JP5621200B2 - Laminated body of foamed decorative sheet before foaming - Google Patents

Description

  The present invention relates to a foamed decorative sheet useful for decoration of wall surfaces and the like.

  Conventionally, foamed decorative sheets are known in which a foamed resin layer of vinyl chloride resin is formed on a base material (backing paper) such as paper. In recent years, in consideration of the environment, resins that do not contain halogen such as ethylene-vinyl acetate copolymer resin (EVA), acrylic resin, and olefin resin have been used for the foamed resin layer (Patent Document 1). ~ 3 etc.).

  The foamed resin layer is formed, for example, by foaming a foaming agent-containing resin layer containing a pyrolytic foaming agent by heating. The foaming agent-containing resin layer is formed, for example, by forming a resin composition containing a pyrolytic foaming agent by melt extrusion according to an extrusion method.

  When using the above non-vinyl chloride resin (especially ethylene copolymer resin) and a thermal decomposable foaming agent, the foamed resin layer turns yellow when the foaming agent-containing resin layer is foamed by heating, and the whiteness decreases. There is a problem of doing. There is also a problem that further discoloration is likely to occur over time due to the light hitting the foamed resin layer. Such a problem is particularly remarkable when an azodicarbonamide (ADCA) -based foaming agent is used as the pyrolytic foaming agent.

  Accordingly, it is obtained by forming a foaming agent-containing resin layer comprising a resin composition containing an ethylene copolymer and a pyrolytic foaming agent, and further foaming the foaming agent-containing resin layer to form a foaming resin layer. Development of a foamed decorative sheet that is capable of suppressing yellowing during foaming and discoloration with time of the foamed resin layer is desired.

Japanese Patent Laid-Open No. 6-47875 JP 2000-255011 A JP 2001-347611 A

  The present invention particularly forms a foaming agent-containing resin layer comprising a resin composition containing an ethylene copolymer and a thermally decomposable foaming agent, and further foams the foaming agent-containing resin layer to form a foaming resin layer. It is a main object of the present invention to provide a foamed decorative sheet obtained by the above-described method, in which yellowing during foaming and discoloration with time of the foamed resin layer are suppressed.

  As a result of intensive studies, the present inventor has found that the above object can be achieved when the pyrolytic foaming agent and the specific component are used in combination, and has completed the present invention.

That is, this invention relates to the laminated body before foaming of the following foaming decorative sheet.
1. A laminate before foaming of a foam decorative sheet, having at least a foaming agent-containing resin layer on a substrate,
(1) The foaming agent-containing resin layer is composed of a resin composition containing a pyrolytic foaming agent, perchlorates, and an ethylene copolymer resin,
(2) The perchlorates are selected from the group consisting of cesium perchlorate, nickel perchlorate, silver perchlorate, zinc perchlorate, copper perchlorate, iron perchlorate and aluminum perchlorate. At least one
The laminated body before foaming of the foaming decorative sheet characterized by this.
2. Item 2. The laminate before foaming of the foamed decorative sheet according to Item 1, wherein the pyrolyzable foaming agent is azodicarbonamide.
3. Item 3. The laminate before foaming of the foamed decorative sheet according to Item 1 or 2, wherein a non-foamed resin layer A is further formed on the front surface of the foaming agent-containing resin layer.
4). Item 4. The laminate before foaming of the foamed decorative sheet according to any one of Items 1 to 3, wherein a non-foamed resin layer B is further formed between the base material and the foaming agent-containing resin layer.
5. The said non-foaming resin layer A is a laminated body before foaming of the foaming decorative sheet of said claim | item 3 or 4 which contains the ethylene-methacrylic acid copolymer whose methacrylic acid content is 15 weight% or less as a resin component.
6). Item 6. The laminated body before foaming of the foamed decorative sheet according to any one of Items 1 to 5, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.

  Hereinafter, the foamed decorative sheet of the present invention will be described in detail.

The foam decorative sheet of the present invention is a foam decorative sheet having at least a foam resin layer on a substrate,
(1) The foamed resin layer is formed by foaming a foaming agent-containing resin layer,
(2) The foaming agent-containing resin layer is composed of a resin composition containing a pyrolytic foaming agent, perchlorates, and an ethylene copolymer resin,
(3) The perchlorates are selected from the group consisting of cesium perchlorate, nickel perchlorate, silver perchlorate, zinc perchlorate, copper perchlorate, iron perchlorate and aluminum perchlorate. And at least one kind.

  The foamed decorative sheet of the present invention having the above-described features is particularly suppressed in yellowing when the foaming agent-containing resin layer is heated and foamed by using a pyrolytic foaming agent and the specific perchlorate in combination. Yes. Moreover, the discoloration with time of the foamed resin layer is also suppressed.

  Hereinafter, each requirement will be described separately.

The base material is not particularly limited as long as it has mechanical strength, heat resistance and the like suitable as a decorative sheet base material. For example, a resin sheet, a fiber sheet (paper, etc.) can be generally used.

  Of these, fiber sheets such as paper are preferable. Specifically, flame retardant paper (pulp-based sheets treated with flame retardants such as guanidine sulfamate and guanidine phosphate); aluminum hydroxide, magnesium hydroxide Inorganic paper containing inorganic additives such as: high-quality paper; thin paper.

Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / ^{m 2,} about 50 to 80 g / ^{m 2} is more preferable.

Non-foamed resin layer B
In the present invention, a non-foamed resin layer (non-foamed resin layer B) may be formed between the substrate and the foamed resin layer as necessary. In particular, when the non-foamed resin layer B is formed as an adhesive layer, excellent adhesion can be obtained. As the non-foamed resin layer B, for example, ethylene-vinyl acetate copolymer (EVA) or the like can be suitably used.

  The non-foamed resin layer B may contain known additives in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight.

  The thickness of the non-foamed resin layer B is not limited, but is preferably about 5 to 50 μm, more preferably about 8 to 20 μm.

Foamed resin layer The foamed resin layer is formed by foaming a foaming agent-containing resin layer. In particular, in the present invention, the foaming agent-containing resin layer is formed of a resin composition containing a pyrolytic foaming agent, the specific perchlorates, and an ethylene copolymer resin.

  As the resin component contained in the resin composition, one containing an ethylene copolymer resin is used. As the ethylene copolymer resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-methyl methacrylate (EMMA), ethylene-ethyl acrylate (EEA), ethylene-methyl acrylate (EMA), or the like can be used. . In particular, it is desirable that the resin component is formed of a resin composition containing EVA resin.

  When EVA resin is used as the resin component, the vinyl acetate content (copolymerization ratio) of the EVA resin is not limited, but is preferably about 5 to 30% by weight, more preferably about 10 to 20% by weight. . The melting point of the EVA resin is not limited, but is preferably about 60 to 100 ° C, more preferably about 65 to 80 ° C. The melting point in this specification is a measured value based on JIS K7121.

  The melt flow rate value (MFR) of the resin component is not particularly limited, but is preferably about 5 to 75 g / 10 minutes, and more preferably about 15 to 70 g / 10 minutes.

  In addition, MFR of this specification is the value measured by the test method of JISK7210 (flow test method of thermoplastics). As test conditions, “190 ° C., 21.18 N (2.16 kgf)” described in JIS K 6760 is adopted.

  As the pyrolytic foaming agent, for example, an azodicarbonamide (ADCA) foaming agent, an oxybisbenzenesulfonyl hydrazide (OBSH) foaming agent, or the like can be used. Among these, ADCA-based foaming agents are preferable from the viewpoint of high film-forming properties because of their high thermal decomposition temperature, and less risk of abnormal foaming during film formation. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 1.5 times or more, preferably about 3 to 7 times, and the pyrolytic foaming agent is preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the resin component, About 0.1-10 weight part is more preferable.

  Examples of perchlorates include at least one of cesium perchlorate, nickel perchlorate, silver perchlorate, zinc perchlorate, copper perchlorate, iron perchlorate, and aluminum perchlorate. . By using such perchlorates together, yellowing when foaming the foaming agent-containing resin layer and discoloration over time of the foamed resin layer can be prevented. Since these perchlorates are powders at room temperature and are not kneadable with resin components as they are, it is preferable to add them in advance by dissolving them in alcohol or water. In addition, when melt | dissolving and adding to water, it adds in the state of a hydrate.

  Examples of the alcohol include isopropyl alcohol, methyl glycol, methyl diglycol, methyl triglycol, butyl glycol, butyl diglycol, and ethylene glycol. From the viewpoint of reducing VOC, use water instead of alcohol. Is preferred. The content of perchlorates is not limited, but is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.1 to 0 parts per 100 parts by weight of the resin component. .4 parts by weight is most preferred.

  Various additives may be added to the resin composition. For example, inorganic fillers, pigments and foam stabilizers, antioxidants, foaming aids (zinc compounds), crosslinking agents, surface treatment agents, fluorescent whitening agents, antifungal agents, lubricants and the like can be used as additives. .

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including an inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. About 0-100 weight part is preferable with respect to 100 weight part of resin components, and, as for content of an inorganic filler, about 20-70 weight part is more preferable.

  As for pigments, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), cadmium red Inorganic pigments such as ultramarine, bituminous, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, zinc sulfide; for example, aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), Polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthro , And organic pigments halogenated phthalocyanine), or the like. The content of the pigment is preferably about 10 to 50 parts by weight and more preferably about 15 to 30 parts by weight with respect to 100 parts by weight of the resin component.

  Examples of the foam stabilizer include alkyl sulfonate and alkyl benzene sulfonate. Specifically, at least one of sodium dodecylbenzenesulfonate and calcium dodecylbenzenesulfonate is preferable.

  Further, a metal soap such as zinc stearate and a surfactant can be used. These contents are preferably about 0.3 to 10 parts by weight, and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.

  Examples of the antioxidant include 2,6-ditert-butyl-p-cresol and tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxy-phenyl), which are phenolic antioxidants. Propionate] methane, phosphorous antioxidant tris (2,4-di-butylphenyl) phosphite, distearyl pentaerythritol diphosphite and the like.

  Examples of the foaming aid (zinc compound) include zinc oxide, hydroxide, carbonate, basic carbonate, sulfate, nitrate, phosphite, carboxylate and the like. Such a zinc compound is preferably added from the viewpoint of improving the foaming speed. Examples of the carboxylate include acetic acid, propionic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, Examples include aliphatic acids such as 12-hydroxystearic acid, ricinoleic acid, and behenic acid, and aromatic acids such as benzoic acid, p-tert-butylbenzoic acid, toluic acid, salicylic acid, and naphthenic acid. The zinc carboxylate using these carboxylic acids may be in the form of a normal salt, an acid salt, or a basic salt. The above-mentioned carboxylic acids constituting the zinc carboxylate can be used, but from the viewpoint of reducing VOC, those which are powders at room temperature using fatty acids having 12 or more carbon atoms, such as zinc stearate And zinc laurate are preferred. When other carboxylic acid is used, it may be liquid or may need to be dissolved in an organic solvent in order to improve handling properties.

  The content of the zinc compound is preferably about 0.001 to 20 parts by weight, more preferably about 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin composition. The thickness of the foamed layer is not limited, but is preferably 70 to 150 μm in a non-foamed state (before foaming). 300-900 micrometers is preferable after foaming.

  What is necessary is just to implement according to the method described in the manufacturing method of the postscript as a method of foaming a foaming agent containing resin layer.

Non-foamed resin layer A
A non-foamed resin layer A may be further formed on the front surface of the foamed resin layer.

The non-foamed resin layer (non-foamed resin layer A) mainly protects the foamed resin layer. In the present invention, a layer formed of a resin composition containing, as a resin component, a polymer obtained using at least one of acrylic acid (CH ₂ ═CHCOOH) and methacrylic acid (CH ₂ ═C (CH ₃ ) COOH) as a monomer. Is preferably a non-foamed resin layer.

  As the resin component, for example, a copolymer obtained by a combination of at least one monomer of acrylic acid and methacrylic acid and ethylene can be suitably used as the resin component. More specifically, it is desirable to use at least one of EMAA, ethylene-acrylic acid copolymer, and ionomer resin. As the ionomer resin, a resin having a structure in which EMAA and / or ethylene-acrylic acid copolymer molecules are intermolecularly bonded with metal ions such as sodium and zinc can be used. When such a resin component is used, it is possible to form a strong layer particularly due to hydrogen bonds in the resin, so that excellent scratch resistance, abrasion resistance, and the like can be obtained. These may be known or commercially available.

  The content of acrylic acid or methacrylic acid in the copolymer is not limited, but is preferably 15% by weight or less, more preferably about 4 to 15% by weight. Such a resin can also use a commercial item. A known additive can also be blended in the resin composition.

  The thickness of the non-foamed resin layer is not limited, but is preferably about 5 to 50 μm, more preferably about 8 to 20 μm.

  Although the melt flow rate value of the resin component depends on the type of the resin component to be used, etc., it is generally set as appropriate within a range of 10 g / 10 min or more. Usually, it is preferably 10 to 100 g / 10 minutes, particularly preferably 10 to 95 g / 10 minutes, and more preferably 20 to 80 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained.

  Moreover, although content of the said resin component in a resin composition is not limited, Usually, it is preferable to set suitably in the range of 70 to 100 weight%.

Pattern Pattern Layer In the present invention, a pattern pattern layer may be provided on the front surface of the non-foamed resin layer A as necessary.

  The design pattern layer imparts design properties to the foamed decorative sheet. Examples of the design pattern include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. A design pattern can be selected according to the kind of foaming decorative sheet.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern on the front surface of the non-foamed resin layer A. In addition, when forming a picture pattern layer, you may form a primer layer previously as needed. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent (or a dispersion medium) can be used. These inks may be known or commercially available.

  As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.

  The binder resin is, for example, an acrylic resin, a styrene resin, a polyester resin, a urethane resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl butyral resin, an alkyd resin, or a petroleum resin. Examples include resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents; and water.

  The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.

Surface protective layer (overcoat layer)
In the present invention, a surface protective layer may be provided on the surface of the design pattern layer for the purpose of adjusting the gloss and / or protecting the design pattern layer. The kind of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed. In addition, when the adhesiveness of a pattern pattern layer and a surface protective layer is not fully acquired, a surface protective layer can also be provided after carrying out the adhesion process (primer process) of the surface of a pattern pattern layer.

  When forming a surface protective layer for the purpose of surface strength (scratch resistance, etc.), stain resistance, and protection of a pattern layer of a foamed decorative sheet, those containing an ionizing radiation curable resin as a resin component are suitable. It is. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

  The thickness of the surface protective layer is not limited, but is preferably about 0.1 to 15 μm.

Embossing In this invention, you may attach | subject an embossing pattern suitably. In this case, what is necessary is just to emboss from the uppermost surface layer (opposite side of a base material) of a foaming decorative sheet. Embossing can be performed by known means such as pressing an embossed plate. For example, when the outermost surface layer is a surface protective layer, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.

<Method for producing foamed decorative sheet>
The manufacturing method of a foaming decorative sheet is not specifically limited. For example, in order to produce a foamed decorative sheet having a foamed resin layer and a non-foamed resin layer A on a substrate such as paper, simultaneous extrusion with a T-die extruder is suitable. A multi-manifold type T-die capable of simultaneously forming two layers by simultaneously extruding molten resin corresponding to two layers can be used. In this case, the resin composition for forming the foaming agent-containing resin layer and the resin composition for forming the non-foamed resin layer are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. That's fine. In this method, the coextruded laminate is simultaneously laminated (film formation) on the substrate. Since the resin layer laminated simultaneously with extrusion on the base material has adhesiveness by heat melting, it is bonded to the base material.

  In addition, a laminate in which two types and two layers are simultaneously formed in advance may be prepared, placed on the substrate, and bonded to the substrate by thermal lamination.

  In addition, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, an inorganic filler residue (so-called eyes) is easily generated at the extrusion port (so-called die) of the extrusion molding machine. It tends to be a foreign material on the sheet surface. Therefore, when the inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, the non-foaming resin layer A and the non-foaming resin layer B can be coextruded together with the foaming agent-containing resin layer. preferable. The coextrusion molding can be performed, for example, by using a multi-manifold type T die. Thus, by simultaneously extruding and molding the foaming agent-containing resin layer between the non-foamed resin layers, it is possible to suppress the occurrence of the eyes.

  After simultaneous lamination on the substrate, the foamed resin layer is formed by heating the foaming agent-containing resin layer. The heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

  Electron beam irradiation may be performed before the heat treatment. Thereby, since a resin component can be bridge | crosslinked, the surface strength of a foaming decorative sheet, a foaming degree, etc. can be controlled. The energy of the electron beam is preferably about 150 to 250 kV. The irradiation amount is preferably about 10 to 70 kGy. A known electron beam irradiation apparatus can be used as the electron beam source. The crosslinking can also be performed using a chemical crosslinking agent (also referred to as a crosslinking agent or a crosslinking aid).

  In the case of performing electron beam irradiation, the composition may contain a crosslinking agent. Any crosslinking agent that promotes crosslinking by electron beam irradiation may be used. Examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like. The crosslinking agent is preferably about 0 to 10 parts by weight, more preferably 0 to 4 parts by weight, based on 100 parts by weight of the resin component.

  When a surface protective layer containing an ionizing radiation curable resin is formed, the surface protective layer can be cured by electron beam irradiation. Such electron beam irradiation can be performed simultaneously (same processing) as electron beam irradiation performed to crosslink the resin contained in the foaming agent-containing resin layer. That is, after forming a foaming agent-containing resin layer, a non-foaming resin layer, a pattern layer, and a surface protective layer containing an ionizing radiation curable resin in this order, the resin contained in the foaming agent-containing resin layer is irradiated with an electron beam. The resin contained in the surface protective layer can be cured while being crosslinked.

  When producing a foam decorative sheet having a pattern layer, it is preferable to form the pattern layer on the surface of the non-foamed resin layer before the heat treatment. The pattern pattern layer may be formed as described above.

  In the foamed decorative sheet of the present invention, yellowing is suppressed when the foaming agent-containing resin layer is heated and foamed, particularly by using a pyrolytic foaming agent and the specific perchlorate. Moreover, the discoloration with time of the foamed resin layer is also suppressed.

It is a schematic diagram of the foaming decorative sheet produced by the Example and the comparative example.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Examples 1-7 and Comparative Examples 1-2
Using a three-type, three-layer multi-manifold T-die extruder, the base material (backing paper) has a thickness of 10 μm / 60 μm / 10 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B. The film was formed by extrusion. Thereby, the laminated body which consists of non-foaming resin layer A / foaming agent containing resin layer / non-foaming resin layer B / base material was obtained.

  As a base material, backing paper “WK-665 (manufactured by Kojin)” was prepared, heated to 90 ° C., and then the above three layers were extruded to form a film.

  Extrusion conditions were such that the cylinder temperature containing the resin for forming the non-foamed resin layer A was 140 ° C., the cylinder temperature containing the resin composition for forming the foaming agent-containing resin layer was 120 ° C., and non-foamed The cylinder temperature in which the resin for forming the resin layer B was accommodated was 100 ° C. The die temperature was 120 ° C. for all.

  The laminate was irradiated with an electron beam (200 kV, 30 kGy) from the non-foamed resin layer A side, and the foaming agent-containing resin layer was particularly resin-crosslinked. Further, a corona discharge treatment was performed on the non-foamed resin layer A.

Next, an EVA-based aqueous emulsion was applied on the non-foamed resin layer A (2 g / m ² ) to form a primer layer, and a fabric pattern was printed with an aqueous ink “Hydric” (manufactured by Dainichi Seika Kogyo). .

  Next, the laminate on which the texture pattern was printed was heated in a gear oven (at 25O <0> C for 25 to 45 seconds) to foam the foaming agent-containing resin layer.

  Finally, the foam was embossed with a texture pattern to obtain a foamed decorative sheet.

  Each layer was formed using the following components.

  The non-foamed resin layer A was formed by EMAA “Nucleel N1560 (MMA content: 15% by weight), manufactured by Mitsui DuPont Polychemical”.

  The foaming agent-containing resin layer is composed of 100 parts by weight of EVA “Evaflex V406 (VA content: 20% by weight, MFR = 20), manufactured by Mitsui DuPont Polychemical), 30 parts by weight of titanium oxide“ CR63, manufactured by Ishihara Sangyo ”, It contains 6 parts by weight of ADCA foaming agent “Uniform Ultra AZ3050I manufactured by Otsuka Chemical” and 5.3 parts by weight of foaming aid “MFX50-E, manufactured by Daikyo Kasei”. The other components are shown in Table 1 below.

  The non-foamed resin layer B was formed by EVA “Evaflex EV150 (VA content: 33 wt%, melting point: 61 ° C.), manufactured by Mitsui DuPont Polychemical”.

Test example 1
With respect to the foamed decorative sheets prepared in Examples and Comparative Examples, the color of the foamed resin layer was measured with a colorimetric device “color difference meter CR-300, manufactured by Konica Minolta”. Colorimetric value (a value) is less than 0.3 and (b) value is 7 or less (that is, whiteness is high), (a value) is 0.3 or more, or (a value) is 0 Less than 3 and (b) value exceeding 7 (that is, low whiteness) was evaluated as x.

  The results are shown in Table 2 below.

  As is clear from the results in Table 2, the foamed resin layer of the present invention containing specific perchlorates in the foaming step has higher whiteness than the foamed resin layers of Comparative Examples 1 and 2, and suppresses yellowing. You can see that. In addition, the foamed resin layers of the examples had not only high whiteness at the beginning of production but also suppressed discoloration over time.

1. Backing paper2. Non-foamed resin layer B
3. 3. Foamed resin layer Non-foamed resin layer A

Claims (6)

A laminate before foaming of a foam decorative sheet, having at least a foaming agent-containing resin layer on a substrate,
(1) The foaming agent-containing resin layer is composed of a resin composition containing a pyrolytic foaming agent, perchlorates, and an ethylene copolymer resin,
(2) The perchlorates are selected from the group consisting of cesium perchlorate, nickel perchlorate, silver perchlorate, zinc perchlorate, copper perchlorate, iron perchlorate and aluminum perchlorate. At least one
The laminated body before foaming of the foaming decorative sheet characterized by this.   The laminate of the foamed decorative sheet before foaming according to claim 1, wherein the pyrolyzable foaming agent is an azodicarbonamide type.   The laminated body before foaming of the foaming decorative sheet of Claim 1 or 2 with which the non-foaming resin layer A is further formed in the front surface of the said foaming agent containing resin layer.   The laminated body before foaming of the foaming decorative sheet in any one of Claims 1-3 in which the non-foaming resin layer B is further formed between the said base material and the said foaming agent containing resin layer.   The said non-foamed resin layer A is a laminated body before foaming of the foaming decorative sheet of Claim 3 or 4 which contains the ethylene-methacrylic acid copolymer whose methacrylic acid content is 15 weight% or less as a resin component. The laminate before foaming of the foamed decorative sheet according to any one of claims 1 to 5 , wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.

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