WO2016147680A1 - Feuille de mousse autoadhésive - Google Patents

Feuille de mousse autoadhésive Download PDF

Info

Publication number
WO2016147680A1
WO2016147680A1 PCT/JP2016/050315 JP2016050315W WO2016147680A1 WO 2016147680 A1 WO2016147680 A1 WO 2016147680A1 JP 2016050315 W JP2016050315 W JP 2016050315W WO 2016147680 A1 WO2016147680 A1 WO 2016147680A1
Authority
WO
WIPO (PCT)
Prior art keywords
self
meth
sheet
adsorbing
adsorbing foam
Prior art date
Application number
PCT/JP2016/050315
Other languages
English (en)
Japanese (ja)
Inventor
真資 芦田
曽根　篤
Original Assignee
日本ゼオン株式会社
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.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2017506110A priority Critical patent/JPWO2016147680A1/ja
Publication of WO2016147680A1 publication Critical patent/WO2016147680A1/fr

Links

Images

Classifications

    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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

Definitions

  • the present invention relates to a self-adsorbing foam sheet and a self-adsorbing foam laminated sheet, a production method thereof, and a resin composition used for obtaining them.
  • a sheet-like member made of a foam material having many fine pores and having a self-adsorbing property (hereinafter referred to as “self-adsorbing property”) Foamed sheet ”).
  • the adhesive mode of the self-adsorbing foam sheet is not adhesive bonding, but adsorption to the adherend using fine pores, so there is no adhesive residue and it is easy to reattach, including wallpaper and other interior decoration materials It is suitably used for various applications such as decorative materials for construction, and adhering materials for advertisement such as posters and stickers.
  • a substrate such as a resin film is usually laminated on the self-adsorbing foam sheet, and decoration such as printing is applied to the substrate.
  • a laminated sheet having an adsorption layer made of a self-adsorbing foam sheet and a support layer made of a substrate is referred to as a “self-adsorbing foam laminated sheet”.
  • a resin is used as the foam material constituting the self-adsorbing foam sheet, and among them, an acrylate copolymer is preferably used from the viewpoint of excellent mechanical strength and weather resistance.
  • acrylic ester copolymers often have an N-methylol group for the purpose of improving the strength when wet, and a melamine-based crosslinking agent is used in combination for the purpose of further increasing the strength. There were many cases. When an acrylic ester copolymer having an N-methylol group and a melamine crosslinking agent are used in combination, a large amount of formaldehyde is generated during the crosslinking reaction and remains in the self-adsorbing foam sheet.
  • Formaldehyde was generated during the use of the adsorptive foam laminate sheet.
  • Formaldehyde is known as a causative agent of so-called sick house syndrome, and environmental standards are established, and there is a strong demand to reduce the amount of its generation, so such self-adsorbing foam sheets or self-adsorbing foam laminated sheets are used as wallpaper, etc. There was a problem to use.
  • Patent Document 1 discloses a (meth) acrylic acid ester copolymer resin having no N-methylol group in the molecule and an oxazoline crosslinking agent. It is disclosed that a self-adsorbing foam sheet that generates no or almost no formaldehyde is produced by using a resin composition that contains bismuth.
  • Patent Document 1 a (meth) acrylic acid ester copolymer resin having a carboxyl group is used in place of the conventionally used (meth) acrylic acid ester copolymer resin having an N-methylol group.
  • a (meth) acrylic acid ester copolymer resin having a carboxyl group is used in place of the conventionally used (meth) acrylic acid ester copolymer resin having an N-methylol group.
  • the present invention provides a self-adsorbing foam sheet and a self-adsorbing foam laminate sheet having a very small amount of formaldehyde generated, having an appropriate self-adhesive force, and excellent in smoothness, a production method thereof, and these. It is an object to provide a resin composition used for the purpose.
  • the present inventors have satisfied the above required characteristics by combining a predetermined (meth) acrylic acid ester copolymer resin, a crosslinking agent, and a formaldehyde catcher agent. Found to get.
  • (meth) acrylate copolymer resin having an N-methylol group and a glass transition temperature of ⁇ 10 ° C. or less 100 parts by weight of (meth) acrylate copolymer resin having an N-methylol group and a glass transition temperature of ⁇ 10 ° C. or less, and 1 to 20 parts by weight of a crosslinking agent are used.
  • (meth) acryl means “acryl and / or methacryl”.
  • a foam obtained by foaming the resin composition for a self-adsorbing foam sheet according to the first aspect of the present invention is molded into a sheet shape, and then a (meth) acrylic acid ester copolymer is used. It is a self-adsorbing foam sheet obtained by performing a crosslinking reaction of a coalesced resin.
  • a third aspect of the present invention is a self-adsorbing foam laminated sheet having an adsorbing layer made of the self-adsorbing foam sheet according to the second aspect of the present invention and a support layer made of a substrate.
  • a process for producing a resin composition for a self-adsorbing foam sheet comprising 0.1 to 20 parts by mass of a formaldehyde catcher agent, and foaming the resin composition for a self-adsorbing foam sheet to form a self-adsorbing foam sheet
  • a method for producing a self-adsorbing foam sheet comprising: a step of obtaining a foam of a resin composition; and a step of crosslinking a (meth) acrylate copolymer resin after forming the foam into a sheet shape It is.
  • a method for producing a self-adsorbing foam laminated sheet having an adsorbing layer comprising a self-adsorbing foam sheet and a support layer comprising a substrate, and having an N-methylol group there is provided a method for producing a self-adsorbing foam laminated sheet having an adsorbing layer comprising a self-adsorbing foam sheet and a support layer comprising a substrate, and having an N-methylol group. And 100 parts by weight of (meth) acrylic acid ester copolymer resin having a glass transition temperature of ⁇ 10 ° C. or lower, 1 to 20 parts by weight of a crosslinking agent, and 0.1 to 20 parts by weight of a formaldehyde catcher agent.
  • a step of preparing a resin composition for a self-adsorbing foam sheet a step of foaming the resin composition for a self-adsorbing foam sheet to obtain a foam of the resin composition for a self-adsorbing foam sheet, And a step of laminating an adsorption layer on a support layer by performing a crosslinking reaction of a (meth) acrylic ester copolymer resin after forming the foam into a sheet, and a self-adsorbing foam laminated sheet Manufacturing of It is the law.
  • the crosslinking agent is preferably a melamine-based crosslinking agent or a carbodiimide-based crosslinking agent.
  • the gel fraction of the (meth) acrylic ester copolymer resin is preferably 70% or less.
  • the formaldehyde catcher agent is preferably an organic amide compound.
  • the substrate is preferably a resin film.
  • the amount of formaldehyde generated is extremely small, has a suitable self-adhesive force, and is excellent in smoothness.
  • Self-adsorbing foam sheet and self-adsorbing foam laminate sheet, production methods thereof, and The resin composition used for obtaining can be provided.
  • Resin composition for self-adsorbing foam sheet has a N-methylol group and a (meth) acrylic ester copolymer having a glass transition temperature of -10 ° C or lower. 100 parts by mass of resin, 1 to 20 parts by mass of a crosslinking agent, and 0.1 to 20 parts by mass of a formaldehyde catcher agent are included.
  • the (meth) acrylic acid ester copolymer resin has an N-methylol group, and its glass transition temperature is ⁇ 10 ° C. or lower.
  • the glass transition temperature of the (meth) acrylic acid ester copolymer resin is ⁇ 10 ° C. or lower, and preferably ⁇ 13 ° C. or lower.
  • (Meth) acrylic acid ester copolymer resin is 50% by mass or more of monomer units from (meth) acrylic acid ester monomers and 50% by mass of monomer units from monomers copolymerizable therewith. It is preferably composed of 70% by mass or more of monomer units from (meth) acrylic acid ester monomers and 30% by mass or less of monomer units from monomers copolymerizable therewith. More preferably, it is composed of 80% by mass or more of a monomer unit from a (meth) acrylic acid ester monomer and 20% by mass or less of a monomer unit from a monomer copolymerizable therewith.
  • the monomer unit consists of 85% by mass or more of the acrylate monomer and 15% by mass or less of the monomer unit from the monomer copolymerizable therewith.
  • the content of the monomer unit from the (meth) acrylic acid ester monomer within the above range, it is possible to impart appropriate tackiness.
  • the N-methylol group of the (meth) acrylic acid ester copolymer resin is included in the monomer unit copolymerizable with the (meth) acrylic acid ester monomer. It may be contained in the ester monomer unit.
  • the (meth) acrylic acid ester monomer that can be used in the present invention is not particularly limited. From the viewpoint of making the glass transition temperature of the (meth) acrylic acid ester copolymer resin easy to be ⁇ 10 ° C. or lower, the glass transition temperature. It is preferable to contain a unit of a (meth) acrylate monomer that forms a homopolymer having a temperature of ⁇ 20 ° C. or lower.
  • the (meth) acrylate monomer that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is not particularly limited.
  • ethyl acrylate the glass transition temperature of the homopolymer is ⁇ 24 ° C.
  • (meth) acrylic acid alkoxyalkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower (meth) acrylic acid alkoxyalkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is more preferable. If the glass transition temperature of the (meth) acrylic acid ester copolymer resin can be adjusted to ⁇ 10 ° C.
  • methyl acrylate (the glass transition temperature of the homopolymer is 10 ° C.), methyl methacrylate (same as above) 105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.
  • acrylic acid ester monomers may be used alone or in combination of two or more.
  • Monomers copolymerizable with (meth) acrylic acid ester monomers include N-methylol groups such as N-methylolacrylamide and N-methylolmethacrylamide. It is necessary to use a monomer having By using a monomer having an N-methylol group, the gel fraction, which will be described later, can be easily set to a predetermined upper limit value or less, and as a result, the self-adsorbing property has an appropriate self-adhesive force and excellent smoothness. It becomes easy to produce a foam sheet and a self-adsorbing foam laminate sheet.
  • the proportion of the monomer having an N-methylol group is such that the monomer introduced from the monomer having an N-methylol group, with the (meth) acrylic acid ester copolymer resin being 100% by mass.
  • the unit is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.
  • the monomer having an N-methylol group may be used in combination as the copolymerization monomer.
  • the monomer used in combination with the monomer having an N-methylol group is not particularly limited as long as the glass transition temperature of the (meth) acrylate copolymer resin can be ⁇ 10 ° C. or lower. Specific examples include ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester, alkenyl aromatic monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, and other functional groups. And the like. These monomers may be used individually by 1 type, and may use 2 or more types together.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester examples include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
  • alkenyl aromatic monomer examples include styrene, ⁇ -methylstyrene, methyl ⁇ -methylstyrene, vinyltoluene and the like.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
  • olefin monomer examples include ethylene, propylene, butene, pentene and the like.
  • a monomer having a functional group may be used for the purpose of efficiently performing cross-linking between the inside of the copolymer or between the copolymers.
  • the functional group include an organic acid group, a hydroxyl group, an amino group, an amide group, a mercapto group, and an epoxy group.
  • the monomer having an organic acid group is not particularly limited, and typical examples thereof include monomers having an organic acid group such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. In addition to these, monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.
  • the monomer having a carboxyl group include, for example, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and ⁇ , ⁇ such as itaconic acid, maleic acid, and fumaric acid.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be exemplified.
  • the monomer having a sulfonic acid group examples include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.
  • the monomer unit derived therefrom is 100% by mass of (meth) acrylic acid ester copolymer resin, preferably 0.1% by mass or more and 20% by mass or less, More preferably, it is used for the polymerization in such an amount that it is 0.5 to 15% by mass.
  • the amount of the monomer having an organic acid group is within the above range, it becomes easy to keep the viscosity of the polymerization system in an appropriate range at the time of polymerization, and the crosslinking of the copolymer proceeds excessively. Thus, it is easy to prevent the self-adsorption property of the self-adsorbing foam sheet and the self-adsorbing foam laminate sheet from being impaired.
  • the monomer unit having an organic acid group can be easily and preferably introduced into the (meth) acrylic acid ester copolymer resin by polymerization of a monomer having an organic acid group. After the acrylic ester copolymer resin is formed, an organic acid group may be introduced by a known polymer reaction.
  • Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.
  • Examples of the monomer having an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
  • Examples of the monomer having an amide group include ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, and N, N-dimethylacrylamide.
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
  • the monomer unit derived therefrom is 10% by mass or less based on 100% by mass of the (meth) acrylic acid ester copolymer resin. It is preferable to use it for polymerization in such an amount.
  • the amount of the functional group other than the organic acid group used is 10% by mass or less, it becomes easy to keep the viscosity of the polymerization system at the time of polymerization within an appropriate range, and the crosslinking of the copolymer proceeds excessively. Thus, it is easy to prevent the self-adsorption property of the self-adsorbing foam sheet and the self-adsorbing foam laminate sheet from being impaired.
  • a polyfunctional monomer having a plurality of polymerizable unsaturated bonds may be used in combination as a monomer for copolymerization.
  • the polyfunctional monomer preferably has the unsaturated bond at the terminal.
  • polyfunctional monomer examples include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloro Other substituted triazines, such as chill)
  • monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used.
  • Polyfunctional (meth) acrylates are preferred, and pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are more preferred.
  • a polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
  • the (meth) acrylic acid ester copolymer resin can be obtained by copolymerizing a (meth) acrylic acid ester monomer and a copolymerization monomer.
  • the polymerization method for obtaining the (meth) acrylic acid ester copolymer resin is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like, and may be other methods.
  • the property of the (meth) acrylic acid ester copolymer resin may be a solid or a dispersion, but if a product obtained as an emulsion or a dispersion by emulsion polymerization or dispersion polymerization is used as it is, crosslinking occurs. In mixing with an agent or a conductive compound, the operation is easy, and it is convenient for foaming the obtained emulsion or dispersion.
  • the gel fraction of the (meth) acrylic acid ester copolymer resin is preferably 70% or less, and more preferably 65% or less.
  • the gel fraction means that a 500 mg sample of an acrylate copolymer resin is immersed in 100 ml of ethyl acetate at room temperature for 3 days, and then the insoluble matter is filtered through a 200 mesh wire net and air-dried at room temperature for 15 hours. Then, it is dried at 100 ° C.
  • the crosslinking agent used for this invention is not specifically limited,
  • the melamine type crosslinking agent conventionally used for the foaming material can be used.
  • a large amount of formaldehyde is generated during the reaction between the (meth) acrylic acid ester copolymer resin having an N-methylol group and the melamine crosslinking agent.
  • formaldehyde catcher agent which will be described later, formaldehyde can be captured and detoxified, an acrylic ester copolymer resin and a melamine-based cross-linking that are preferable combinations from the viewpoint of increasing strength and the like.
  • a self-adsorbing foamed sheet and a self-adsorbing foamed laminated sheet with a very small amount of formaldehyde can be produced while using the agent in combination.
  • the melamine-based crosslinking agent used in the present invention is not particularly limited, and conventionally known melamine crosslinking agents can be used.
  • melamine, methylol melamine obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting methylol melamine with a lower alcohol, and a mixture thereof can be used.
  • the melamine-based crosslinking agent may be a monomer, a condensate composed of a dimer or higher polymer, or a mixture thereof.
  • methylol melamine examples include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and the like.
  • the lower alcohol used for the etherification of methylolmelamine methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used.
  • the compound contained in the melamine-based crosslinking agent has, for example, an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule as a functional group.
  • imino group type methylated melamine methylol group type melamine
  • methylol group type methylated melamine methylol group type methylated melamine
  • fully alkyl type methylated melamine fully alkyl type methylated melamine.
  • the melamine-based cross-linking agent is obtained by reacting the functional group it has with the N-methylol group in the (meth) acrylic acid ester copolymer resin to give an intramolecular or intermolecular (meth) acrylic acid ester copolymer.
  • a melamine-based crosslinking agent is preferable because it is excellent in a crosslinking effect at a high temperature of 120 ° C. or more and can form a self-adsorbing foam sheet excellent in strength and self-adsorption.
  • the amount of the melamine-based crosslinking agent used is 1 part by mass or more and 20 parts by mass or less as a solid content with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer resin. It is preferable that it is 3 mass parts or more and 15 mass parts or less.
  • the usage-amount of a melamine type crosslinking agent exists in the said range, it has moderate self-adhesion force and can raise the resin strength after bridge
  • a carbodiimide crosslinking agent may be used instead of or together with the melamine crosslinking agent.
  • a carbodiimide-based cross-linking agent By using a carbodiimide-based cross-linking agent, the amount of formaldehyde generated during the cross-linking reaction of the (meth) acrylic acid ester copolymer resin having an N-methylol group can be reduced. Containing a self-adsorbing foam sheet and a self-adsorbing foam laminate sheet that contain less formaldehyde than when using a melamine-based crosslinking agent (for example, the amount generated is less than the detection limit) can do.
  • the carbodiimide-based crosslinking agent used in the present invention is not particularly limited, but a compound having two or more carbodiimide groups in one molecule is preferably used.
  • a known carbodiimide compound can be used as such a compound.
  • the known carbodiimide compound may be synthesized or a commercially available product may be used.
  • Examples of commercially available carbodiimide compounds include “DICNAL HX” manufactured by DIC, “Carbodilite” manufactured by Nisshinbo Chemical, and the like.
  • a polycarbodiimide compound obtained by carbodiimidizing a polyisocyanate by a decarboxylation condensation reaction in the presence of a carbodiimidization catalyst can be used.
  • raw material polyisocyanate examples include hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (H6XDI), xylylene diisocyanate (XDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), and 1,12-diisocyanate decane.
  • HDI hexamethylene diisocyanate
  • H6XDI hydrogenated xylylene diisocyanate
  • XDI xylylene diisocyanate
  • TMHDI 2,2,4-trimethylhexamethylene diisocyanate
  • 1,12-diisocyanate decane examples include 1,12-diisocyanate decane.
  • DI norbornane diisocyanate
  • NBDI norbornane diisocyanate
  • OCDI 2,4-bis- (8-isocyanate octyl) -1,3-dioctylcyclobutane
  • HMDI 4,4′-dicyclohexylmethane diisocyanate
  • TMXDI tetramethylxylylene diene Isocyanate
  • IPDI isophorone diisocyanate
  • TIDI 2,4,6-triisopropylphenyl diisocyanate
  • TCDI 4,4′diphenylmethane diiso Anate
  • MDI tolylene diisocyanate
  • TDI tolylene diisocyanate
  • HTDI hydrogenated tolylene diisocyanate
  • HTDI hydrogenated tolylene diisocyanate
  • the carbodiimidization catalyst is preferably an organophosphorus compound, and phospholene oxides are particularly preferred from the viewpoint of activity.
  • phospholene oxides are particularly preferred from the viewpoint of activity.
  • the carbodiimide-based cross-linking agent is obtained by reacting the carbodiimi group contained therein with the N-methylol group in the (meth) acrylic acid ester copolymer resin so as to be within or between the molecules of the (meth) acrylic acid ester copolymer.
  • a crosslinked structure is formed.
  • a carbodiimide-based crosslinking agent is preferable because it is excellent in a crosslinking effect particularly at a low temperature and can form a self-adsorbing foam sheet excellent in strength and self-adsorption.
  • the amount of the carbodiimide-based crosslinking agent used is 0.5 to 20 parts by mass as a solid content with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer resin. It is preferably 2 parts by mass or less, and more preferably 2 parts by mass or more and 15 parts by mass or less.
  • the amount of the carbodiimide-based crosslinking agent used is within the above range, it has an appropriate self-adhesive force and can increase the resin strength after crosslinking.
  • crosslinking agent instead of the melamine-based crosslinking agent and / or carbodiimide-based crosslinking agent, or together with the melamine-based crosslinking agent and / or carbodiimide-based crosslinking agent, other crosslinking agents (for example, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, Epoxy resins such as sorbitol polyglycidyl ether and bisphenol A polyglycidyl ether; aziridine compounds such as ethyleneimine derivatives such as aldehyde and acrolein; polyfunctional isocyanates such as tolylene diisocyanate, trimethylolpropane tolylene diisocyanate Crosslinking agents; oxazoline-based crosslinking agents; metal salt-based crosslinking agents; metal chelate-based crosslinking agents; peroxide-based crosslinking agents; In addition, according to the present invention, it is possible to use a crosslinking agent that
  • the resin composition for self-adsorbing foam sheets of the present invention contains a formaldehyde catcher agent as an essential component.
  • a formaldehyde catcher agent formaldehyde derived from the components contained in the resin composition for self-adsorbing foam sheets and formaldehyde generated during the crosslinking reaction of the (meth) acrylate copolymer resin are captured and harmless. Therefore, it is possible to reduce the amount of formaldehyde remaining in the self-adsorbing foam sheet, and to produce a self-adsorbing foam sheet and a self-adsorbing foam laminated sheet that generate very little formaldehyde. .
  • the formaldehyde catcher agent that can be used in the present invention is not particularly limited as long as it is a compound that physically adsorbs formaldehyde or chemically reacts with formaldehyde, and is an organic compound including an inorganic compound or a polymer. It may be.
  • formaldehyde catcher agents include hydroxylamine sulfate, hydroxylamine hydrochloride, ammonium acetate, urea, ethylene urea, dicyandiamide, polyamide resins, triazine compounds, hydrazide compounds and other nitrogen-containing compounds; stabilized chlorine dioxide and other halogen oxides And metal salts such as disodium hydrogen phosphate, zinc sulfate, calcium chloride, and magnesium sulfate; Of these, nitrogen-containing compounds are preferable from the viewpoint of availability, and organic amide compounds such as urea, ethyleneurea, polyamide resin, and hydrazide compounds are more preferable from the viewpoint of formaldehyde capturing ability, and adhesion and formaldehyde capturing are preferred. Urea and ethylene urea are more preferable from the viewpoint of compatibility with the properties. These formaldehyde catcher agents may be used alone or in combination of two or more.
  • a mixture of urea and ethylene urea can be particularly preferably used from the viewpoints of availability, handleability, and formaldehyde capture.
  • the amount of the formaldehyde catcher agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less as a solid content with respect to 100 parts by mass of the (meth) acrylic ester copolymer resin, and 0.5 parts by mass More preferably, it is 15 parts by mass or less.
  • amount of formaldehyde catcher used is within the above range, a self-adsorbing foam sheet and a self-adsorbing foam laminate sheet having an extremely small amount of formaldehyde generated, an appropriate self-adhesive force, and excellent smoothness Can be made.
  • the resin composition for a self-adsorbing foam sheet of the present invention is provided with a self-adsorbing foam sheet and a self-adsorbing foam sheet, and a process for improving processability in the manufacturing process of the self-adsorbing foam sheet and the self-adsorbing foam sheet.
  • various additives can be contained. Examples of additives include foam stabilizers, foaming aids, thickeners, fillers, preservatives, fungicides, gelling agents, flame retardants, anti-aging agents, antioxidants, pigments, dyes, tackifiers An agent, a conductive compound, etc. can be mentioned.
  • fatty acid ammonium such as ammonium stearate, sulfonic acid type anionic surfactant such as alkyl sulfosuccinate, quaternary alkyl ammonium chloride, alkylbetaine amphoteric compound, fatty acid alkanolamine and the like can be used.
  • sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkylphenol ether sulfate and the like can be used.
  • inorganic polymer fine particles such as acrylic polymer particles, fine silica, and reactive inorganic compounds such as magnesium oxide can be used.
  • filler calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium hydroxide, clay, kaolin, glass powder and the like can be used.
  • antiseptics and fungicides examples include dihydroxydichlorophenylmethane, sodium pentachlorophenate, 2,3,4,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3,5,6-tetrachloro- 4- (Methylsulfonyl) pyridine, bis (tributyltin) oxide, hexahydro-1,3,5-triethyl-s-triazine, silver complex, zinc complex and the like can be used.
  • ammonium salts such as ammonium acetate, ammonium chloride, and ammonium carbonate, alkylphenol alkylene oxide adducts, polyvinyl methyl ether, polypropylene glycol, polyether poly formal, methyl cellulose, hydroxyethyl cellulose, silicone-based heat sensitive agents, etc. are used. it can.
  • Flame retardants include phosphate ester compounds, halogen phosphate ester compounds, ammonium polyphosphate, antimony trioxide, zinc borate, barium metaborate, ammonium hydroxide, magnesium hydroxide, tin compounds, organophosphorus compounds, Red phosphorus compounds, silicone flame retardants and the like can be used.
  • antioxidant polyphenol-based, hydroquinone-based, hindered amine-based antioxidants and the like can be used.
  • pigments and dyes examples include titanium oxide, carbon black, bengara and quinacridone.
  • tackifiers include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin / glycerin ester, hydrogenated rosin / glycerin ester and other rosin resins; terpene resins, Terpene resins such as terpene phenol resins and aromatic modified terpene resins; petroleum resins such as aliphatic petroleum resins, alicyclic petroleum resins and aromatic petroleum resins; coumarone indene resins; terpene phenol resins; A compound selected from a series resin; a hydrogenated rosin ester; a disproportionated rosin ester; a xylene resin and the like can be used.
  • the self-adsorbing foam sheet of the present invention is obtained by molding a foam obtained by foaming the resin composition for a self-adsorbing foam sheet of the present invention into a sheet shape. ) A crosslinking reaction of an acrylate copolymer resin is performed. Moreover, the self-adsorbing foam laminated sheet of the present invention has an adsorption layer made of the self-adsorbing foam sheet of the present invention and a support layer made of a substrate.
  • the base material used for the self-adsorbing foam laminated sheet include, for example, a paper base material, a synthetic paper, a plastic sheet, and the like.
  • the paper base material include high-quality paper, art paper, coated paper, kraft paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials.
  • Synthetic paper is a paper whose surface is formed by a combination of a thermoplastic resin and an inorganic filler.
  • polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polystyrene resins, polyvinyl chloride resins, acrylic resins, polycarbonate resins, polyamide resins, and fluorine resins such as polytetrafluoroethylene
  • seat which consists of a mixture or laminated body of these resin
  • the thickness of the support layer made of the substrate is not particularly limited, but is usually 10 ⁇ m to 200 ⁇ m.
  • a substrate having releasability is used as a substrate, after forming an adsorption layer composed of a self-adsorbing foam sheet on the substrate as described later, the substrate is peeled off and used as a self-adsorbing foam sheet. be able to.
  • FIG. 1 is a flowchart for explaining a self-adsorbing foam sheet production method S10 of the present invention (hereinafter sometimes abbreviated as “the present production method S10”). As shown in FIG. 1, this manufacturing method S10 includes a resin composition preparation step S1, a foaming step S2, and a sheet forming step S3 in this order. Hereinafter, each step will be described.
  • Resin composition preparation step S1 In the resin composition preparation step S1, 100 parts by weight of a (meth) acrylate copolymer resin having an N-methylol group and a glass transition temperature of ⁇ 10 ° C. or less, 1 to 20 parts by weight of a crosslinking agent, This is a step of preparing a self-adsorbing foam sheet resin composition containing 0.1 to 20 parts by mass of a formaldehyde catcher agent.
  • (Meth) acrylate copolymer resin having a N-methylol group as an essential component and having a glass transition temperature of ⁇ 10 ° C. or lower, a crosslinking agent, and a formaldehyde catcher agent in the resin composition preparation step S1;
  • the resin composition for self-adsorption foaming sheets can be produced by mixing the other component used as needed by arbitrary methods.
  • Each substance used in this step, the use ratio of each substance, and the like are as described above, and a description thereof is omitted here.
  • the (meth) acrylic acid ester copolymer resin is an emulsion or a dispersion
  • a cross-linking agent, a formaldehyde catcher agent, and other components are added to this under stirring in the state of an aqueous dispersion or an aqueous solution. It can be easily mixed only by adding.
  • the mixing method is not particularly limited, and may be mixed using, for example, a roll, a Henschel mixer, a kneader or the like. Mixing may be batch or continuous.
  • the batch mixer include a high viscosity raw material kneader and a stirrer such as a crusher, a kneader, an internal mixer, and a planetary mixer.
  • the continuous mixer include a Farrell type continuous kneader in which a rotor and a screw are combined, and a screw type kneader having a special structure.
  • the single screw extruder and the twin screw extruder currently used for the extrusion process are mentioned. Two or more of these extruders and kneaders may be combined, or a plurality of machines of the same type may be connected and used.
  • the form of the resin composition for a self-adsorbing foam sheet of the present invention is not particularly limited, but when it is in the form of an emulsion or dispersion, it is convenient to obtain a self-adsorbing foam sheet.
  • the viscosity of the emulsion or dispersion is preferably 2,000 to 10,000 mPa ⁇ s, more preferably 3,500 to 5,500 mPa ⁇ s.
  • the foaming step S2 is a step of foaming the self-adsorbing foam sheet resin composition to obtain a foam of the self-adsorbing foam sheet resin composition.
  • an unsolidified foam can be obtained by foaming the self-adsorbing foam sheet resin composition produced in the resin composition production step S1.
  • the resin composition for a self-adsorbing foam sheet is in the form of an emulsion or a dispersion, a foamed emulsion or a foamed dispersion is obtained.
  • the expansion ratio may be appropriately adjusted, but is usually 1.2 to 5 times, preferably 1.5 to 4 times.
  • the method of mechanical foaming is not particularly limited, but it can be carried out by mixing a certain amount of air into the emulsion of the resin composition for self-adsorbing foam sheet and stirring it continuously or batchwise with an Oaks mixer, whipper or the like. it can. The foamed emulsion thus obtained becomes creamy.
  • a heat-expandable microcapsule containing a suitable synthetic resin such as a vinylidene chloride copolymer as a shell wall and encapsulating a low-boiling hydrocarbon-based compound is used as an acrylic resin emulsion or a butadiene-based synthetic rubber.
  • the foamable resin composition can also be prepared by a method of adding to the emulsion.
  • Sheeting process S3 is a process of performing the crosslinking reaction of (meth) acrylic acid ester copolymer resin, after shape
  • the method for forming the foam into a sheet is not particularly limited. Suitable methods include, for example, a method of coating the foam on a process paper such as a polyester film that has been subjected to a release treatment, and forming the sheet into a sheet.
  • coating apparatuses such as a roll coater, reverse roll coater, screen coater, doctor knife coater, comma knife coater can be used. Coating thickness can be obtained.
  • a self-adsorbing property is obtained by solidifying the sheet-like foam on the process paper by performing a crosslinking reaction of the (meth) acrylate copolymer resin.
  • a foam sheet can be formed.
  • the self-adsorbing foam sheet can be easily separated from the process paper.
  • the self-adsorbing foam laminated sheet in the case of producing a self-adsorbing foam laminated sheet, by using the above-mentioned base material as the process paper, in the sheet forming step S3, the self-adsorbing foam laminated sheet can be formed on the base material.
  • a self-adsorbing foam laminated sheet having an adsorbing layer made of an adsorbing foam sheet and a support layer made of a substrate can be produced.
  • a (meth) acrylic acid ester copolymer resin is subjected to a crosslinking reaction, it is preferably dried by heating.
  • the method of heat drying is not particularly limited as long as the foamed emulsion coated on the process paper can be dried and cross-linked.
  • a normal hot air circulation type oven, hot oil circulation hot air chamber, far infrared heater chamber Etc. can be used.
  • the drying temperature is suitably 60 ° C. to 180 ° C., and the drying conditions can be appropriately selected depending on the properties of the emulsion, the coating amount, the coating thickness, and the like.
  • it is preferable to perform multi-stage drying in which the drying is performed from the inside at a low temperature in the initial stage and the drying is sufficiently performed at a higher temperature in the later stage.
  • the density, thickness, hardness and the like of the resulting self-adsorbing foam sheet are adjusted by the mixing ratio of bubbles, the composition of the resin composition for the self-adsorbing foam sheet, the solid content concentration, the heat drying and solidification conditions, and the like.
  • the thickness of the self-adsorbing foam sheet is preferably 0.03 to 3 mm, more preferably 0.05 to 1 mm, and particularly preferably 0.05 to 0.5 mm.
  • the thickness is less than 0.03 mm, when the self-adsorbing foam sheet of the present invention is used as an article holding material or an article surface protecting material, the impact absorbability is inferior, the article holding force and the article surface protecting function are not sufficient, If it is thicker than 3 mm, the strength of the self-adsorbing foam sheet is inferior.
  • the density of the self-adsorbing foam sheet is not particularly limited, but is preferably 0.1 to 1.0 g / cm 3 from the viewpoint of impact absorption.
  • the self-adsorbing foam sheet or the self-adsorbing foam laminated sheet obtained in the sheet forming step S3 is usually wound by a winder after a separator film is pasted on the surface having self-adsorption, press cutting, Cut to a size that is easy to use by cutting with a slitter.
  • the self-adsorbing foam laminate sheet of the present invention is subjected to printing on the substrate surface by, for example, offset printing, seal printing, flexographic printing, silk screen printing, gravure printing, laser printer, thermal transfer printer, inkjet printer, etc. Can do.
  • the self-adsorbing foam laminated sheet having the substrate surface printed thereon can be used as a decorative material for construction, a sticking material for advertisement, a stationery, or a material for toys.
  • sales promotion cards so-called POP cards (posters, stickers, displays, etc.), underlays (lunch mats, table mats, stationery, etc.), hamburgers, sushi, fried buckwheat menus, catalogs, panels, Plate (alternative to metal plate), bromide, store price list, information board (sales guidance, direction / destination guidance, confectionery / food, etc.), gardening POP (feed label, etc.), road sign (funeral / house exhibition place) Etc.), display boards (forbidden to enter, forest road work, etc.), calendars (with images), simple whiteboards, mouse pads, coasters, label writer substitute prints, adhesive labels, etc.
  • the self-adsorbing foam sheet and the self-adsorbing foam laminated sheet of the present invention are excellent in peelability, a part thereof does not remain on the protected article side after peeling. Therefore, it can be suitably used as an article surface protecting material or article holding material for various optical parts, precision parts, and the like.
  • the self-adsorbing foam sheet and the self-adsorbing foam laminate sheet of the present invention are very few even if formaldehyde is generated, and by appropriately setting the composition of the resin composition for the self-adsorbing foam sheet, The generation amount can be less than the detection limit (for example, less than 0.1 ppm). Therefore, it is suitable for use in places and applications where the generation of formaldehyde is prohibited or undesirable. That is, the self-adsorbing foam sheet and the self-adsorbing foam laminated sheet of the present invention are suitable for use as an interior decoration material for construction, a stationery, or a toy material.
  • the glass transition temperature (Tg) of the acrylate copolymer resin used as a material for the self-adsorbing foam laminate sheet described later was measured by the following method.
  • the acrylic ester copolymer resin was applied onto a 50 ⁇ m thick polyethylene terephthalate film with a 250 ⁇ m applicator and dried at room temperature for 24 hours to obtain a resin film.
  • the glass transition temperature was measured according to JIS K 7121 using a measurement temperature of ⁇ 50 ° C. to 160 ° C., a heating rate of 10 ° C./min, and a differential scanning calorimeter (SII Nanotechnology, DSC 6220). (° C.) was measured. The results are shown in Table 1.
  • the gel fraction of the acrylate copolymer resin used in the self-adsorbing foam laminate sheet produced as described later was measured by the following method.
  • the acrylic ester copolymer resin was applied onto a 50 ⁇ m thick polyethylene terephthalate film with a 250 ⁇ m applicator and dried at room temperature for 24 hours to obtain a resin film.
  • a predetermined amount (X) (about 500 mg) was precisely weighed and immersed in 100 ml of ethyl acetate at room temperature for 3 days, and then the insoluble matter was filtered through a 200-mesh wire net for 15 hours at room temperature. And then dried at 100 ° C.
  • test piece cut out to a size of 125 mm ⁇ 25 mm was prepared after producing a self-adsorbing foam laminated sheet as described later.
  • the adsorbing surface of the test piece was bonded to a glass plate with a smooth surface, pressed from above the test piece with a 2 kgf load roller, and allowed to stand in an environment of 23 ° C. and 50% RH for 1 hour.
  • the end of the test piece was fixed to the upper chuck of an autograph (AG-IS manufactured by Shimadzu Corporation), the glass plate was fixed to the lower chuck, and the 180 ° peel test was performed at 23 ° C. and 50% RH.
  • the test force at this time was defined as self-adhesion force (N / cm). The results are shown in Table 1. If the result of this evaluation is 0.01 to 1 N / cm, it can be said that it has an appropriate self-adhesive force.
  • Example 1 In a mixing container, 100 parts of N-methylol group-containing acrylate copolymer resin (I) (composition: ethyl acrylate 46.9 / butyl acrylate 45.8 / acrylonitrile 5.9 / N— Copolymer resin of methylol acrylamide 1.4, glass transition temperature: ⁇ 25.9 ° C., gel fraction: 43.1%), 7.3 parts of melamine-based crosslinking agent in terms of solid content (manufactured by DIC, BECKAMINE M3), 0.3 part of a crosslinking accelerator in terms of solid content (Catalyst ACX, manufactured by DIC) and 4.2 parts of a titanium oxide aqueous dispersion (DIC, DISPERSE WHITE HG-701) in terms of solid content.
  • N-methylol group-containing acrylate copolymer resin (I) composition: ethyl acrylate 46.9 / butyl acrylate 45.8 /
  • Foam stabilizer [Alkyl betaine amphoteric compound / fatty acid alkanolamide mixture (DIC Corporation, DICNAL M-20) / sulfonic acid type anionic surfactant (DIC Corporation, DICNAL M-40) 1/1 mixture], solid content 2.8 parts of a formaldehyde catcher agent (mixture of Riken Resin C-40 urea and 2-imidazolidinone, manufactured by Miki Riken Kogyo Co., Ltd.) was added in this order and filtered through 150 mesh. Finally, ammonia was added to adjust the viscosity to 4,500 mPa ⁇ s to obtain a foamable resin composition.
  • a formaldehyde catcher agent mixture of Riken Resin C-40 urea and 2-imidazolidinone, manufactured by Miki Riken Kogyo Co., Ltd.
  • the foamable resin composition was stirred with a whisk, foamed so that the foaming ratio was doubled, and the stirring speed was further reduced and stirring was continued for 5 minutes.
  • the obtained foamed mixture was applied onto a substrate (polyethylene terephthalate film having a thickness of 50 ⁇ m) using a 0.3 mm applicator. This was put into a drying furnace and held at 80 ° C. for 1.33 minutes, 120 ° C. for 1.33 minutes, and 140 ° C. for 1.33 minutes to allow dry crosslinking to be performed on the substrate to form an adsorption layer (self-adsorbing property)
  • a self-adsorbing foam laminated sheet according to Example 1 was obtained.
  • Example 2 The composition of the N-methylol group-containing acrylate copolymer resin (I) used in Example 1 was changed so that the glass transition temperature was ⁇ 15.3 ° C. and the gel fraction was 41.5%.
  • a group-containing acrylic ester copolymer resin (II) was used instead of the melamine-based crosslinking agent (DIC Corporation, BECKAMINE M3) and the crosslinking accelerator (DIC Corporation, CATALYST ACX) used in Example 1.
  • the same procedure as in Example 1 was conducted, except that 3.6 parts by weight of carbodiimide-based crosslinking agent (DIC Corporation, DICNAL HX) was used and the content of the formaldehyde catcher agent was 0.9 parts by weight.
  • a sheet according to Example 2 was produced.
  • Comparative Example 1 A sheet according to Comparative Example 1 was produced in the same manner as in Example 1 except that the formaldehyde catcher agent was not used.
  • Comparative Example 3 Instead of the N-methylol group-containing acrylate copolymer resin (I) used in Example 1, the composition of the carboxyl group-containing acrylate copolymer resin (I ′) used in Comparative Example 1 was changed to glass. Example 1 except that the carboxyl group-containing acrylate copolymer resin (II ′) was changed so as to have a transition temperature of 6.2 ° C. and a gel fraction of 65.4%, and no formaldehyde catcher was used. In the same manner, a sheet according to Comparative Example 3 was produced.
  • each of the sheets according to Examples 1 and 2 had a low formaldehyde emission amount, an appropriate self-adhesive force, and excellent smoothness.
  • seat which concerns on the comparative example 1 which did not use a formaldehyde catcher agent had the high amount of formaldehyde emission.
  • the sheet according to Comparative Example 2 that uses an acrylic ester copolymer resin that does not contain an N-methylol group, contains a carboxyl group, and has a high gel fraction has poor smoothness.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de mousse auto-adhésive comprenant : 100 parties en masse d'une résine de copolymère d'ester de (méth)acrylate contenant un groupe N-méthylol et présentant une température de transition vitreuse d'au plus -10 °C ; de 1 à 20 parties en masse d'un agent de réticulation ; et de 0,1 à 20 parties en masse d'un capteur de formaldéhyde. La feuille de mousse autoadhésive comprend un corps moussé façonné en forme de feuille puis soumis à une réaction de réticulation avec la résine de copolymère d'ester de (méth)acrylate, ledit corps moussé étant une composition de résine pour feuilles de mousse autoadhésives qui a été moussée. L'invention concerne également une feuille stratifiée de mousse autoadhésive comprenant : une couche adhésive comprenant la feuille de mousse auto-adhésive ; et une couche de support comprenant un matériau de base. La feuille de mousse autoadhésive et la feuille stratifiée de mousse autoadhésive génèrent une quantité de formaldéhyde extrêmement faible et présentent une valeur appropriée d'autoadhésion et un excellent lissé.
PCT/JP2016/050315 2015-03-17 2016-01-07 Feuille de mousse autoadhésive WO2016147680A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017506110A JPWO2016147680A1 (ja) 2015-03-17 2016-01-07 自己吸着性発泡シート

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-053001 2015-03-17
JP2015053001 2015-03-17

Publications (1)

Publication Number Publication Date
WO2016147680A1 true WO2016147680A1 (fr) 2016-09-22

Family

ID=56920329

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/050315 WO2016147680A1 (fr) 2015-03-17 2016-01-07 Feuille de mousse autoadhésive

Country Status (2)

Country Link
JP (1) JPWO2016147680A1 (fr)
WO (1) WO2016147680A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017188120A1 (fr) * 2016-04-28 2017-11-02 日本ゼオン株式会社 Couche auto-adhésive
WO2017188118A1 (fr) * 2016-04-28 2017-11-02 日本ゼオン株式会社 Couche auto-adhésive
WO2020196406A1 (fr) * 2019-03-27 2020-10-01 日本ゼオン株式会社 Composition pour une feuille en mousse auto-adsorbante et feuille stratifiée en mousse auto-adsorbante
EP3584278A4 (fr) * 2017-02-20 2020-12-23 Zeon Corporation Feuille stratifiée expansée auto-adsorbable et composition pour feuille expansée auto-adsorbable
WO2021166861A1 (fr) * 2020-02-19 2021-08-26 日本ゼオン株式会社 Composition pour feuille expansée auto-adsorbante, et feuille stratifiée expansée auto-adsorbante
US11124679B2 (en) * 2016-09-16 2021-09-21 Zeon Corporation Laminated sheet and method for producing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01115982A (ja) * 1987-10-29 1989-05-09 Nitto Denko Corp 貼り付けシート
JP2000109614A (ja) * 1998-10-08 2000-04-18 Asahi Chem Ind Co Ltd ホルムアルデヒド捕捉用水性ラテックス組成物
JP2000177038A (ja) * 1998-10-08 2000-06-27 Shinto Print Kk 吸着シートとその利用品
JP2003001653A (ja) * 2001-06-20 2003-01-08 Achilles Corp 自己接着性のある吸水性フォーム
WO2004104126A1 (fr) * 2003-05-23 2004-12-02 Achiless Corporation Feuille de mousse auto-adhesive a double face

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01115982A (ja) * 1987-10-29 1989-05-09 Nitto Denko Corp 貼り付けシート
JP2000109614A (ja) * 1998-10-08 2000-04-18 Asahi Chem Ind Co Ltd ホルムアルデヒド捕捉用水性ラテックス組成物
JP2000177038A (ja) * 1998-10-08 2000-06-27 Shinto Print Kk 吸着シートとその利用品
JP2003001653A (ja) * 2001-06-20 2003-01-08 Achilles Corp 自己接着性のある吸水性フォーム
WO2004104126A1 (fr) * 2003-05-23 2004-12-02 Achiless Corporation Feuille de mousse auto-adhesive a double face

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017188120A1 (fr) * 2016-04-28 2017-11-02 日本ゼオン株式会社 Couche auto-adhésive
WO2017188118A1 (fr) * 2016-04-28 2017-11-02 日本ゼオン株式会社 Couche auto-adhésive
CN109072020A (zh) * 2016-04-28 2018-12-21 日本瑞翁株式会社 自粘合性层
CN109072020B (zh) * 2016-04-28 2021-08-03 日本瑞翁株式会社 自粘合性层
US11124679B2 (en) * 2016-09-16 2021-09-21 Zeon Corporation Laminated sheet and method for producing the same
EP3584278A4 (fr) * 2017-02-20 2020-12-23 Zeon Corporation Feuille stratifiée expansée auto-adsorbable et composition pour feuille expansée auto-adsorbable
WO2020196406A1 (fr) * 2019-03-27 2020-10-01 日本ゼオン株式会社 Composition pour une feuille en mousse auto-adsorbante et feuille stratifiée en mousse auto-adsorbante
CN113544201A (zh) * 2019-03-27 2021-10-22 日本瑞翁株式会社 自吸附性发泡片用组合物和自吸附性发泡层叠片
JP7552584B2 (ja) 2019-03-27 2024-09-18 日本ゼオン株式会社 自己吸着性発泡シート用組成物および自己吸着性発泡積層シート
WO2021166861A1 (fr) * 2020-02-19 2021-08-26 日本ゼオン株式会社 Composition pour feuille expansée auto-adsorbante, et feuille stratifiée expansée auto-adsorbante

Also Published As

Publication number Publication date
JPWO2016147680A1 (ja) 2017-12-28

Similar Documents

Publication Publication Date Title
WO2016147679A1 (fr) Feuille de mousse auto-adhésive
WO2016147680A1 (fr) Feuille de mousse autoadhésive
JP6897675B2 (ja) 自己粘着性層
JP6897674B2 (ja) 自己粘着性層
CN109641433B (zh) 层叠片及其制造方法
WO2016199523A1 (fr) Récipient, procédé permettant de fabriquer un corps autoadhésif et procédé permettant d'utiliser un corps autoadhésif
WO2018151274A1 (fr) Feuille stratifiée expansée auto-adsorbable et composition pour feuille expansée auto-adsorbable
JP2006176693A (ja) 樹脂組成物、自己吸着性発泡シート、並びに保護材料
JP2017179116A (ja) ストライプ模様状自己吸着性発泡シート
JP2016172805A (ja) 自己吸着性発泡シート用樹脂組成物、自己吸着性発泡シート、及び、自己吸着性発泡積層シート
JP4281434B2 (ja) 導電自己吸着性発泡シート
TWI710593B (zh) 自吸附性發泡片
JP2017179114A (ja) 木目調自己吸着性発泡シート

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16764511

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017506110

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16764511

Country of ref document: EP

Kind code of ref document: A1