1, except that adhesion between the substrate and the film layer was prevented at the edges.

Example 6 conformed to Example 1 except that the base material was changed to inorganic paper (aluminum hydroxide paper).

Example 7 conformed to Example 1 except that a film layer made of a polypropylene-based resin was laminated, and the width difference between the film layer and the resin layer and the width difference between the substrate and the resin layer were changed.

Example 8 conformed to Example 1 except that the basis weight of the resin layer was changed and the print layer was applied by gravure printing.

In Comparative Example 1, the foaming agent was changed from p,p'-oxybisbenzenesulfonyl hydrazide to azodicarbonamide, and the width of the film layer was made larger than the width of the base material to prevent adhesion at the edges of the base material and the film layer. Example 1 was followed except for the above.

In Comparative Example 2, p,p'-oxybisbenzenesulfonyl hydrazide and azodicarbonamide were used as foaming agents in combination, and the width of the film layer was made smaller than the width of the resin layer to prevent adhesion between the substrate and the edge of the film layer. Example 1 was followed except for the above.

In Tables 1 and 2, "○" in the columns of "film layer", "base material", and "printing layer" indicates that the corresponding layer is present, and "-" indicates that the corresponding layer is present. indicate that you have not. In addition, "○" in the column "Adhesion between base material and film layer" indicates that the base material and film layer are adhered, and "X" indicates that the base material and film layer are not adhered. show. For example, Example 1 has an ethylene-vinyl alcohol copolymer film layer and a plain paper base material, does not have a printed layer, and shows that the base material and the film layer are bonded together. ing.
The "FR" column represents the value of film layer width (F) - resin layer width (R), that is, the difference between the film layer width (F) and the resin layer width (R). . Similarly, the "P - F" column of "Width difference" is the value of the width (P) of the substrate - the width (F) of the film layer, that is, the width (P) of the substrate and the width (F) of the film layer. represents the difference.

"Evaluation results"
Examples 1-8 reduce the yellowness index to less than 3.0 and also demonstrate excellent smudge resistance, mar resistance and adhesion. In particular, Examples 1, 2 and 4 are all excellent and are desirable embodiments of the present invention.

On the other hand, in Comparative Examples 1 and 2, since azodicarbonamide is contained, the yellowness index is as high as 4.0 or more, and the adhesiveness is particularly poor because there is no adhesion between the substrate and the film layer.

Claims (4)

A base material, a resin layer containing a polyvinyl chloride resin laminated on the base material, and a film layer laminated on the upper side of the resin layer, wherein the resin layer contains an oxybisbenzenesulfonylhydrazide-based blowing agent. is added, substantially no azodicarbonamide foaming agent is added , the width of the base material and the width of the film layer are wider than the width of the resin layer, and the base material and the film layer are separated at both ends A wallpaper characterized by being directly glued . A base material, a resin layer containing a polyvinyl chloride resin laminated on the base material, and a film layer laminated on the upper side of the resin layer, wherein the resin layer contains an oxybisbenzenesulfonylhydrazide-based blowing agent. With respect to the width (R) of the resin layer and the width (F) of the film layer, with substantially no azodicarbonamide foaming agent added,
A wallpaper characterized by satisfying "film layer width (F)−resin layer width (R)≦4 mm" . A base material, a resin layer containing a polyvinyl chloride resin laminated on the base material, and a film layer laminated on the upper side of the resin layer, wherein the resin layer contains an oxybisbenzenesulfonylhydrazide-based blowing agent. added, substantially no azodicarbonamide foaming agent is added, and the width (P) of the base material
A wallpaper characterized by satisfying "Width of base material (P) - Width of film layer (F) > 0 mm" . A step of laminating a resin layer containing a polyvinyl chloride resin on the upper side of the base material;
A film lamination step of laminating a film layer on the upper side of the resin layer,
The wallpaper according to any one of claims 1 to 3 , wherein the width of the film layer is wider than the width of the resin layer, and both ends of the base material and the film layer are directly adhered in the film lamination step. manufacturing method.

Images