WO2009093544A1 - Resin composition for foam production and foam using the same - Google Patents
Resin composition for foam production and foam using the same Download PDFInfo
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- WO2009093544A1 WO2009093544A1 PCT/JP2009/050663 JP2009050663W WO2009093544A1 WO 2009093544 A1 WO2009093544 A1 WO 2009093544A1 JP 2009050663 W JP2009050663 W JP 2009050663W WO 2009093544 A1 WO2009093544 A1 WO 2009093544A1
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- foam
- resin
- foamed
- resin composition
- resin layer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
Definitions
- the present invention relates to a resin composition for producing a foam and a foam using the same.
- Examples of the foam include a foamed resin layer used for a foam decorative sheet.
- a foamed decorative sheet in which a vinyl chloride resin foamed resin layer is formed on a paper base (backing paper).
- resins that do not contain a halogen component 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 obtained, for example, by heating and foaming a foaming agent-containing resin layer formed from a resin composition containing a resin component, a pyrolytic foaming agent, and a foaming aid.
- a foaming agent-containing resin layer formed from a resin composition containing a resin component, a pyrolytic foaming agent, and a foaming aid.
- the composition of the resin composition include, for example, resin components such as EVA, ethylene-methyl methacrylate copolymer (EMMA), azodicarbonamide-based foaming agent (ADCA-based foaming agent), metal oxide-based foaming aid, Formulation examples containing a fatty acid metal salt foaming aid (for example, zinc stearate, zinc oxide, magnesium oxide, etc.) are known.
- the above-mentioned problem is a problem common to not only foamed decorative sheets but also resin compositions for foam production containing a carboxyl group-containing resin, an ADCA-based foaming agent, and a foaming aid (metal oxide-based and fatty acid metal salt-based). is there.
- a carboxyl group-containing resin especially EMAA
- EMAA EMAA
- the foam surface strength is higher than when using other resins, the above problems have been improved by devising the type of foaming aid. It is desired to develop a resin composition for foam production and a foam.
- the present invention relates to a resin composition for foam production comprising a carboxyl group-containing resin and an ADCA-based foaming agent, and a foam with improved problems such as discoloration (yellowing) of the foam obtained by heating and foaming. It aims at providing the resin composition for manufacture. Moreover, it aims also at providing the foam obtained using the said resin composition for foam manufacture.
- the present inventor has found that the above object can be achieved when a specific compound is used as a foaming aid, and has completed the present invention.
- a resin composition for producing a foam which comprises a resin containing a carboxyl group, an azodicarbonamide-based foaming agent, and a carboxylic acid hydrazide compound.
- the carboxyl group-containing resin is at least one selected from the group consisting of ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, and ionomers containing these copolymers.
- Resin composition for foam production. 3.
- the foaming decorative sheet which laminated
- Item 9 The foamed decorative sheet according to Item 8, further comprising a non-foamed resin layer B between the paper substrate and the foamed resin layer. 10.
- Item 10 The foamed decorative sheet according to any one of Items 7 to 9, which is embossed from above the outermost surface layer.
- Resin composition for foam production of the present invention contains a carboxyl group-containing resin, an azodicarbonamide foaming agent (ADCA foaming agent), and a carboxylic acid hydrazide compound.
- a carboxylic acid hydrazide compound acts as a foaming aid.
- a carboxyl group-containing resin and a foaming aid metal oxide type and fatty acid metal salt type: for example, zinc oxide, zinc stearate, etc.
- the carboxylic acid hydrazide compound By using the carboxylic acid hydrazide compound, the effect of the foaming aid was obtained. It is possible to provide a foam which is not impaired and has improved problems such as discoloration.
- Carboxyl group-containing resin is not particularly limited as long as it contains a carboxyl group in the resin.
- the carboxyl group-containing resin 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. Specifically, it is desirable to use at least one of ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA), and an ionomer containing these copolymers.
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-acrylic acid copolymer
- an ionomer a resin having a structure in which EMAA and / or EAA molecules are intermolecularly bonded with metal ions such as sodium and zinc can be used.
- an azodicarbonamide (ADCA) foaming agent is used as the foaming agent.
- the ADCA-based blowing agent has a high thermal decomposition temperature, and thus has high film-forming properties, and is preferable from the viewpoint of less risk of in-machine foaming during extrusion film formation.
- an ADCA foaming agent may be used alone as the thermal decomposition foaming agent, but within the range not impairing the effects of the invention, an oxybisbenzenesulfonyl hydrazide (OBSH) foaming agent, etc. together with the ADCA foaming agent, etc.
- OBSH oxybisbenzenesulfonyl hydrazide
- Other pyrolytic foaming agents may be used in combination.
- the content of the pyrolytic foaming agent in the resin composition can be appropriately set according to the expansion ratio.
- the expansion ratio is adjusted to 1.5 times or more, preferably about 3 to 7 times.
- 3 to 6 parts by weight is preferable with respect to 100 parts by weight of the resin component, and 3.5 to 5 parts by weight is more preferable.
- the content of the ADCA foaming agent contained in 100% by weight of the foaming agent is 50% by weight. The above is preferable.
- Carboxylic acid hydrazide compound in the present invention, a carboxylic acid hydrazide compound is used as a foaming aid. Even when the carboxylic acid hydrazide compound is used in combination with a carboxyl group-containing resin, the efficacy of the foaming aid is not deactivated by a chemical reaction. Therefore, when producing a foam containing a carboxyl group-containing resin as a resin component, the foam can be obtained without causing discoloration of the foam.
- Examples of the carboxylic acid hydrazide compound include a monohydrazide compound having one hydrazide group in the molecule, a dihydrazide compound having two hydrazide groups in the molecule, and a polyhydrazide compound having three or more hydrazide groups in the molecule. Is mentioned.
- the monohydrazide compound include, for example, the general formula (1) R-CO-NHNH 2 (1) [Wherein, R represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent. ]
- R represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent.
- the monohydrazide compound represented by these is mentioned.
- examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, Examples thereof include linear alkyl groups having 1 to 12 carbon atoms such as n-octyl group, n-nonyl group, n-decyl group and n-undecyl group.
- aryl group a phenyl group, a biphenyl group, a naphthyl group etc. can be mentioned, for example, Among these, a phenyl group is preferable.
- substituent for the aryl group examples include a halogen atom such as a hydroxyl group, fluorine, chlorine, bromine, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, iso group.
- a halogen atom such as a hydroxyl group, fluorine, chlorine, bromine, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, iso group.
- -A linear or branched alkyl group having 1 to 4 carbon atoms such as a butyl group.
- hydrazide compound represented by the general formula (1) examples include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy- Examples thereof include 2-naphthoic acid hydrazide.
- dihydrazide compound examples include, for example, the general formula (2) H 2 NHN—X—NHNH 2 (2) [Wherein X represents a group —CO— or a group —CO—A—CO—. A represents an alkylene group or an arylene group which may have a substituent. ]
- the dihydrazide compound represented by these is mentioned.
- examples of the alkylene group represented by A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and a nonamethylene group.
- linear alkylene groups having 1 to 12 carbon atoms such as a decamethylene group and an undecamethylene group.
- substituent for the alkylene group include a hydroxyl group.
- examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group. Among these, a phenylene group and a naphthylene group are preferable.
- examples of the substituent of the arylene group include the same substituents as the aryl group.
- dihydrazide compound of the general formula (2) examples include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecandiohydrazide, maleic acid dihydrazide, And dibasic acid dihydrazides such as fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, and 2,6-naphthoic acid dihydrazide.
- dibasic acid dihydrazides such as fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iso
- 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.
- polyhydrazide compound examples include polyacrylic acid hydrazide.
- dihydrazide compounds are preferable, dibasic acid dihydrazide is particularly preferable, and adipic acid dihydrazide is most preferable.
- the above hydrazide compounds can be used alone or in admixture of two or more.
- the content of the carboxylic acid hydrazide compound is not limited, but is preferably 0.2 to 1 part by weight, more preferably 0.3 to 0.7 part by weight based on 1 part by weight of the ADCA-based blowing agent.
- the resin composition for producing other additive foams may contain an additive as long as the effects of the invention are not impaired.
- Additives include, for example, inorganic fillers, pigments, lubricants, fluidity improvers, crosslinking agents, and the like.
- inorganic fillers examples include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, and molybdenum compounds.
- the amount of the resin component used can be relatively reduced.
- the effect of improving the surface strength can be obtained.
- an effect of suppressing curling of the foamed decorative sheet can be obtained by adding an inorganic filler.
- the content of such an inorganic filler is preferably 0 to 100 parts by weight and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the resin component.
- the pigment examples include titanium oxide, 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, ultramarine blue, Inorganic pigments such as bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica; for example, aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindo) Linone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated lid And organic pigments cyanine), and the like.
- the content of the pigment is preferably 10
- crosslinking agent that promotes crosslinking by electron beam irradiation
- examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like.
- the crosslinking agent is preferably 0 to 10 parts by weight, and more preferably 1 to 4 parts by weight with respect to 100 parts by weight of the resin component.
- the resin composition for foam production is obtained by preparing and kneading a predetermined amount of the above components.
- the kneading method is not particularly limited, and may be kneaded with a known mixer or the like.
- the foam of the present invention is obtained by heating and foaming a resin composition for producing a foam into a desired shape.
- the resin composition for producing a foam in a molten state is formed into a desired shape (for example, a sheet shape), and then obtained by heating and foaming the formed body.
- the heating conditions are not limited as long as the foam is formed by the decomposition of the pyrolytic foaming agent.
- the heating temperature is preferably about 190 to 240 ° C., and the heating time is preferably about 15 to 90 seconds.
- Electron beam irradiation may be performed before the heat treatment. Thereby, since a resin component can be bridge
- the energy of the electron beam is preferably about 150 kV.
- the irradiation dose is preferably about 10 to 70 kGy.
- a known electron beam irradiation apparatus can be used as the electron beam source.
- Crosslinking can also be carried out using a chemical crosslinking agent (crosslinking agent or crosslinking aid).
- the foam of the present invention can be suitably used as a foamed resin layer of a foam decorative sheet.
- stacked the foaming resin layer on the paper-like base material is mentioned.
- a foamed decorative sheet will be described as an example of the foam. Specifically, it has a non-foamed resin layer B (arbitrary layer), a foamed resin layer, a non-foamed resin layer A (arbitrary layer), a pattern layer (arbitrary layer), and a surface protective layer (arbitrary layer) on the substrate.
- the foam decorative sheet will be described.
- 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.
- a resin sheet, a fibrous sheet (paper, etc.) can be generally used.
- fiber sheets such as paper are preferable.
- flame retardant paper pulse-based sheets treated with flame retardants such as guanidine sulfamate and guanidine phosphate
- aluminum hydroxide aluminum hydroxide
- magnesium hydroxide Inorganic paper containing inorganic additives such as: high-quality paper; thin paper.
- the basis weight of the substrate is not critical, preferably about 50 ⁇ 300g / m 2, more preferably about 50 ⁇ 80g / m 2.
- 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.
- 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 10 to 50 ⁇ m, more preferably about 10 to 20 ⁇ m.
- Foamed resin layer is formed by foaming a foaming agent-containing resin layer.
- a foaming agent-containing resin layer In this invention, it is obtained by forming the foaming agent containing resin layer shape
- the thickness of the foamed resin layer is not limited, but is preferably 70 to 150 ⁇ m in a non-foamed state (before foaming). After foaming, 300 to 900 ⁇ m is preferable.
- the foaming agent-containing resin layer may be foamed according to the method described in the production method described later.
- 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.
- 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.
- 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.
- EMAA ethylene-acrylic acid copolymer
- ionomer resin a resin having a structure in which molecules of EMAA and / or ethylene-acrylic acid copolymer 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.
- 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 10 to 50 ⁇ m, more preferably about 10 to 20 ⁇ m.
- the melt flow rate value of the resin component depends on the type of resin component to be used and the like, but generally may be appropriately set within a range of 10 g / 10 minutes or more. Usually, it is preferably in the range of 10 to 100 g / 10 minutes, particularly 10 to 95 g / 10 minutes, 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.
- the content of the resin component in the resin composition is not limited, but it is preferably set appropriately within a range of usually 70 to 100% by weight.
- a pattern pattern layer may be provided on the front surface of the non-foamed resin layer A as necessary.
- the pattern layer gives design to the foamed decorative sheet.
- 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.
- 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.
- the colorant for example, a pigment used in a resin composition for producing a foam can be used.
- Binder resins include, for example, acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins. Examples include resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.
- the solvent examples include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, 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, and 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; dichloromethan
- the thickness of the pattern layer varies depending on the type of pattern, but is generally preferably about 0.1 to 10 ⁇ m.
- 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.
- a method for forming the surface protective layer a known method such as gravure printing can be employed.
- a surface protective layer can also be provided after carrying out the adhesion process (primer process) of the surface of a pattern pattern layer.
- 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 ⁇ m.
- Embossing In this invention, you may attach
- 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.
- the manufacturing method of a foaming decorative sheet is not specifically limited.
- 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.
- the resin composition for forming the foaming agent-containing resin layer and the resin composition for forming the non-foamed resin layer A are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. do it.
- 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.
- a laminate in which two types and two layers are simultaneously formed in advance may be prepared, placed on the substrate, and thermally laminated to adhere to the substrate.
- an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer
- an inorganic filler residue 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 an 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 are co-extruded with the foaming agent-containing resin layer (three types). (Three layer coextrusion molding) is preferable.
- the coextrusion molding can be performed, for example, by using a multi-manifold type T die.
- 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.
- the carboxylic acid hydrazide compound acts as a foaming aid.
- a carboxyl group-containing resin and a foaming aid metal oxide type and fatty acid metal salt type: for example, zinc oxide, zinc stearate, etc.
- metal oxide type and fatty acid metal salt type for example, zinc oxide, zinc stearate, etc.
- Example 1 A resin composition for foam production (resin composition for forming a foaming agent-containing resin layer) comprising the components shown in Table 1 below was prepared.
- the foaming agent-containing resin layer (100 ⁇ m) was extruded and formed on a substrate (backing paper).
- backing paper “WK-665DO (manufactured by Kojin), thickness 110 ⁇ m, basis weight 65 g” was prepared, and a foaming agent-containing resin layer was extruded and formed into a film.
- the temperature of the cylinder containing the resin composition for forming the foaming agent-containing resin layer was 100 ° C.
- the above laminate was irradiated with an electron beam (200 kV, 50 kGy) from the foaming agent-containing resin layer side to crosslink EMAA contained in the foaming agent-containing resin layer.
- the laminate on which the fabric pattern was printed was heated in a gear oven (at 220 ° C. for 45 seconds) to foam the foaming agent-containing resin layer.
- a foamed decorative sheet was produced by embossing the above-mentioned foam with a texture pattern.
- Example 2 A foamed decorative sheet was produced in the same manner as in Example 1 except that the foaming aid was changed to sebacic acid dihydrazide (product name “SDH” manufactured by Otsuka Chemical).
- Example 3 A foamed decorative sheet was produced in the same manner as in Example 1 except that the foaming aid was changed to dodecanediohydrazide (product name “DDH” manufactured by Otsuka Chemical).
- Example 4 A foamed decorative sheet was prepared in the same manner as in Example 1 except that the foaming aid was changed to isophthalic acid dihydrazide (product name “IDH” manufactured by Otsuka Chemical).
- Comparative Example 1 A foamed decorative sheet was prepared by heating at 240 ° C. for 45 seconds in the same manner as in Example 1 except that 5 parts by weight of zinc stearate was used as a foaming aid.
- Comparative Example 2 A foamed decorative sheet was produced in the same manner as in Example 1 by heating at 240 ° C. for 45 seconds without adding a foaming aid.
- Comparative Example 3 A foamed decorative sheet was produced in the same manner as in Example 1 except that 1 part by weight of urea was used as the foaming aid.
- Test Example 1 In-machine foaming
- In-machine foaming means abnormal foaming before extrusion inside the T-die extruder.
- Test Example 2 (Whiteness of foamed resin layer) The whiteness of the foamed resin layer of the foamed wallpaper produced in Examples and Comparative Examples was evaluated using a color difference meter CR-300 (manufactured by Konica Minolta).
- the b value was measured, and when the b value was 5 or less, it was evaluated that the whiteness was high.
- Test Example 3 The scratch resistance of the foamed wallpaper produced in the examples and comparative examples was evaluated.
- test piece (foamed wallpaper) was attached to a Gakushin Abrasion Tester (JIS L0849 Abrasion Tester Type II). Using a metal claw designated by the group as a friction machine of the testing machine, a load of 200 g was applied to the tip of the metal claw and the sample was reciprocated five times. The surface condition of the test piece after the test was visually observed.
- Grade 5 No change
- Grade 4 A little change on the surface
- Grade 3 The surface appears torn
- Grade 2 The surface is torn and a backing material such as paper is visible (long) Less than 1 cm)
- First grade There are five stages in which the surface is torn and the backing material such as paper can be seen (length is 1 cm or more).
- Test Example 4 (Discoloration of paper base material) The discoloration of the paper-based substrate of the foamed wallpaper produced in the examples and comparative examples was confirmed visually.
Landscapes
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- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Molding Of Porous Articles (AREA)
Abstract
Description
1.発泡体製造用樹脂組成物であって、カルボキシル基含有樹脂、アゾジカルボンアミド系発泡剤及びカルボン酸ヒドラジド化合物を含有することを特徴とする発泡体製造用樹脂組成物。
2.前記カルボキシル基含有樹脂は、エチレン-メタクリル酸共重合体、エチレン-アクリル酸共重合体及びこれらの共重合体を含むアイオノマーからなる群から選択される少なくとも1種である、上記項1に記載の発泡体製造用樹脂組成物。
3.前記カルボキシル基含有樹脂は、エチレン-メタクリル酸共重合体である、上記項1に記載の発泡体製造用樹脂組成物。
4.前記カルボン酸ヒドラジド化合物は、アジピン酸ジヒドラジドである、上記項1~3のいずれかに記載の発泡体製造用樹脂組成物。
5.上記項1~4のいずれかに記載の発泡体製造用樹脂組成物を所望の形状に成形後、加熱発泡させて得られる発泡体。
6.上記項1~4のいずれかに記載の発泡体製造用樹脂組成物をシート状に成形後、加熱発泡させて得られる発泡樹脂層。
7.紙質基材上に少なくとも上記項6に記載の発泡樹脂層を有する発泡化粧シート。
8.紙質基材上に上記項6に記載の発泡樹脂層及び非発泡樹脂層Aを順に積層した発泡化粧シート。
9.前記紙質基材と前記発泡樹脂層との間に非発泡樹脂層Bを更に有する、上記項8に記載の発泡化粧シート。
10.最表面層の上からエンボス加工が施されている、上記項7~9のいずれかに記載の発泡化粧シート。 That is, the present invention relates to the following resin composition for foam production and foam.
1. A resin composition for producing a foam, which comprises a resin containing a carboxyl group, an azodicarbonamide-based foaming agent, and a carboxylic acid hydrazide compound.
2. The carboxyl group-containing resin is at least one selected from the group consisting of ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, and ionomers containing these copolymers. Resin composition for foam production.
3. Item 2. The resin composition for foam production according to Item 1, wherein the carboxyl group-containing resin is an ethylene-methacrylic acid copolymer.
4). Item 4. The resin composition for producing a foam according to any one of Items 1 to 3, wherein the carboxylic acid hydrazide compound is adipic acid dihydrazide.
5). 5. A foam obtained by molding the resin composition for foam production according to any one of the above items 1 to 4 into a desired shape, followed by heating and foaming.
6). A foamed resin layer obtained by molding the resin composition for foam production according to any one of the above items 1 to 4 into a sheet shape and then heating and foaming the sheet.
7). Item 7. A foamed decorative sheet having at least the foamed resin layer described in Item 6 above on a paper-based substrate.
8). The foaming decorative sheet which laminated | stacked the foaming resin layer of the said claim | item 6, and the non-foaming resin layer A in order on the paper quality base material.
9. Item 9. The foamed decorative sheet according to Item 8, further comprising a non-foamed resin layer B between the paper substrate and the foamed resin layer.
10. Item 10. The foamed decorative sheet according to any one of Items 7 to 9, which is embossed from above the outermost surface layer.
本発明の発泡体製造用樹脂組成物は、カルボキシル基含有樹脂、アゾジカルボンアミド系発泡剤(ADCA系発泡剤)及びカルボン酸ヒドラジド化合物を含有する。 1. Resin composition for foam production The resin composition for foam production of the present invention contains a carboxyl group-containing resin, an azodicarbonamide foaming agent (ADCA foaming agent), and a carboxylic acid hydrazide compound.
カルボキシル基含有樹脂としては樹脂中にカルボキシル基を含有するものであれば特に限定されない。カルボキシル基含有樹脂としては、例えば、アクリル酸及びメタクリル酸の少なくとも1種のモノマーとエチレンとの組み合わせにより得られる共重合体を好適に用いることができる。具体的には、エチレン-メタクリル酸共重合体(EMAA)、エチレン-アクリル酸共重合体(EAA)及びこれらの共重合体を含むアイオノマーの少なくとも1種を用いることが望ましい。アイオノマーとしては、EMAA及び/又はEAAの分子間をナトリウム、亜鉛等の金属のイオンで分子間結合した構造を有する樹脂が使用できる。上記樹脂(重合体やアイオノマー)を用いることにより、樹脂中の水素結合等に起因する強固な層を形成できるため、発泡体の表面強度を高め易い。 Carboxyl group-containing resin The carboxyl group-containing resin is not particularly limited as long as it contains a carboxyl group in the resin. As the carboxyl group-containing resin, 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. Specifically, it is desirable to use at least one of ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA), and an ionomer containing these copolymers. As the ionomer, a resin having a structure in which EMAA and / or EAA molecules are intermolecularly bonded with metal ions such as sodium and zinc can be used. By using the above resin (polymer or ionomer), a strong layer resulting from hydrogen bonding or the like in the resin can be formed, so that the surface strength of the foam can be easily increased.
本発明では、発泡剤としてアゾジカルボンアミド(ADCA)系発泡剤を用いる。 Azodicarbonamide foaming agent In the present invention, an azodicarbonamide (ADCA) foaming agent is used as the foaming agent.
本発明では、発泡助剤としてカルボン酸ヒドラジド化合物を用いる。カルボン酸ヒドラジド化合物は、カルボキシル基含有樹脂と組み合わせて使用しても、化学的な反応により発泡助剤の効能を失活しない。そのため、樹脂成分としてカルボキシル基含有樹脂を含む発泡体を製造する場合に、発泡体の変色等を生じさせることなく発泡体が得られる。 Carboxylic acid hydrazide compound In the present invention, a carboxylic acid hydrazide compound is used as a foaming aid. Even when the carboxylic acid hydrazide compound is used in combination with a carboxyl group-containing resin, the efficacy of the foaming aid is not deactivated by a chemical reaction. Therefore, when producing a foam containing a carboxyl group-containing resin as a resin component, the foam can be obtained without causing discoloration of the foam.
R-CO-NHNH2 (1)
〔式中、Rは水素原子、アルキル基又は置換基を有してもよいアリール基を示す。〕
で表されるモノヒドラジド化合物が挙げられる。 Specific examples of the monohydrazide compound include, for example, the general formula (1)
R-CO-NHNH 2 (1)
[Wherein, R represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent. ]
The monohydrazide compound represented by these is mentioned.
H2NHN-X-NHNH2 (2)
〔式中、Xは基-CO-又は基-CO-A-CO-を示す。Aはアルキレン基又は置換基を有してもよいアリーレン基を示す。〕
で表わされるジヒドラジド化合物が挙げられる。 Specific examples of the dihydrazide compound include, for example, the general formula (2)
H 2 NHN—X—NHNH 2 (2)
[Wherein X represents a group —CO— or a group —CO—A—CO—. A represents an alkylene group or an arylene group which may have a substituent. ]
The dihydrazide compound represented by these is mentioned.
発泡体製造用樹脂組成物は、発明の効果を損なわない範囲で添加剤を含んでもよい。 The resin composition for producing other additive foams may contain an additive as long as the effects of the invention are not impaired.
本発明の発泡体は、発泡体製造用樹脂組成物を所望の形状に成形後、加熱発泡させることにより得られる。例えば、溶融状態の発泡体製造用樹脂組成物を所望の形状(例えば、シート状)に成形後、成形体を加熱発泡させることにより得られる。 2. Foam of the Present Invention The foam of the present invention is obtained by heating and foaming a resin composition for producing a foam into a desired shape. For example, the resin composition for producing a foam in a molten state is formed into a desired shape (for example, a sheet shape), and then obtained by heating and foaming the formed body.
基材は、化粧シート基材として適した機械強度、耐熱性等を有する限り特に限定されず、例えば、樹脂シート、繊維質シート(紙等)などが一般に使用できる。 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 fibrous sheet (paper, etc.) can be generally used.
本発明では、必要に応じて基材と発泡樹脂層との間に非発泡樹脂層(非発泡樹脂層B)が形成されていてもよい。特に、非発泡樹脂層Bが接着剤層として形成される場合は、優れた密着性を得ることができる。非発泡樹脂層Bとしては、例えば、エチレン-酢酸ビニル共重合体(EVA)等を好適に用いることができる。 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.
発泡樹脂層は、発泡剤含有樹脂層を発泡させることにより形成される。本発明では、発泡体製造用樹脂組成物からシート状に成形された発泡剤含有樹脂層を形成し、それを加熱発泡させることにより得られる。 Foamed resin layer The foamed resin layer is formed by foaming a foaming agent-containing resin layer. In this invention, it is obtained by forming the foaming agent containing resin layer shape | molded in the sheet form from the resin composition for foam manufacture, and making it heat-foam.
発泡樹脂層のおもて面には、更に非発泡樹脂層Aを形成してもよい。 Non-foamed resin layer A
A non-foamed resin layer A may be further formed on the front surface of the foamed resin layer.
本発明では、非発泡樹脂層Aのおもて面に必要に応じて絵柄模様層を有してもよい。 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.
本発明では、絵柄模様層の表面に艶調整及び/又は絵柄模様層の保護を意図して表面保護層を有してもよい。表面保護層の種類は限定的ではない。艶調整を目的とする表面保護層であれば、例えば、シリカなどの既知フィラーを含む表面保護層がある。表面保護層の形成方法としては、グラビア印刷などの公知の方法が採用できる。なお、絵柄模様層と表面保護層との密着性が十分に得られない場合には、絵柄模様層の表面を易接着処理(プライマー処理)した後に表面保護層を設けることもできる。 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.
本発明では、適宜エンボス模様を付してもよい。この場合、発泡化粧シートの最表面層(基材と反対側)の上からエンボス加工すれば良い。エンボス加工は、エンボス版の押圧等、公知の手段により実施することができる。例えば、最表面層が表面保護層である場合は、そのおもて面を加熱軟化後、エンボス版を押圧することにより所望のエンボス模様を賦型できる。エンボス模様としては、例えば木目板導管溝、石板表面凹凸、布表面テクスチャア、梨地、砂目、ヘアライン、万線条溝等がある。 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.
発泡化粧シートの製造方法は特に限定されない。例えば、紙等の基材上に発泡樹脂層と非発泡樹脂層Aとを有する発泡化粧シートを製造するには、Tダイ押出し機による同時押出しが好適である。2つの層に対応する溶融樹脂を同時に押出すことにより2層の同時成膜が可能なマルチマニホールドタイプのTダイを用いることができる。この場合、発泡剤含有樹脂層を形成するための樹脂組成物及び非発泡樹脂層Aを形成するための樹脂組成物をそれぞれ別個のシリンダー中に入れ、2種2層を同時に押出し成膜・積層すればよい。この方法では、同時押出し積層体は、基材上に同時積層(成膜)する。基材上に押出しと同時に積層された樹脂層は、熱溶融により接着性を有するため基材と接着される。 <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 A are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. do it. 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.
下記表1に示す成分からなる発泡体製造用樹脂組成物(発泡剤含有樹脂層を形成するための樹脂組成物)を用意した。 Example 1
A resin composition for foam production (resin composition for forming a foaming agent-containing resin layer) comprising the components shown in Table 1 below was prepared.
発泡助剤をセバシン酸ジヒドラジド(製品名「SDH」大塚化学製)に代えた以外は実施例1と同様にして発泡化粧シートを作製した。 Example 2
A foamed decorative sheet was produced in the same manner as in Example 1 except that the foaming aid was changed to sebacic acid dihydrazide (product name “SDH” manufactured by Otsuka Chemical).
発泡助剤をドデカンジオヒドラジド(製品名「DDH」大塚化学製)に代えた以外は実施例1と同様にして発泡化粧シートを作製した。 Example 3
A foamed decorative sheet was produced in the same manner as in Example 1 except that the foaming aid was changed to dodecanediohydrazide (product name “DDH” manufactured by Otsuka Chemical).
発泡助剤をイソフタル酸ジヒドラジド(製品名「IDH」大塚化学製)に代えた以外は実施例1と同様にして発泡化粧シートを作製した。 Example 4
A foamed decorative sheet was prepared in the same manner as in Example 1 except that the foaming aid was changed to isophthalic acid dihydrazide (product name “IDH” manufactured by Otsuka Chemical).
発泡助剤としてステアリン酸亜鉛を5重量部使用した以外は、実施例1と同様にして240℃で45秒加熱し、発泡化粧シートを作製した。 Comparative Example 1
A foamed decorative sheet was prepared by heating at 240 ° C. for 45 seconds in the same manner as in Example 1 except that 5 parts by weight of zinc stearate was used as a foaming aid.
発泡助剤を添加せずに240℃45秒にて加熱し、実施例1と同様にして発泡化粧シートを作製した。 Comparative Example 2
A foamed decorative sheet was produced in the same manner as in Example 1 by heating at 240 ° C. for 45 seconds without adding a foaming aid.
発泡助剤として尿素を1重量部使用した以外は、実施例1と同様にして発泡化粧シートを作製した。 Comparative Example 3
A foamed decorative sheet was produced in the same manner as in Example 1 except that 1 part by weight of urea was used as the foaming aid.
樹脂成分をEVA(MFR=20g/10分、酢酸ビニル含有量:20重量%)100重量部、発泡助剤としてステアリン酸亜鉛を5重量部、発泡剤含有量を4重量部とした以外は、実施例1と同様にして発泡化粧シートを作製した。 Comparative Example 4
The resin component was EVA (MFR = 20 g / 10 min, vinyl acetate content: 20% by weight) 100 parts by weight, zinc stearate 5 parts by weight as a foaming aid, and foaming agent content 4 parts by weight, A foamed decorative sheet was produced in the same manner as in Example 1.
実施例及び比較例において、押出し時の機内発泡の有無を確認した。機内発泡は、Tダイ押出し機の内部において押出し前に異常発泡することを意味する。 Test Example 1 (In-machine foaming)
In Examples and Comparative Examples, the presence or absence of in-machine foaming during extrusion was confirmed. In-machine foaming means abnormal foaming before extrusion inside the T-die extruder.
実施例及び比較例で作製した発泡壁紙の発泡樹脂層の白度を色彩色差計CR-300(コニカミノルタ製)を用いて評価した。 Test Example 2 (Whiteness of foamed resin layer)
The whiteness of the foamed resin layer of the foamed wallpaper produced in Examples and Comparative Examples was evaluated using a color difference meter CR-300 (manufactured by Konica Minolta).
実施例及び比較例で作製した発泡壁紙の耐スクラッチ性を評価した。 Test Example 3 (Scratch resistance)
The scratch resistance of the foamed wallpaper produced in the examples and comparative examples was evaluated.
実施例及び比較例で作製した発泡壁紙の紙質基材の変色を目視により確認した。 Test Example 4 (Discoloration of paper base material)
The discoloration of the paper-based substrate of the foamed wallpaper produced in the examples and comparative examples was confirmed visually.
Claims (10)
- 発泡体製造用樹脂組成物であって、カルボキシル基含有樹脂、アゾジカルボンアミド系発泡剤及びカルボン酸ヒドラジド化合物を含有することを特徴とする発泡体製造用樹脂組成物。 A resin composition for producing a foam, which comprises a resin containing a carboxyl group, an azodicarbonamide-based foaming agent, and a carboxylic acid hydrazide compound.
- 前記カルボキシル基含有樹脂は、エチレン-メタクリル酸共重合体、エチレン-アクリル酸共重合体及びこれらの共重合体を含むアイオノマーからなる群から選択される少なくとも1種である、請求項1に記載の発泡体製造用樹脂組成物。 The carboxyl group-containing resin is at least one selected from the group consisting of ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, and ionomers containing these copolymers. Resin composition for foam production.
- 前記カルボキシル基含有樹脂は、エチレン-メタクリル酸共重合体である、請求項1に記載の発泡体製造用樹脂組成物。 The resin composition for foam production according to claim 1, wherein the carboxyl group-containing resin is an ethylene-methacrylic acid copolymer.
- 前記カルボン酸ヒドラジド化合物は、アジピン酸ジヒドラジドである、請求項1~3のいずれかに記載の発泡体製造用樹脂組成物。 The resin composition for producing a foam according to any one of claims 1 to 3, wherein the carboxylic acid hydrazide compound is adipic acid dihydrazide.
- 請求項1~4のいずれかに記載の発泡体製造用樹脂組成物を所望の形状に成形後、加熱発泡させて得られる発泡体。 A foam obtained by molding the resin composition for producing a foam according to any one of claims 1 to 4 into a desired shape, followed by heating and foaming.
- 請求項1~4のいずれかに記載の発泡体製造用樹脂組成物をシート状に成形後、加熱発泡させて得られる発泡樹脂層。 A foamed resin layer obtained by molding the resin composition for foam production according to any one of claims 1 to 4 into a sheet and then heat-foaming.
- 紙質基材上に少なくとも請求項6に記載の発泡樹脂層を有する発泡化粧シート。 A foamed decorative sheet having at least the foamed resin layer according to claim 6 on a paper-based substrate.
- 紙質基材上に請求項6に記載の発泡樹脂層及び非発泡樹脂層Aを順に積層した発泡化粧シート。 A foamed decorative sheet in which the foamed resin layer and the non-foamed resin layer A according to claim 6 are sequentially laminated on a paper-based substrate.
- 前記紙質基材と前記発泡樹脂層との間に非発泡樹脂層Bを更に有する、請求項8に記載の発泡化粧シート。 The foamed decorative sheet according to claim 8, further comprising a non-foamed resin layer B between the paper-based substrate and the foamed resin layer.
- 最表面層の上からエンボス加工が施されている、請求項7~9のいずれかに記載の発泡化粧シート。 The foamed decorative sheet according to any one of claims 7 to 9, wherein an embossing process is performed on the outermost surface layer.
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CN200980102685.8A CN101925645B (en) | 2008-01-23 | 2009-01-19 | Resin composition for foam production and foam using the same |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011073202A (en) * | 2009-09-29 | 2011-04-14 | Dainippon Printing Co Ltd | Foamed decorative sheet |
JP2011073279A (en) * | 2009-09-30 | 2011-04-14 | Dainippon Printing Co Ltd | Unfoamed sheet, and method for manufacturing foamed decorative sheet using the same |
KR101392725B1 (en) * | 2013-02-08 | 2014-05-08 | 전북대학교산학협력단 | Water-basesd fireproofing coating composition, method of preparing fireproofing wood, and fireproofing wood thereof |
JP2014205357A (en) * | 2014-06-16 | 2014-10-30 | 大日本印刷株式会社 | Laminate before foaming foamed laminated sheet, production method of laminate before forming foamed laminated sheet, and production method of foamed laminated sheet |
JP2016216672A (en) * | 2015-05-25 | 2016-12-22 | 凸版印刷株式会社 | Resin composition, resin sheet, laminate sheet and foam wall paper |
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JP5699319B2 (en) * | 2010-09-16 | 2015-04-08 | 大日本印刷株式会社 | Foam laminated sheet |
WO2014049792A1 (en) | 2012-09-27 | 2014-04-03 | 大日本印刷株式会社 | Multilayer sheet and method for producing multilayer foam sheet |
JP5949396B2 (en) | 2012-09-27 | 2016-07-06 | 大日本印刷株式会社 | Laminated sheet and foam laminated sheet |
CN203901880U (en) | 2013-06-03 | 2014-10-29 | 大日本印刷株式会社 | Laminated sheet for foaming wallpaper |
CN108570294A (en) * | 2017-03-14 | 2018-09-25 | 仁宝电脑工业股份有限公司 | Decorative film configuration and its production method |
JP2019171788A (en) | 2018-03-29 | 2019-10-10 | 大日本印刷株式会社 | Foamed laminated sheet and unfoamed laminated sheet |
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- 2009-01-19 WO PCT/JP2009/050663 patent/WO2009093544A1/en active Application Filing
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JPH04117467A (en) * | 1990-09-06 | 1992-04-17 | Shinto Paint Co Ltd | Formable powder coating composition |
JPH0841234A (en) * | 1994-07-29 | 1996-02-13 | Sekisui Chem Co Ltd | Flame-retardant polyolefin resin foam |
JP2007291599A (en) * | 2006-03-31 | 2007-11-08 | Dainippon Printing Co Ltd | Foamed wall paper |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011073202A (en) * | 2009-09-29 | 2011-04-14 | Dainippon Printing Co Ltd | Foamed decorative sheet |
JP2011073279A (en) * | 2009-09-30 | 2011-04-14 | Dainippon Printing Co Ltd | Unfoamed sheet, and method for manufacturing foamed decorative sheet using the same |
KR101392725B1 (en) * | 2013-02-08 | 2014-05-08 | 전북대학교산학협력단 | Water-basesd fireproofing coating composition, method of preparing fireproofing wood, and fireproofing wood thereof |
JP2014205357A (en) * | 2014-06-16 | 2014-10-30 | 大日本印刷株式会社 | Laminate before foaming foamed laminated sheet, production method of laminate before forming foamed laminated sheet, and production method of foamed laminated sheet |
JP2016216672A (en) * | 2015-05-25 | 2016-12-22 | 凸版印刷株式会社 | Resin composition, resin sheet, laminate sheet and foam wall paper |
Also Published As
Publication number | Publication date |
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CN101925645B (en) | 2014-05-28 |
JP5649693B2 (en) | 2015-01-07 |
KR20100112593A (en) | 2010-10-19 |
JP2013189649A (en) | 2013-09-26 |
JP5300499B2 (en) | 2013-09-25 |
CN101925645A (en) | 2010-12-22 |
KR101376430B1 (en) | 2014-03-20 |
JP2009197219A (en) | 2009-09-03 |
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