WO2019188204A1 - Feuille de mousse stratifiée - Google Patents

Feuille de mousse stratifiée Download PDF

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Publication number
WO2019188204A1
WO2019188204A1 PCT/JP2019/009735 JP2019009735W WO2019188204A1 WO 2019188204 A1 WO2019188204 A1 WO 2019188204A1 JP 2019009735 W JP2019009735 W JP 2019009735W WO 2019188204 A1 WO2019188204 A1 WO 2019188204A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
foamed
layer
foamed resin
olefin
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PCT/JP2019/009735
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English (en)
Japanese (ja)
Inventor
恵子 平川
立原　健一
智史 山内
夏生 杉田
貴史 野本
Original Assignee
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to JP2020509824A priority Critical patent/JPWO2019188204A1/ja
Priority to CN201980034955.XA priority patent/CN112203856A/zh
Publication of WO2019188204A1 publication Critical patent/WO2019188204A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer

Definitions

  • This disclosure relates to a foamed laminated sheet.
  • a foamed laminated sheet in which a foamed resin layer is provided on a fibrous base material such as backing paper is known.
  • a foam laminate sheet a PVC foam laminate sheet having a foamed resin layer of vinyl chloride (PVC) resin is frequently used.
  • PVC vinyl chloride
  • Patent Documents 1 and 2 development of a foamed laminated sheet having a foamed resin layer of a non-chlorine thermoplastic resin instead of PVC resin has been promoted.
  • a foamed laminated sheet having a foamed resin layer using an olefin resin is likely to curl.
  • the present disclosure has been made in view of the above circumstances, and has as its main object to provide a foamed laminated sheet that has a foamed resin layer having good surface strength and that suppresses curling.
  • a foam laminated sheet having a fibrous base material and a resin layer disposed on one surface side of the fibrous base material and containing at least one of an olefinic resin and a cross-linked product thereof.
  • the resin layer has at least a foamed resin layer
  • the elongation of the resin layer is measured in a range of 20 ° C. or more and 100 ° C. or less by thermomechanical analysis, and the linear expansion coefficient is determined by 1 ° C.
  • providing a foamed laminated sheet having a peak value of the linear expansion coefficient of 0.020 [1 / ° C.] or more and 0.050 [1 / ° C.] or less.
  • the foamed laminated sheet having a foamed resin layer having good surface strength and suppressing the occurrence of curling can do.
  • the resin layer may have a non-foamed resin layer A at a position opposite to the fibrous base material with respect to the foamed resin layer.
  • the resin layer may have a non-foamed resin layer B at a position on the fibrous base material side with respect to the foamed resin layer.
  • the basis weight of the fibrous base material may be 50 g / m 2 or more and 70 g / m 2 or less.
  • the foamed resin layer may contain an olefin-vinyl ester copolymer as the olefin resin.
  • the foamed resin layer may contain an olefin-unsaturated carboxylic acid copolymer as the olefin resin.
  • the foamed laminated sheet of the present disclosure has an effect that it has a foamed resin layer having good surface strength and can suppress the occurrence of curling.
  • FIG. 1 is a schematic cross-sectional view showing an example of a foamed laminated sheet of the present disclosure.
  • a foamed laminated sheet 10 shown in FIG. 1 has a fibrous base material 1 and a resin layer X that is disposed on one surface side of the fibrous base material 1 and contains at least one of an olefinic resin and a cross-linked product thereof. .
  • the resin layer X has at least the foamed resin layer 2 which has the foam cell S inside.
  • the elongation of the resin layer X is measured in the range of 20 ° C. or more and 100 ° C. or less by thermomechanical analysis, and the linear expansion coefficient is determined by 1 ° C., the peak value of the linear expansion coefficient is obtained. Is characterized by being within a predetermined range.
  • the resin layer X in FIG. 1 is comprised only from the foamed resin layer 2, as shown in FIG. 2, the resin layer X is the opposite side to the fibrous base material 1 on the basis of the foamed resin layer 2.
  • the non-foamed resin layer A non-foamed resin layer 3 containing at least one of the olefin resin and the cross-linked product thereof may be provided.
  • the resin layer X is a non-foamed resin layer B (non-foamed resin layer 4) containing at least one of an olefin resin and a cross-linked product thereof at a position on the fibrous base material 1 side with respect to the foamed resin layer 2. You may have.
  • the foamed laminated sheet 10 may have a pattern layer 5 and a protective layer 6 in addition to the fibrous base material 1 and the resin layer X.
  • the foamed laminated sheet having a foamed resin layer having good surface strength and suppressing the occurrence of curling can do.
  • the foamed laminated sheet having the foamed resin layer using the olefin resin is likely to curl. The reason is that the difference between the linear expansion coefficient of the fibrous base material and the linear expansion coefficient of the foamed resin layer using the olefin resin is large.
  • various heat treatments such as a heat treatment for forming a foaming agent-containing resin layer, a heat treatment for foaming the foaming agent-containing resin layer, and a heat treatment for emboss formation
  • the conventional foamed resin layer using olefin resin has a very large dimensional change compared to the fibrous base material, so curling occurs during cooling (solidification).
  • Cheap the upper limit of the peak value of the linear expansion coefficient of the resin layer is sufficiently low.
  • the difference between the linear expansion coefficient of the fibrous base material and the linear expansion coefficient of the foamed resin layer using the olefin resin is small, and curling can be suppressed. Therefore, it can be set as a foaming lamination sheet with favorable workability.
  • the peak value of the linear expansion coefficient of the resin layer is too low, the surface strength of the foamed resin layer also tends to decrease.
  • the present disclosure by setting the lower limit of the peak value of the linear expansion coefficient of the resin layer to a predetermined value or more, a foamed laminated sheet having a foamed resin layer having good surface strength can be obtained. it can.
  • the resin layer in the present disclosure is a layer that is disposed on one side of the fibrous base material and contains at least one of an olefin resin and a cross-linked product thereof. Moreover, the resin layer has at least a foamed resin layer, may have only the foamed resin layer, or may further have another layer. Examples of other layers include non-foamed resin layers A and B described later.
  • the peak value of the linear expansion coefficient of the resin layer is, for example, 0.020 [1 / ° C.] or more, 0.022 [1 / ° C.] or more, and 0.025 [1 / ° C.]. [° C.] or higher. If the peak value is too small, the surface strength of the foamed resin layer tends to be low. On the other hand, the peak value of the linear expansion coefficient of the resin layer is, for example, 0.050 [1 / ° C.] or less and may be 0.045 [1 / ° C.] or less. When the peak value is too large, the foamed laminated sheet tends to be curled.
  • the elongation of the resin layer is measured in the range of 20 ° C. or higher and 100 ° C. or lower by thermomechanical analysis, and the linear expansion coefficient is determined in increments of 1 ° C. That is, the linear expansion coefficient from 20 ° C. (293 K) to 21 ° C. (294 K) is obtained, and this is repeated by 1 ° C. (1 K) and increased to 100 ° C. (373 K).
  • L is the length of the sample
  • ⁇ L is the amount of change in length
  • ⁇ t is the amount of change in temperature.
  • the measurement conditions for thermomechanical analysis are preferably those described in the examples described later.
  • the peak value of the linear expansion coefficient of the resin layer can be adjusted by, for example, the composition of the olefin resin contained in the resin layer (particularly the foamed resin layer).
  • the olefin resin is a copolymer of an olefin and a comonomer
  • the linear expansion coefficient of the resin layer tends to decrease when the proportion of the olefin is decreased and the proportion of the comonomer is increased.
  • the amount of resin in the foamed resin layer can also be changed by changing the type and amount of the inorganic filler, the type and amount of the inorganic filler, the type and amount of the plasticizer, and the irradiation conditions of the active energy ray (for example, the irradiation amount and irradiation intensity) Can be adjusted.
  • the foamed resin layer contains at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • the foamed resin layer may further contain an inorganic filler and other additives.
  • the foamed resin layer may contain an olefin resin as a resin component.
  • an olefin resin may be used alone, or two or more olefin resins may be used.
  • the olefin resin include polyolefin, olefin-vinyl ester copolymer, olefin-unsaturated carboxylic acid copolymer, and olefin-unsaturated carboxylic acid ester copolymer.
  • polystyrene examples include polyethylene (PE) and polypropylene (PP), and among them, PE is preferable.
  • PE examples include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE).
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • the olefin-vinyl ester copolymer is a copolymer containing olefin and vinyl ester as monomer components, and may be a binary or ternary or higher copolymer.
  • the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene.
  • examples of the vinyl ester include vinyl acetate, vinyl caproate, vinyl propionate, vinyl caprylate, vinyl laurate, and vinyl stearate.
  • the olefin-vinyl ester copolymer examples include ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl caproate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl caprylate copolymer. And ethylene-vinyl laurate copolymer and ethylene-vinyl stearate copolymer.
  • EVA ethylene-vinyl acetate copolymer
  • ethylene-vinyl caproate copolymer ethylene-vinyl propionate copolymer
  • ethylene-vinyl caprylate copolymer ethylene-vinyl laurate copolymer and ethylene-vinyl stearate copolymer.
  • the ratio of the vinyl ester in the olefin-vinyl ester copolymer is not particularly limited, but is, for example, 5% by mass or more, and may be 15% by mass or more.
  • the ratio of the vinyl ester is, for example, 45% by mass or less, and may be 35% by mass or less.
  • the vinyl acetate content can be measured according to JIS K 7192: 1999. Further, when the proportion of the vinyl ester in the olefin-vinyl ester copolymer is increased, the linear expansion coefficient of the obtained foamed resin layer tends to decrease.
  • the olefin-unsaturated carboxylic acid copolymer is a copolymer containing an olefin and an unsaturated carboxylic acid as monomer components, and may be a binary or ternary or higher copolymer.
  • the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene.
  • examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and fumaric acid.
  • the olefin-unsaturated carboxylic acid copolymer examples include an ethylene-acrylic acid copolymer (EAA) and an ethylene-methacrylic acid copolymer (EMAA).
  • EAA ethylene-acrylic acid copolymer
  • EMA ethylene-methacrylic acid copolymer
  • the acid content in the olefin-unsaturated carboxylic acid copolymer is not particularly limited, but is, for example, 1% by mass or more, and may be 5% by mass or more. On the other hand, the acid content is, for example, 20% by mass or less, and may be 17% by mass or less.
  • the acid content can be determined, for example, by measurement using a Fourier transform infrared spectrophotometer (FT-IR). Further, when the acid content in the olefin-unsaturated carboxylic acid copolymer is increased, the linear expansion coefficient of the obtained foamed resin layer tends to decrease.
  • FT-IR Fourier
  • olefin-unsaturated carboxylic acid ester copolymer examples include ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), ethylene- An ethyl methacrylate copolymer (EEMA) is mentioned.
  • EMA ethylene-methyl acrylate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EEMA ethylene- An ethyl methacrylate copolymer
  • the melt flow rate (MFR) value of the olefin-based resin is, for example, 5 g / 10 minutes or more, or 20 g / 10 minutes or more from the viewpoint of melt extrusion suitability.
  • the MFR value of the olefin resin is, for example, 500 g / 10 min or less, and may be 200 g / 10 min or less.
  • the MFR value was determined according to the test method described in JIS K7210: 2014 “Plastics-Determination of melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics” at a temperature of 190 ° C. and a load of 21.18 N (2 .16 kgf).
  • the foamed resin layer may contain a cross-linked product of an olefin resin as a resin component.
  • This cross-linked product is a cross-linked product in which the molecular chains of the olefin resin are cross-linked, and may be, for example, a cross-linked product cross-linked by electron beam irradiation or a cross-linked product cross-linked by a cross-linking agent.
  • the foamed resin layer preferably contains as a main component at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • the foamed resin layer may contain an olefin resin as a main component, may contain a olefin resin cross-linked product as a main component, and contains a mixture of the olefin resin and the cross-linked product thereof. You may contain as a main component.
  • the ratio of at least one of the olefin resin and its cross-linked product to all the resin components of the foamed resin layer is, for example, 70% by mass or more, may be 80% by mass or more, and is 90% by mass or more. May be.
  • the foamed resin layer may contain only at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • the resin component content in the foamed resin layer is, for example, 30% by mass or more and 80% by mass or less, may be 40% by mass or more and 70% by mass or less, and is 50% by mass or more and 60% by mass or less. There may be. If the content of the resin component is too large, a sufficient expansion ratio may not be obtained. On the other hand, when there is too little content of a resin component, it may be inferior to extrusion film forming property.
  • the foamed resin layer may contain an inorganic filler for the purpose of imparting flame retardancy, suppressing see-through, improving surface strength, and the like.
  • the inorganic filler is not particularly limited, and examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, a molybdenum compound, and titanium dioxide. In addition, these may be used individually by 1 type and may be used in combination of 2 or more types.
  • content of an inorganic filler is not specifically limited, For example, it is 0 mass part or more and 100 mass parts or less with respect to 100 mass parts of resin components, and 20 mass parts or more and 70 mass parts or less may be sufficient. .
  • Foamed resin layers can be added to pigments, antioxidants, crosslinking agents, crosslinking aids, surface treatment agents, fungicides, insecticides, antiseptics, antibacterial agents, diluents, and deodorizers as necessary.
  • additives such as a light stabilizer and a plasticizer may be included.
  • an unfoamed foaming agent may be included.
  • the foamed resin layer has foam cells inside.
  • the foam cell may be a closed cell or an open cell, and a closed cell and an open cell may be mixed.
  • the number, size, density, shape, and the like of the foamed cells are not particularly limited, and can be appropriately designed according to the type, use, and the like of the foamed laminated sheet of the present disclosure.
  • the foam cell can be formed by foaming the foaming agent contained in the foaming agent-containing resin composition used for forming the foamed resin layer.
  • the thickness of the foamed resin layer is not particularly limited, but may be, for example, 350 ⁇ m or more and 1500 ⁇ m or less, and may be 500 ⁇ m or more and 1200 ⁇ m or less.
  • Non-foamed resin layer A The resin layer in the present disclosure may have a non-foamed resin layer A at a position opposite to the fibrous base material with respect to the foamed resin layer.
  • the non-foamed resin layer A for example, the surface strength of the foamed resin layer can be increased. That is, the non-foamed resin layer A preferably functions as a protective layer for the foamed resin layer.
  • the non-foamed resin layer A contains at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • the olefin resin and the cross-linked product thereof include the same materials as those in the above-described foamed resin layer.
  • the non-foamed resin layer A preferably contains, as a main component, at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • Preferred olefin-based resins used for the non-foamed resin layer A include, for example, polyethylene (low density polyethylene (LDPE), high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, polyisoprene, and other resins alone, ethylene and Copolymer of ⁇ -olefin having 4 or more carbon atoms (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene -Ethylene (meth) acrylic acid copolymers such as methacrylic acid copolymers, ethylene-vinyl acetate copolymers (EVA), saponified ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ionomers Can be mentioned.
  • “(Meth) acrylic acid” means at least one of acrylic acid and
  • the non-foamed resin layer A may contain known additives such as fillers, colorants, light stabilizers, foaming agents, other lubricants, and antibacterial agents.
  • the non-foamed resin layer A may be transparent, non-colored, or colored.
  • the thickness of the non-foamed resin layer A is not particularly limited, but is, for example, 2 ⁇ m or more and 50 ⁇ m or less.
  • Non-foamed resin layer B The resin layer in the present disclosure may have a non-foamed resin layer B at a position on the fibrous base material side with respect to the foamed resin layer.
  • the non-foamed resin layer B is disposed between the fibrous base material and the foamed resin layer.
  • the non-foamed resin layer B can enhance the adhesion between the foamed resin layer and the fibrous base material, for example, by having an adhesive function.
  • the non-foamed resin layer B contains at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • the olefin resin and the cross-linked product thereof include the same materials as those in the above-described foamed resin layer and non-foamed resin layer A.
  • the non-foamed resin layer B preferably contains, as a main component, at least one of an olefin resin and a cross-linked product thereof as a resin component.
  • ethylene-vinyl acetate copolymer (EVA) As a preferred olefin-based resin used for the non-foamed resin layer B, for example, ethylene-vinyl acetate copolymer (EVA) can be mentioned.
  • the content (copolymerization ratio) of the vinyl acetate component (VA component) in the ethylene-vinyl acetate copolymer (EVA) is, for example, 10% by mass or more and 46% by mass or less, and 15% by mass or more and 41% by mass. It may be the following.
  • the thickness of the non-foamed resin layer B is not particularly limited, but is, for example, 5 ⁇ m or more and 50 ⁇ m or less.
  • Fibrous base material is a member holding a foamed resin layer.
  • a fibrous base material include known materials used for wallpaper, such as paper, nonwoven fabric, and woven fabric.
  • the paper may be general paper or flame retardant paper.
  • Flame retardant paper is paper that contains a flame retardant in general paper.
  • the flame retardant include nitrogen compounds such as urea and ammonium compounds; hydroxides (preferably hydrates) such as magnesium hydroxide and aluminum hydroxide; and flame retardants containing self-extinguishing phosphorus or halogen elements. It is done.
  • a compound containing crystal water such as magnesium hydroxide can be made flame-retardant by the heat of vaporization of crystal water during combustion decomposition.
  • the non-woven fabric may be a wet non-woven fabric such as a papermaking type, or may be a dry non-woven fabric such as an adhesive type, a mechanical bond type (needle punch, stitch bond), or a spun bond type.
  • Specific examples of the nonwoven fabric include rayon paper, nonwoven fabric mixed with pulp, Japanese paper, glass nonwoven fabric, asbestos nonwoven fabric, polyester nonwoven fabric, and polycarbonate nonwoven fabric.
  • the fibrous base material can contain any material such as a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, and a fixing agent as necessary.
  • the thickness of the fibrous base material is not particularly limited, and can be appropriately set according to the use of the foamed laminated sheet of the present disclosure.
  • the basis weight of the fibrous base material is, for example, 30 g / m 2 or more, and may be 50 g / m 2 or more. If the basis weight of the fibrous base material is too small, the foamed resin layer may not be sufficiently retained.
  • the basis weight of the fibrous base material is, for example, 100 g / m 2 or less, and may be 70 g / m 2 or less. As the basis weight of the fibrous base material decreases, curling is likely to occur. However, in the present disclosure, the peak value of the linear expansion coefficient of the foamed resin layer is within a predetermined range. Even when the basis weight is 100 g / m 2 or less, the occurrence of curling can be suppressed.
  • the foamed laminated sheet of the present disclosure may have a patterned pattern layer at a position opposite to the fibrous base material with respect to the foamed resin layer.
  • a patterned pattern layer By providing the pattern layer, it is possible to easily impart designability to the foamed laminated sheet.
  • the foaming lamination sheet of this indication does not need to have a pattern pattern layer.
  • the pattern layer may be in direct contact with the foamed resin layer, or may be in contact with the primer layer or the adhesive layer.
  • the foaming lamination sheet may have a foaming resin layer, the non-foaming resin layer A, and a design pattern layer in this order.
  • the pattern layer may be in direct contact with the non-foamed resin layer A, or may be in contact with the primer layer or the adhesive layer.
  • the design pattern layer has at least a design pattern portion, and may have a support portion that supports the design pattern portion according to a method of forming the design pattern layer.
  • the design pattern in the design pattern section is not particularly limited, and can be appropriately selected according to the purpose.
  • 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, an abstract pattern, and a flower pattern.
  • the pattern pattern layer can be formed, for example, by printing the pattern pattern portion on one surface of the support portion using printing ink. Moreover, you may form by printing a pattern part directly on the surface of a foamed resin layer or the non-foamed resin layer A using printing ink instead of a support part.
  • the printing ink contains at least a colorant, a binder resin and a solvent, for example.
  • a colorant for example, the same composition as the composition of the printing ink used for forming the pattern layer disclosed in Japanese Patent Application Laid-Open No. 2017-43009 and Japanese Patent Application Laid-Open No. 2011-179161 can be employed.
  • well-known or commercially available ink can be used as printing ink.
  • the printing method is not particularly limited, and a known printing method can be used.
  • a known coating method can be used.
  • the thickness of the design pattern layer is not particularly limited, and can be set as appropriate according to the type of design pattern.
  • the thickness of the pattern layer is, for example, 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the foamed laminated sheet of the present disclosure may have a surface protective layer at a position opposite to the fibrous base material with respect to the foamed resin layer. By providing the surface protective layer, the surface strength of the foamed laminated sheet can be increased.
  • the type of the surface protective layer is not particularly limited and can be appropriately selected depending on the purpose of providing the surface protective layer.
  • the surface protective layer may contain a known matting agent such as silica.
  • the surface protective layer contains, for example, a cured product of an ionizing radiation curable resin as a resin component. You may do it.
  • the thickness of the surface protective layer is not particularly limited and can be set as appropriate.
  • the thickness of the surface protective layer is, for example, 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the thickness of the surface protective layer is usually sufficiently smaller than the thickness of the foamed resin layer, the influence on the curling property is slight.
  • the surface protective layer may be in direct contact with the foamed resin layer, or may be in contact via a primer layer or an adhesive layer.
  • the foamed laminated sheet When the foamed laminated sheet has the non-foamed resin layer A, the foamed laminated sheet preferably has the foamed resin layer, the non-foamed resin layer A, and the surface protective layer in this order.
  • the surface protective layer may be in direct contact with the non-foamed resin layer A, or may be in contact with the primer layer or the adhesive layer.
  • the foamed laminated sheet when the foamed laminated sheet has a pattern layer, the foamed laminated sheet preferably has a foamed resin layer, a pattern layer, and a surface protective layer in this order.
  • the surface protective layer may be in direct contact with the pattern layer or may be in contact with the primer layer or the adhesive layer.
  • a foaming lamination sheet has the non-foaming resin layer A and a design pattern layer, it is preferable that a foaming lamination sheet has a foaming resin layer, the non-foaming resin layer A, a design pattern layer, and a surface protection layer in this order.
  • the foamed laminated sheet of the present disclosure may have a primer layer between the layers constituting the foamed laminated sheet.
  • the resin contained in the primer layer examples include acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyurethane resin, chlorinated polypropylene resin, and chlorinated polyethylene resin. Of these, acrylic resins and chlorinated polypropylene resins are preferred.
  • the thickness of the primer layer is not particularly limited and can be set as appropriate.
  • the thickness of the primer layer is, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, and may be 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the primer layer for example, an interlayer between the fibrous base material and the non-foamed resin layer B, an interlayer between the non-foamed resin layer B and the foamed resin layer, an interlayer between the foamed resin layer and the non-foamed resin layer A
  • examples include an interlayer between the non-foamed resin layer A and the pattern pattern layer, an interlayer between the non-foamed resin layer A and the surface protective layer, and an interlayer between the pattern pattern layer and the surface protective layer.
  • the foamed laminated sheet of the present disclosure may have an embossed pattern on the outermost surface opposite to the fibrous base material with the foamed resin layer as a reference.
  • Examples of the embossed pattern include a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove, and may be a combination thereof.
  • the foamed laminated sheet of the present disclosure can be used as interior materials such as foamed wallpaper and various decorative materials. Among them, it is useful as a foam wallpaper.
  • the production method of the foamed laminated sheet of the present disclosure is not particularly limited. For example, using a foaming agent-containing resin composition containing at least an olefin resin and a foaming agent, a foaming agent-containing resin layer is formed on a fibrous base material. And a foaming step of forming the foamed resin layer by heating and foaming the foaming agent-containing resin layer.
  • the olefin resin used in the foaming agent-containing resin composition and other additives are the same as described above.
  • the foaming agent contained in the foaming agent-containing resin composition can be selected from known foaming agents.
  • the foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; organic thermal decomposition type foaming agents such as hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide, and microcapsules.
  • examples thereof include inorganic foaming agents such as mold foaming agents and baking soda. These may be contained individually by 1 type in the foaming agent containing resin composition, and may be contained 2 or more types.
  • the content of the foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like.
  • the expansion ratio is, for example, 1.5 times or more, and may be 3 times or more and 10 times or less.
  • content of a foaming agent is 1 mass part or more and 20 mass parts or less with respect to 100 mass parts of resin components contained in a foaming agent containing resin composition, and 3 mass parts or more and 10 mass parts or less. It may be.
  • foaming aid used in the foaming agent-containing resin composition examples include known materials used as foaming aids such as metal oxides and fatty acid metal salts, and may be appropriately selected according to the type of foaming agent. Can do. Specific examples of foaming aids include zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, magnesium laurate, zinc oxide, magnesium oxide, carvone And acid hydrazide compounds. These may be contained individually by 1 type in the foaming agent containing resin composition, and may be contained 2 or more types.
  • the foaming agent-containing resin composition contains an olefin-unsaturated carboxylic acid copolymer
  • a carboxylic acid hydrazide compound as a foaming aid. Even when the carboxylic acid hydrazide compound is used in combination with an olefin-unsaturated carboxylic acid copolymer having a carboxyl group, the effectiveness of the foaming auxiliary agent is hardly deactivated by a chemical reaction. For this reason, it can suppress that a foaming resin layer, a fiber base material, etc. turn yellow by the formation or the formation of a chromophore which arises in the case of foaming of a foaming agent containing resin layer.
  • 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. Specific monohydrazide compounds, dihydrazide compounds, and polyhydrazide compounds can be compounds disclosed in, for example, JP-A-2009-197219. These may be contained individually by 1 type in the foaming agent containing resin composition, and may be contained 2 or more types.
  • content of a foaming adjuvant is not specifically limited, For example, it is 0.3 mass part or more and 10 mass parts or less with respect to 100 mass parts of resin components contained in a foaming agent containing resin composition, and 1 mass Part or more and 5 parts by mass or less.
  • the foaming agent-containing resin composition preferably contains azodicarbonamide (ADCA) as a foaming agent and a carboxylic acid hydrazide compound as a foaming aid.
  • ADCA azodicarbonamide
  • carboxylic acid hydrazide compound as a foaming aid.
  • the content of the carboxylic acid hydrazide compound is, for example, 0.2 parts by mass or more and 1 part by mass or less with respect to 1 part by mass of azodicarbonamide (ADCA).
  • the method for forming the foaming agent-containing resin layer on the fibrous base material using the foaming agent-containing resin composition is not particularly limited.
  • the foaming agent-containing resin composition is formed on the fibrous base material by a T-die extruder.
  • An extrusion laminating method in which an article is extruded to form a film can be used.
  • the sheet of the foaming agent-containing resin layer may be laminated on the fibrous base material in a separate step. The cylinder temperature and the die temperature during extrusion film formation can be adjusted as appropriate.
  • an electron beam irradiation step of irradiating the foaming agent-containing resin layer with an electron beam to crosslink the resin component may be performed.
  • the resin component contained in the foaming agent-containing resin layer can be crosslinked to form a crosslinked product, and the surface strength, foaming characteristics, and the like of the finally obtained foamed resin layer can be adjusted.
  • the energy intensity of the electron beam is, for example, 150 kV or more and 250 kV or less, and may be 175 kV or more and 200 kV or less.
  • the irradiation amount is, for example, 10 kGy or more and 100 kGy or less, and may be 10 kGy or more and 60 kGy or less.
  • a known electron beam irradiation apparatus can be used as the electron beam source.
  • a non-foamed resin layer forming step of forming a non-foamed resin layer on one side or both sides of the foaming agent-containing resin layer may be performed.
  • the non-foamed resin layer may be formed by extrusion film formation, or may be formed by heat laminating each film. Of these, coextrusion film formation by a T-die extruder is preferred.
  • a multi-manifold type T die capable of simultaneous film formation of three layers is used, and the foaming agent-containing resin composition and each non-foamed resin are used.
  • the non-foaming resin layer A, the foaming agent-containing resin layer, and the non-foaming agent-containing resin layer A By simultaneously extruding the resin composition for forming the resin layer, that is, by simultaneously performing the foaming agent-containing resin layer forming step and the non-foaming resin layer forming step, the non-foaming resin layer A, the foaming agent-containing resin layer, and the non-foaming agent-containing resin layer A three-layer laminate in which the foamed resin layer B is laminated in this order can be formed.
  • the foaming agent-containing resin composition when an inorganic substance such as a pigment is contained in the foaming agent-containing resin composition, it is preferable to use a method by three-layer coextrusion film formation.
  • the foaming agent-containing resin layer is formed by extrusion film formation, an inorganic residue (in the eyes) tends to be generated at the extrusion port of the extruder, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer.
  • the foaming agent-containing resin layer and the non-foaming resin layer are simultaneously formed by sandwiching the foaming agent-containing resin layer between the inorganic material-free non-foaming resin layers by using a method of three-layer coextrusion film formation. Therefore, it is possible to suppress the occurrence of eyes.
  • each process of forming a pattern pattern layer, a primer layer, and a surface protective layer may perform as needed.
  • the formation method of each layer of a pattern pattern layer, a primer layer, and a surface protective layer is not specifically limited, For example, the usual coating methods, such as printing and application
  • the foaming agent is disposed on one surface side of the fibrous base material 1 and the fibrous base material 1 and contains an olefinic resin and a foaming agent.
  • An unfoamed laminated sheet 11 having the containing resin layer 2a is obtained.
  • the foaming agent-containing resin layer is heated and foamed to form a foamed resin layer.
  • the heating temperature and heating time in the foaming step are not particularly limited as long as the foamed cells can be formed in the layer by decomposition of the foaming agent contained in the foaming agent-containing resin layer, and the composition of the foaming agent-containing resin layer is not limited. It can be set accordingly.
  • Example 1 to 3 and Comparative Examples 1 and 2 A resin composition for forming a foaming agent-containing resin layer with the formulation shown in Table 1 below was prepared by melt kneading.
  • an ethylene-methacrylic acid copolymer (EMAA) Nucrel N1560 (manufactured by Mitsui DuPont Polychemical) is prepared, and the resin for forming the non-foamed resin layer B As an ethylene-vinyl acetate copolymer (EVA) Ultrasen 750 (manufactured by Tosoh Corporation) was prepared.
  • EVA ethylene-methacrylic acid copolymer
  • EVA ethylene-vinyl acetate copolymer
  • a resin layer is formed by extrusion so as to have the thickness shown in Table 2 below.
  • a non-foamed laminated sheet was formed by laminating a backing paper (fibrous substrate) on the surface of the non-foamed resin layer B.
  • WK-665DO manufactured by Kojin
  • the extrusion conditions were a cylinder temperature of 110 ° C. and a die temperature of 120 ° C.
  • the resulting unfoamed laminated sheet was irradiated with an electron beam from the non-foamed resin layer A side.
  • the electron beam irradiation conditions were as follows.
  • a non-foamed resin layer A was coated with an acrylic water-based ink (manufactured by Showa Ink) using a gravure printing machine to form a pattern layer.
  • a surface protective layer was formed by applying water-based ink (ALTOP, acrylic one-component curable resin emulsion, manufactured by Dainichi Seika Kogyo Co., Ltd.) onto the pattern layer using a gravure printing machine.
  • the foamed resin layer was formed by heating in a gear oven at 220 ° C. for 30 to 40 seconds to foam the foaming agent-containing resin layer.
  • the metal roll which has a texture pattern pattern was pressed and embossed by embossing, and the foaming lamination sheet which has an emboss shape was obtained.
  • the elongation in the flow direction of the resin layer placed on the jig with an initial chuck distance of 9.6 mm is in the range of 20 ° C. or higher and 100 ° C. or lower depending on the measurement conditions shown below.
  • the linear expansion coefficient was measured at 1 ° C. from the data obtained in Step 3 and measured. The same measurement was performed three times, and the average value of each linear expansion coefficient was taken as the linear expansion coefficient at each temperature.
  • Step 1 (10 / -10 / 10/5): Decrease the temperature from 10 ° C to -10 ° C at 10 ° C / min, then hold for 5 minutes
  • Step 2 (-10 / -10 / 0.01 / 15): -10 ° C Hold for 15 minutes (Practically constant temperature because the heating rate is very small)
  • Step 3 (-10/110/5/3): Increase the temperature from -10 ° C to 110 ° C at 5 ° C / min, then hold for 3 minutes
  • Step 4 110/10/30/15): 110 ° C to 10 ° C The temperature is lowered to 30 °C / min until 15 minutes, then hold / load program start load (mN) / target load (mN) / loading speed (mN)
  • the foamed laminated sheets obtained in Examples 1 to 3 had good curling load evaluation and surface strength evaluation because the peak value of the linear expansion coefficient was in a predetermined range.
  • the curling load evaluation of Example 2 was better than that of Examples 1 and 3, but the surface strength evaluation was slightly lower.
  • the foamed laminated sheets obtained in Comparative Examples 1 and 2 had a high linear expansion coefficient peak value and a low curling load evaluation.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'objectif principal de la présente invention est de fournir une feuille de mousse stratifiée qui a une couche de mousse de résine ayant une excellente résistance superficielle, l'enroulement de la feuille de mousse stratifiée étant supprimé. Dans la présente invention, le problème ci-dessus est résolu en fournissant une feuille de mousse stratifiée ayant un substrat fibreux et une couche de résine disposée sur une surface du substrat fibreux, la couche de résine contenant une résine à base d'oléfine et/ou un produit réticulé de celle-ci, la couche de résine ayant au moins une couche de résine expansée ; l'étirement de la couche de résine telle que mesurée par analyse thermomécanique est mesuré à l'intérieur de la plage de 20 à 100 °C ; et lorsque le coefficient de dilatation linéaire est déterminé pour chaque 1 °C, la valeur de pic du coefficient de dilatation linéaire est de 0,020 (1/°C) à 0,050 (1/°C).
PCT/JP2019/009735 2018-03-30 2019-03-11 Feuille de mousse stratifiée WO2019188204A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002096433A (ja) * 2000-09-22 2002-04-02 Dainippon Printing Co Ltd 壁 紙
JP2007055232A (ja) * 2005-07-28 2007-03-08 Dainippon Printing Co Ltd 発泡壁紙の製造方法
JP2007224485A (ja) * 2006-01-27 2007-09-06 Dainippon Printing Co Ltd 発泡壁紙用原反及び発泡壁紙
JP2007224484A (ja) * 2006-01-27 2007-09-06 Dainippon Printing Co Ltd 発泡壁紙用原反の製造方法
JP2007268937A (ja) * 2006-03-31 2007-10-18 Dainippon Printing Co Ltd 発泡壁紙
JP2011144494A (ja) * 2011-04-11 2011-07-28 Dainippon Printing Co Ltd 壁装用化粧シート
JP2013079454A (ja) * 2011-09-30 2013-05-02 Dainippon Printing Co Ltd 機能性発泡壁紙
JP2014144644A (ja) * 2009-09-30 2014-08-14 Dainippon Printing Co Ltd 発泡化粧シートの発泡前のシート、並びに発泡化粧シートの発泡前のシートの製造方法及び発泡化粧シートの製造方法
JP2019064081A (ja) * 2017-09-29 2019-04-25 大日本印刷株式会社 発泡積層シートおよび積層シート

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2902185B1 (fr) * 2012-09-27 2017-08-02 Dai Nippon Printing Co., Ltd. Procédé de fabrication d'une feuille de mousse multicouches
EP2915839A1 (fr) * 2014-03-06 2015-09-09 JSC Veika Feuille composite et procédé de fabrication d'une feuille décorative en mousse exempte de PVC et de plastifiants
CN105936172B (zh) * 2016-06-20 2018-09-25 湖北祥源新材科技股份有限公司 一种软质环保多功能装饰用纸及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002096433A (ja) * 2000-09-22 2002-04-02 Dainippon Printing Co Ltd 壁 紙
JP2007055232A (ja) * 2005-07-28 2007-03-08 Dainippon Printing Co Ltd 発泡壁紙の製造方法
JP2007224485A (ja) * 2006-01-27 2007-09-06 Dainippon Printing Co Ltd 発泡壁紙用原反及び発泡壁紙
JP2007224484A (ja) * 2006-01-27 2007-09-06 Dainippon Printing Co Ltd 発泡壁紙用原反の製造方法
JP2007268937A (ja) * 2006-03-31 2007-10-18 Dainippon Printing Co Ltd 発泡壁紙
JP2014144644A (ja) * 2009-09-30 2014-08-14 Dainippon Printing Co Ltd 発泡化粧シートの発泡前のシート、並びに発泡化粧シートの発泡前のシートの製造方法及び発泡化粧シートの製造方法
JP2011144494A (ja) * 2011-04-11 2011-07-28 Dainippon Printing Co Ltd 壁装用化粧シート
JP2013079454A (ja) * 2011-09-30 2013-05-02 Dainippon Printing Co Ltd 機能性発泡壁紙
JP2019064081A (ja) * 2017-09-29 2019-04-25 大日本印刷株式会社 発泡積層シートおよび積層シート

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