JP2012213940A - Laminated sheet and foamed laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which has a foaming agent-containing resin layer containing an ethylene-(meth)acrylic acid copolymer as a resin component, suppresses variation in the fluidity of a resin mixture containing an ethylene-(meth)acrylic acid copolymer resin, and can be produced stably; and a foamed laminated sheet which is obtained by using the laminated sheet.SOLUTION: The laminated sheet includes at least the foaming agent-containing resin layer formed on a base material. In the laminated sheet, the foaming agent-containing resin layer contains the ethylene-(meth) acrylic acid copolymer resin and surface-untreated titanium oxide.

Description

  The present invention relates to a laminated sheet and a foam laminated sheet. The foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like. Moreover, the said laminated sheet is a state before foaming of the said foaming laminated sheet, and means what is called an unfoamed original fabric.

  As a foam laminated sheet (for example, foam wallpaper), a sheet in which a foamed resin layer of vinyl chloride resin is formed on a fibrous sheet and a pattern layer is further formed is known. In addition, resin compositions containing halogen, such as vinyl chloride resin, have taken into account the disadvantage of generating harmful gases in the event of a fire or incineration. Building interior using non-vinyl chloride resin such as copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-methacrylic acid copolymer (EMAA) and ethylene-acrylic acid copolymer (EAA) Materials are known (Patent Documents 1 to 3, etc.). Among these, when using an ethylene- (meth) acrylic acid copolymer (EAA and EMAA), it is preferable at the point from which the flaw resistance excellent in the foaming laminated sheet is obtained.

  However, since the ethylene- (meth) acrylic acid copolymer has a polar group, it should be stored in a humid environment in a state of being kneaded with an inorganic component for imparting whiteness or hiding to the foamed laminated sheet. If so, the fluidity of the kneaded product is lowered, and there is a problem that problems such as foaming occur in the extruder during melt extrusion of the kneaded product (at the time of extrusion film formation).

  Therefore, a laminating sheet having a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer as a resin component, wherein the fluidity of the resin kneaded product containing the ethylene- (meth) acrylic acid copolymer resin Development of a laminated sheet that can be stably produced while suppressing fluctuations and a foamed laminated sheet obtained using the laminated sheet is desired.

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

  The present invention is a laminated sheet having a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer as a resin component, and the flow of a resin kneaded material containing an ethylene- (meth) acrylic acid copolymer resin It aims at providing the lamination sheet which suppresses the fluctuation | variation of property, and can be produced stably, and the foaming lamination sheet obtained using the same.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by using a specific inorganic component as an inorganic component imparting white color or hiding contained in the foaming agent-containing resin layer. It came to be completed.

That is, the present invention relates to the following laminated sheet and foamed laminated sheet.
1. A laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
The laminate sheet, wherein the foaming agent-containing resin layer contains an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated.
2. The content of the titanium oxide that is not surface-treated in the foaming agent-containing resin layer is 10 to 60 parts by mass with respect to 100 parts by mass of the resin component of the foaming agent-containing resin layer. Laminated sheet.
3. Item 3. The laminated sheet according to Item 1 or 2, wherein the substrate is a fibrous sheet.
4). The foaming lamination sheet obtained by foaming the said foaming agent containing resin layer of the lamination sheet in any one of said claim | item 1-3.
5. Item 5. The foamed laminated sheet according to Item 4, wherein embossing is performed from above the outermost surface layer.
6). A method for producing a laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
(1) Step 1 of forming a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated by extrusion film formation, and (2) the foaming agent-containing resin layer Step 2 for sticking on the base material,
The manufacturing method of the lamination sheet which has this.
7). The manufacturing method of a foaming lamination sheet which foams the foaming agent containing resin layer of the lamination sheet obtained by the manufacturing method of the said claim | item 6.
8). Item 8. The method for producing a foamed laminated sheet according to Item 7, comprising a step of embossing after foaming the foaming agent-containing resin layer.

  Hereinafter, the present invention will be described in detail.

≪Laminated sheet≫
In the laminated sheet of the present invention, at least a foaming agent-containing resin layer is formed on a substrate, and the foaming agent-containing resin layer is oxidized with an ethylene- (meth) acrylic acid copolymer resin and no surface treatment. It contains titanium.

Not limited as the substrate base material, a known wallpaper substrate (backing sheet), etc. can be used.

  Specifically, wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate) ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper.

The basis weight of the paper quality substrate is not limited, but preferably about 50 to 300 g / ^{m 2,} about 50 to 120 / ^{m 2} is more preferable.

Foaming agent-containing resin layer The foaming agent-containing resin layer used in the present invention contains an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated. The foaming agent-containing resin layer is an unfoamed foamed resin layer before heat treatment.

As the resin component, ethylene- (meth) acrylic acid copolymer resin is used. This is an ethylene copolymer obtained by using at least one of acrylic acid (CH ₂ ═CHCOOH) and methacrylic acid (CH ₂ ═C (CH ₃ ) COOH) as a monomer. By using this resin component, it is possible to form a strong layer resulting from hydrogen bonding or the like in the resin, and to obtain excellent scratch resistance, wear resistance, and the like.

  In the present invention, when expressed as an ethylene- (meth) acrylic acid copolymer resin, it means both an ethylene-acrylic acid copolymer resin and an ethylene-methacrylic acid copolymer resin.

  In the present invention, a resin other than the ethylene- (meth) acrylic acid copolymer resin may be used in combination. For example, polyolefin resin such as polypropylene, polystyrene and ethylene-vinyl acetate copolymer resin (EVA), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin, nylon, polyacetal resin And at least one of acrylic resins, polycarbonate resins, polyester resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyurethane resins, and polyvinyl chloride resins.

  When the other resin is used in combination, the content of the ethylene- (meth) acrylic acid copolymer resin in the resin component of the foaming agent-containing resin layer is preferably 60% by mass or more, and 70% by mass or more. More preferably, it may be 100% by mass. By using ethylene- (meth) acrylic acid copolymer resin as a main component as the resin component of the ethylene- (meth) acrylic acid copolymer resin-containing resin layer, the foamed resin layer of the foamed laminated sheet described below is used. The surface strength can be improved.

  The melt flow rate value (MFR) (JIS K7210: 190 ° C., 2.16 kg) of the ethylene- (meth) acrylic acid copolymer depends on the type of polymer used, but is usually 150 g / 10 min or less. Is preferred. Considering the workability and the foamed state when the foamed resin layer described below is taken into consideration, it is preferable to set it within a range of 10 to 100 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained. When the MFR is within the above range, there is little increase in temperature when the resin layer containing the ethylene- (meth) acrylic acid copolymer resin is formed by extrusion film formation, and the film can be formed in a non-foamed state. When a layer is formed, a printing process can be performed on a smooth surface, and pattern loss or the like is small. Moreover, when MFR is too large, there exists a possibility that the flaw resistance at the time of forming as a foamed resin layer may become inadequate because resin is too soft.

  In this invention, the titanium oxide which is not surface-treated is used for the purpose of providing white or concealment to a lamination sheet.

  By using titanium oxide that has not been surface-treated, a laminated sheet that can be produced while suppressing fluctuations in the fluidity of the resin kneaded product can be obtained.

  The content of the titanium oxide that has not been surface-treated in the foaming agent-containing resin layer is the resin component of the foaming agent-containing resin layer because it can be produced while suppressing fluctuations in concealability and fluidity of the resin kneaded product. 10-60 mass parts is preferable with respect to 100 mass parts, 20-50 mass parts is more preferable, and 30-45 mass parts is still more preferable.

  When blending titanium oxide not surface-treated and surface-treated titanium oxide in the foaming agent-containing resin layer, titanium oxide not surface-treated and 65-100 mass% is preferable with respect to the total compounding quantity of surface-treated titanium oxide, 65-100 mass% is preferable, 90-100 mass% is more preferable, and titanium oxide which is not surface-treated as titanium oxide It is more preferable to blend only.

  The average particle diameter of the titanium oxide not subjected to surface treatment used in the present invention is preferably 0.1 to 0.6 μm, more preferably 0.15 to 0.4 μm, because of the hiding property. The particle size can be measured with an electron microscope.

  A well-known or commercially available foaming agent can be used. For example, when a foaming agent is added to a composition such as plastisol or organosol of the above-described polyolefin resin and mechanically foamed by stirring with a stirrer such as a planetary mixer, a commercially available foaming agent can be used. good. Examples of the foaming agent include a pyrolytic foaming agent and a microcapsule foaming agent. Examples of the pyrolytic foaming agent include azo compounds such as azodicarbonamide (ADCA) and azobisformamide; hydrazide compounds such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide; N, N′-dinitrosopenta Nitroso compounds such as methylenetetramine; ammonium carbonate, sodium boron hydride, potassium bicarbonate, sodium bicarbonate and the like. Examples of the microcapsule type foaming agent include a foaming agent in which a thermal expansion gas such as hexane, heptane, butane, and air is encapsulated in a resin shell made of acrylonitrile, methyl (meth) acrylate, or the like. These can be used alone or in combination of two or more.

  The content of the 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 foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  A foaming aid can be further used for the resin composition forming the foaming agent-containing resin layer.

  Although there is no limitation in particular as a foaming adjuvant, it is preferable to use things other than a metal compound (metal oxide, fatty acid metal). When a metal compound is used as a foaming aid, the foaming promotion effect is impaired, and it tends to react with the polar group in the foaming agent-containing resin layer and easily color. Therefore, the following hydrazide compounds are preferably used as the foaming aid.

As a hydrazide compound, general formula (1):
R—CO—NHNH ₂ (1)
And a monohydrazide compound represented by formula (2):
_{H 2 NHN-X-NHNH 2} (2)
The dihydrazide compound shown by can be used suitably.

  More specific examples of the hydrazide compound of the general formula (1) include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy- Examples include 2-naphthoic acid hydrazide.

  Specific examples of the dihydrazide compound of the general formula (2) include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecane-2-acid dihydrazide, and maleic acid. Examples include dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, and dibasic acid dihydrazide such as 2,6-naphthoic acid dihydrazide. Furthermore, various dibasic acid dihydrazide compounds described in Japanese Patent Publication No. 2-4607, 2,4-dihydrazino-6-methylamino-sym-triazine, and the like can also be used as the dihydrazide of the present invention.

  About 0.3-10 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of a foaming adjuvant, about 1-6 mass parts is more preferable.

  The resin composition for forming the foaming agent-containing resin layer includes a resin component mainly composed of the ethylene- (meth) acrylic acid copolymer, titanium oxide not subjected to surface treatment, a foaming agent, and a foaming aid. For example, inorganic fillers, pigments, crosslinking aids, stabilizers and lubricants can be used.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, 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 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of an inorganic filler, about 20-70 mass parts is more preferable.

  For pigments, for example, carbon black, black iron oxide, yellow iron oxide, chrome lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), cadmium red, ultramarine , Bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica and the like. Examples of organic pigments include 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, indanthrone, halogenated phthalocyanine). About 3-50 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of a pigment, about 15-30 mass parts is more preferable.

  You may irradiate an electron beam with respect to a foaming agent containing resin layer. What is necessary is just to implement according to the method described in the manufacturing method of the postscript as the method.

  In addition, as for the thickness of a foaming agent containing resin layer, about 40-100 micrometers is preferable.

Non-foamed resin layers A and B
The foaming agent-containing resin layer may have a non-foamed resin layer on one side or both sides.

  For example, the back surface (surface on which the base material is laminated) of the foaming agent-containing resin layer may have a non-foamed resin layer B (adhesive resin layer) for the purpose of improving the adhesive force with the base material.

  The resin component of the adhesive resin layer is not particularly limited, but an ethylene-vinyl acetate copolymer (EVA) is preferable. EVA can be a known or commercially available one. In particular, the vinyl acetate component (VA component) is preferably 10 to 46 mass%, more preferably 15 to 41 mass%.

  The thickness of the adhesive resin layer is not limited, but is preferably about 5 to 50 μm.

  On the upper surface of the foaming agent-containing resin layer, a non-foamed resin layer A may be provided for the purpose of clarifying the design pattern when forming the design pattern layer or improving the scratch resistance of the foamed resin layer.

  Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluorine resins, and the like, among which polyolefin resins are preferable.

  Examples of polyolefin resins include polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, copolymers of α-olefins having 4 or more carbon atoms (linear low density polyethylene), and ethylene-acrylic acid copolymers. Resin, ethylene-methyl acrylate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene (meth) acrylic acid copolymer resin such as ethylene-methacrylic acid copolymer resin, ethylene-vinyl acetate copolymer Examples thereof include at least one of coalesced (EVA), ethylene-vinyl acetate copolymer resin saponified product, and ionomer.

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

  In the present invention, an embodiment in which the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are sequentially formed on the substrate is also preferable from the viewpoint of manufacturing described later.

A pattern layer may be formed on the pattern layer foaming agent-containing resin layer (or on the non-foamed resin layer A).

  The design pattern layer imparts design properties to the resin laminate. 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. The pattern can be selected according to the type of foam wallpaper.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent 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 can be set according to the type of the base sheet. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin 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. These solvents (or dispersion media) can be used alone or in the form of a mixture.

  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 foaming agent-containing resin layer or 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.), contamination resistance, and protection of the pattern layer of the laminated sheet or the foam laminated sheet described later, ionizing radiation curable resin is used as the resin component. What is contained is suitable. 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.

≪Laminated sheet manufacturing method≫
The laminated sheet of the present invention is a laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
(1) Step 1 of forming a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated by extrusion film formation, and (2) the foaming agent-containing resin layer Step 2 for sticking on the base material,
It is manufactured by the manufacturing method which has this.

  First, in Step 1, a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated is formed by extrusion film formation. For example, the foaming agent-containing resin layer can be formed by melt-extruding the foaming agent-containing resin layer forming composition containing the ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated. .

  When the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides, simultaneous extrusion film formation by a T-die extruder is suitable. For example, in the case of having non-foamed resin layers on both sides, a multi-manifold type T-die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers can be used.

  Next, in the process 2, the said foaming agent containing resin layer is stuck on the said base material. The method of sticking the foaming agent-containing resin layer on the substrate is not limited. For example, the foaming agent-containing resin layer forming composition containing the above components is extruded and formed by a T-die extruder. It is preferable to form by sticking on top. In addition, although the cylinder temperature and die temperature at the time of extrusion film formation should just be set suitably according to the kind of resin, generally it is about 100-140 degreeC.

≪Foamed laminated sheet and foamed laminated sheet manufacturing method≫
The foamed laminated sheet of the present invention can be obtained by heating and foaming the foaming agent-containing resin layer of the laminated sheet.

  The heating conditions at the time of foaming 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.

  The expansion ratio of the foamed resin layer (the ratio as viewed from the foaming agent-containing resin layer) is not particularly limited, but is usually 4 times or more, preferably about 4 to 8 times. If the expansion ratio is too low, it is difficult to give an excellent appearance design. On the other hand, if the expansion ratio is too high, the foamed resin layer becomes mechanically weak, and the scratch resistance tends to decrease.

  When the foamed laminated sheet is produced, the foaming agent-containing resin layer can be irradiated with an electron beam before foaming before the foaming agent-containing resin layer is heated and foamed. Thereby, the resin component can be cross-linked to adjust the surface strength, foaming characteristics, etc. of the foamed resin layer. The energy of the electron beam is preferably about 150 to 250 kV, more preferably about 175 to 200 kV. The irradiation amount is preferably about 10 to 100 kGy, and more preferably about 10 to 50 kGy. A known electron beam irradiation apparatus can be used as the electron beam source.

  Further, the surface of the non-foamed resin layer may be subjected to corona discharge treatment. The corona discharge treatment can be performed according to a known method.

  The foamed laminated sheet of the present invention may be embossed from the top surface layer. Embossing can be performed by known means such as an embossed plate. For example, when the outermost surface layer is the surface protective layer, a desired embossed pattern can be formed by pressing the embossed plate after heat softening the surface resin layer. 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.

  According to the laminated sheet of the present invention, when the foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin as a resin component is included, the resin containing the ethylene- (meth) acrylic acid copolymer resin. A laminated sheet that can be produced while suppressing fluctuations in the fluidity of the kneaded product can be provided.

  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.

Example 1
The foaming agent-containing resin layer forming composition (containing ethylene-methacrylic acid copolymer resin (EMAA resin)) was stored in an environment of 40 ° C. and 90% for 7 days.

  Next, the foaming agent-containing resin layer forming composition is melt-extruded at 120 ° C. to form a foaming agent-containing resin layer at 120 ° C. so that the layer thickness is 100 μm. Bonded with the material (backing paper). Next, the foaming agent-containing resin layer is irradiated with an electron beam (200 kV, 50 kGy) to crosslink the EMAA resin, and then printed on the foaming agent-containing resin layer by a gravure printing machine to obtain a laminated sheet. Obtained.

  Subsequently, it heated in the foaming furnace, the foaming agent contained in the said foaming agent containing resin layer was made to foam, and the foaming lamination sheet was obtained by giving the uneven | corrugated embossing of the texture pattern further on the outermost surface layer.

  Table 1 below shows the composition of the foaming agent-containing resin layer forming composition.

Example 2
A foamed laminated sheet was produced in the same manner as in Example 1 except that “CR-EL (Ishihara Sangyo)” was used as titanium oxide.

Example 3
A foamed laminated sheet was produced in the same manner as in Example 2 except that “20 parts by mass” of the titanium oxide was used.

Example 4
A foamed laminated sheet was produced in the same manner as in Example 2 except that “60 parts by mass” of the titanium oxide was used.

Example 5
A foamed laminated sheet was produced in the same manner as in Example 1 except that “CR-63 15 parts by mass, CR-EL 45 parts by mass” was used as titanium oxide.

Comparative Example 1
A foamed laminated sheet was produced in the same manner as in Example 1 except that “A-220: manufactured by Ishihara Sangyo” was used as the titanium oxide.

Comparative Example 2
A foamed laminated sheet was produced in the same manner as in Example 1 except that “CR-63: manufactured by Ishihara Sangyo” was used as the titanium oxide.

Comparative Example 3
A foamed laminated sheet was produced in the same manner as in Example 1 except that “CR-60-2: manufactured by Ishihara Sangyo” was used as the titanium oxide.

Comparative Example 4
A foamed laminated sheet was produced in the same manner as in Example 1 except that “CR-60: manufactured by Ishihara Sangyo” was used as the titanium oxide.

Comparative Example 5
A foamed laminated sheet was produced in the same manner as in Example 1 except that “PF-740: manufactured by Ishihara Sangyo” was used as the titanium oxide.

  The physical properties of titanium oxide used in Examples and Comparative Examples are shown in Table 2 below.

Test example 1 (change in fluidity)
The foaming agent-containing resin layer forming composition kneaded with each titanium oxide species was measured at 120 ° C./2.16 kgf using “Toyo Seiki Melt Indexer”, and the change in fluidity before and after storage was measured. Calculated.

  The evaluation criteria are as follows.

Fluidity change △ Greater than 0: No problem Fluidity change △ -1 to 0: Slightly fluidity decline Fluidity change △ Less than -1: Fluidity decline

Test example 2 (foaming in the extruder)
The cylinder temperature was set to 120 ° C., and the presence or absence of foaming in the foaming agent-containing resin layer when extruded and taken at a constant speed was visually confirmed.

  The evaluation criteria are as follows.

○: Foaming is not recognized.
Δ: Slight foaming is observed.
X: Foaming is recognized.

  The results of Test Examples 1 and 2 are shown in Tables 3 and 4.

  As shown in Table 3, as a titanium oxide to be added to a foaming agent-containing resin layer made of an ethylene- (meth) acrylic acid copolymer resin, a surface untreated titanium oxide is blended so that the resin can be used under high humidity. Even when stored, the MFR did not decrease, foaming in the extruder could be prevented, and a laminated sheet could be produced stably.

Claims (8)

A laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
The laminate sheet, wherein the foaming agent-containing resin layer contains an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated.   The content of the titanium oxide not subjected to the surface treatment in the foaming agent-containing resin layer is 10 to 60 parts by mass with respect to 100 parts by mass of the resin component of the foaming agent-containing resin layer. Laminated sheet.   The laminated sheet according to claim 1 or 2, wherein the substrate is a fibrous sheet.   The foaming lamination sheet obtained by foaming the said foaming agent containing resin layer of the lamination sheet in any one of Claims 1-3.   The foamed laminated sheet according to claim 4, wherein embossing is performed from above the outermost surface layer. A method for producing a laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
(1) Step 1 of forming a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin and titanium oxide that has not been surface-treated by extrusion film formation, and (2) the foaming agent-containing resin layer Step 2 for sticking on the base material,
The manufacturing method of the lamination sheet which has this.   The manufacturing method of a foaming lamination sheet which foams the foaming agent containing resin layer of the lamination sheet obtained by the manufacturing method of Claim 6.   The manufacturing method of the foaming lamination sheet of Claim 7 which has the process of embossing, after making a foaming agent containing resin layer foam.