WO2019009351A1 - 樹脂発泡体、樹脂発泡体シート、粘着テープ、車両用部材及び建築部材 - Google Patents
樹脂発泡体、樹脂発泡体シート、粘着テープ、車両用部材及び建築部材 Download PDFInfo
- Publication number
- WO2019009351A1 WO2019009351A1 PCT/JP2018/025473 JP2018025473W WO2019009351A1 WO 2019009351 A1 WO2019009351 A1 WO 2019009351A1 JP 2018025473 W JP2018025473 W JP 2018025473W WO 2019009351 A1 WO2019009351 A1 WO 2019009351A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin foam
- weight
- resin
- preferable
- adhesive tape
- Prior art date
Links
Classifications
-
- 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
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
-
- 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
- C08J2207/00—Foams characterised by their intended use
- C08J2207/02—Adhesive
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/346—Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2459/00—Presence of polyacetal
- C09J2459/006—Presence of polyacetal in the substrate
Definitions
- the present invention relates to a resin foam that is flexible and has excellent shapeability, a resin foam sheet made of the resin foam, an adhesive tape, a vehicle member, and a building member.
- Resin foams are lightweight, flexible, and excellent in impact resistance, sound insulation, etc., so they can be used as vehicles, such as automobiles, aircrafts, ships, etc., members for construction of buildings, electronic parts, carpet backings, etc. It is used for all uses, such as a member, household-use, and an electric appliance for business use (patent documents 1 grade).
- a resin foam having a high open cell rate is considered to be particularly excellent in flexibility.
- conventional resin foams have a problem that they are easily broken when forming into a required shape, and are inferior in shapeability. For example, when attempting to form a conventional resin foam into a plate shape, the resin foam may be broken or the like due to spreading.
- the present invention aims to provide a resin foam which is flexible and excellent in formability, a resin foam sheet made of the resin foam, an adhesive tape, a member for vehicles and a building member. Do.
- the present invention is a resin foam having a large number of cells, which contains a polyvinyl acetal and a plasticizer, and has an elongation strain of 300% or more and a 50% compression stress of 70 kPa or less.
- the present invention will be described in detail below.
- a resin foam containing a polyvinyl acetal and a plasticizer is flexible by setting the elongation strain to 300% or more and the 50% compression stress to 70 kPa or less.
- the present invention has been found to be excellent in formability, for example, when tearing or the like does not occur even when forming into a plate shape.
- the resin foam of the present invention contains polyvinyl acetal and a plasticizer.
- the polyvinyl acetal is not particularly limited as long as it is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol with an aldehyde, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetals as needed.
- the lower limit of the degree of acetalization of the polyvinyl acetal is preferably 40 mol%, preferably 85 mol%, more preferably 60 mol%, and still more preferably 75 mol%.
- a preferable lower limit of the amount of hydroxyl groups is 15 mol%, and a preferable upper limit is 40 mol%.
- the said degree of acetalization and the amount of hydroxyl groups can be measured based on JISK6728 "the polyvinyl butyral test method", for example.
- the polyvinyl acetal can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a degree of saponification of 70 to 99.8 mol% is generally used.
- the saponification degree of the polyvinyl alcohol is preferably 80 to 99.8 mol%.
- the preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000.
- the degree of polymerization of the polyvinyl alcohol is 500 or more, the handleability of the resulting resin foam is excellent.
- the degree of polymerization of the polyvinyl alcohol is 4,000 or less, molding of the resin foam becomes easy.
- the more preferable lower limit of the polymerization degree of the polyvinyl alcohol is 1000, and the more preferable upper limit is 3600.
- the aldehyde is not particularly limited, but generally, aldehydes having 1 to 10 carbon atoms are preferably used.
- the above-mentioned aldehyde having 1 to 10 carbon atoms is not particularly limited.
- aldehydes may be used alone or in combination of two or more. Among them, aldehydes having 2 to 10 carbon atoms are preferable, and n-butyraldehyde, n-hexylaldehyde and n-valeraldehyde are more preferable, from the viewpoint of easily designing a high loss coefficient of a resin foam to be obtained. Particularly preferred is n-butyraldehyde.
- the plasticizer is not particularly limited, and examples thereof include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers, etc. Can be mentioned.
- the plasticizer is preferably a liquid plasticizer.
- the said monobasic organic acid ester is not specifically limited,
- the glycol ester etc. which were obtained by reaction of a glycol and a monobasic organic acid are mentioned.
- the glycol include triethylene glycol, tetraethylene glycol, tripropylene glycol and the like.
- the monobasic organic acids include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid and the like. It can be mentioned.
- triethylene glycol dicaproic acid ester triethylene glycol di-2-ethylbutyric acid ester, triethylene glycol di-n-octylic acid ester, triethylene glycol di-2-ethylhexylic acid ester and the like are preferable.
- polybasic organic acid ester is not particularly limited, for example, an ester compound of a polybasic organic acid such as adipic acid, sebacic acid, azelaic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms Can be mentioned. Among them, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like are preferable.
- the organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl hexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl Butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di- -Ethylhexanoate, dipropylene glycol di-2-ethyl butyrate
- the organic phosphoric acid plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecyl phenyl phosphate, triisopropyl phosphate and the like.
- the content of the plasticizer in the resin foam of the present invention is not particularly limited, but a preferable lower limit is 5 parts by weight and a preferable upper limit is 60 parts by weight with respect to 100 parts by weight of the polyvinyl acetal.
- a preferable lower limit of the content of the plasticizer is 20 parts by weight, and a more preferable upper limit is 55 parts by weight.
- the resin foam of the present invention preferably further contains an adhesive.
- the resin foam of the present invention can exhibit adhesiveness and handleability is improved.
- the pressure-sensitive adhesive is not particularly limited, and examples thereof include known pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives and rubber pressure-sensitive adhesives.
- the resin foam of the present invention contains, in addition to the polyvinyl acetal and the plasticizer, for example, additives such as an adhesion regulator, a heat ray absorbent, an ultraviolet shielding agent, an antioxidant, a light stabilizer, and an antistatic agent. You may Moreover, in order to adjust the external appearance of the resin foam obtained, you may contain pigments, dyes, etc., such as carbon black.
- the resin foam of the present invention has an elongation strain of 300% or more and a 50% compression stress of 70 kPa or less.
- elongation strain means a value indicating the degree of deformation applied to a resin foam when it is uniaxially deformed in an axial direction with respect to a resin foam molded into a sheet shape.
- the elongation strain is preferably 400% or more, more preferably 500% or more.
- the upper limit of the elongation strain is not particularly limited, but substantially the upper limit is about 800%.
- 50% compressive stress means a value indicating stress applied to a resin foam when compressed 50% in the thickness direction of the resin foam molded into a sheet.
- the 50% compressive stress is preferably 30 kPa or less, more preferably 20 kPa or less.
- the lower limit of the 50% compressive stress is not particularly limited, but the lower limit is substantially about 5 kPa.
- the elongation strain and the 50% compressive stress can be measured by a method according to JIS K 6767.
- the elongation strain and 50% compression stress can be achieved by adjusting the foamed state of the resin foam. Specifically, for example, it is preferable to set the open cell rate of the resin foam to 20% or more. By setting the open cell ratio to 20% or more, the 50% compression stress of the obtained resin foam can be adjusted to the desired range, and extremely high flexibility can be exhibited.
- the open cell ratio is more preferably 30% or more, still more preferably 40% or more, and particularly preferably 50% or more.
- the upper limit of the said open-cell rate is not specifically limited, About 98% is a substantial upper limit.
- the open cells mean that the cells forming the resin foam are connected to each other.
- the above-mentioned open cell ratio is defined by the volume ratio of the cells connected to the outside of the resin foam to the apparent volume of the resin foam obtained by the dimension measurement, and is measured by the picnometer method described in JIS K7138. be able to.
- the resin foam of the present invention preferably has an apparent density of 50 kg / m 3 or more.
- the apparent density is more preferably 60 kg / m 3 or more, still more preferably 80 kg / m 3 or more, and particularly preferably 100 kg / m 3 or more.
- the resin foam of the present invention preferably has an apparent density of 500 kg / m 3 or less. When the apparent density is 500 kg / m 3 or less, more excellent shapeability can be exhibited.
- the apparent density is more preferably 300 kg / m 3 or less, and still more preferably 200 kg / m 3 or less.
- the preferable lower limit of the average cell diameter is 100 ⁇ m, and the preferable upper limit is 1000 ⁇ m.
- the average cell diameter is in this range, higher flexibility and shapeability can be exhibited.
- a more preferable lower limit of the average cell diameter is 120 ⁇ m, a more preferable upper limit is 500 ⁇ m, and a further preferable lower limit is 200 ⁇ m.
- the said average bubble diameter can be measured by the method of observing a bubble wall part and a void part from the cross-sectional observation photograph of a bubble, and measuring the size of a void part.
- the resin foam of the present invention preferably has an average aspect ratio of 2 or less.
- the average aspect ratio of the bubbles is 2 or less, higher flexibility and shapeability can be exhibited.
- the average aspect ratio of the bubbles is more preferably 1.5 or less.
- the average aspect ratio of the said bubble can be measured by the method of measuring the major axis and minor axis of a space
- the method for producing the resin foam of the present invention is not particularly limited, for example, a thermal decomposition-type foaming agent is blended with the above-mentioned polyvinyl acetal, a plasticizer and an additive added as needed to prepare a resin composition, It is preferable to heat the resin composition to the foaming temperature to decompose the thermal decomposition type foaming agent.
- the type of the thermal decomposition type foaming agent at the time of production is extremely important. Above all, setting of the foaming temperature is essential to achieve a high open cell rate. It is preferable that the said foaming temperature is 180 degreeC or more. At a temperature of 180 ° C. or higher, the resin composition is sufficiently softened at the time of foaming to easily cause the cells to communicate with each other, so that it is considered that open cells are likely to be generated.
- the thermal decomposition type foaming agent is not particularly limited as long as it has a decomposition temperature of about 120 to 240 ° C., and conventionally known ones can be used.
- a thermal decomposition-type foaming agent whose decomposition temperature is 20 ° C. or more higher than the molding temperature of the resin composition which is a raw material before foaming, since the above-mentioned open cell rate can be further increased. It is more preferable to use a thermal decomposition type foaming agent.
- thermal decomposition type foaming agent examples include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide), urea, sodium hydrogen carbonate, and These mixtures etc. are mentioned.
- thermal decomposition type foaming agents commercially available ones include, for example, Cellmike series (manufactured by Sankyo Kasei Co., Ltd.), Binihall series, Cellular series, Neocelbon series (all manufactured by Eiwa Kasei Kogyo Co., Ltd.), etc. Be
- the compounding quantity of the said thermal decomposition type foaming agent in the said resin composition is not specifically limited,
- the preferable minimum with respect to 100 weight part of said polyvinyl acetals is 3 weight part, and a preferable upper limit is 20 weight part. If the compounding quantity of the said thermal decomposition type foaming agent is in this range, a foam with an open cell rate of 10% or more can be manufactured.
- the more preferable lower limit of the compounding amount of the thermal decomposition type foaming agent is 5 parts by weight, and the more preferable upper limit is 15 parts by weight.
- the resin foam of the present invention can exhibit extremely high shapeability which can not be achieved by the conventional resin foam while having the above-mentioned constitution.
- the resin foam of the present invention is, for example, members for vehicles such as automobiles, aircrafts and ships, construction members, electronic components, living members such as backings of carpets, household appliances, household electrical appliances and the like. It can be used for applications.
- the resin foam of the present invention formed into a sheet can be used in a wide range of applications.
- the resin foam sheet which consists of a resin foam of this invention is also one of this invention.
- the adhesive tape in which the adhesive layer is formed on at least one surface of the resin foam sheet of the present invention is extremely excellent in handleability.
- a pressure-sensitive adhesive tape having the resin foam sheet of the present invention and a pressure-sensitive adhesive layer formed on at least one surface of the resin foam sheet is also one of the present invention.
- an adhesive which comprises the said adhesive layer For example, well-known adhesives, such as an acrylic adhesive, a urethane adhesive, and a rubber adhesive, are mentioned.
- a pressure-sensitive adhesive layer having high plasticizer resistance As the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive composition containing, for example, an acrylic polymer (X), a tackifying resin (Y) having a softening point of 140 to 160 ° C., and a crosslinking agent (Z) as the pressure-sensitive adhesive layer having high plasticizer resistance.
- the acrylic polymer (X) is an alkyl methacrylate monomer (A) containing 60% by weight or more of (meth) acrylic acid alkyl ester monomer (a) having 4 or less carbon atoms in the alkyl group, 100 parts by weight And a polymer obtained by polymerizing a monomer mixture containing 5 to 18 parts by weight of a carboxyl group-containing monomer (B).
- (meth) acrylic acid indicates acrylic acid or methacrylic acid
- (meth) acrylate indicates acrylate or methacrylate.
- the (meth) acrylic acid alkyl ester monomer (A) preferably contains 60% by weight or more of a (meth) acrylic acid alkyl ester monomer (a) having 4 or less carbon atoms in the alkyl group.
- a (meth) acrylic acid alkyl ester monomer (a) having 4 or less carbon atoms in the alkyl group is 60% by weight or more, the plasticizer resistance of the obtained pressure-sensitive adhesive layer becomes high.
- the content of the (meth) acrylic acid alkyl ester monomer (a) is more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably from the viewpoint of suppressing a decrease in adhesion to soft polyvinyl chloride Is 100% by weight.
- (meth) acrylic acid alkyl ester monomer (a) examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate and n-butyl (meth) acrylate. ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate and the like.
- These (meth) acrylic acid alkyl ester monomers (a) may be used alone or in combination of two or more.
- n-butyl (meth) acrylate is preferably contained, and it is more preferable to contain only n-butyl (meth) acrylate alone.
- the (meth) acrylic acid alkyl ester monomer (A) may contain a (meth) acrylic acid alkyl ester monomer (b) in which the alkyl group has 5 or more carbon atoms.
- Specific examples of the (meth) acrylic acid alkyl ester monomer (b) include 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and the like.
- the content is preferably 20% by weight or less, more preferably 10% by weight or less.
- the carboxyl group-containing monomer (B) is a polymerizable monomer that contains a carboxyl group in the molecule and is preferably a carboxyl group-containing vinyl monomer.
- Specific examples of the carboxyl group-containing monomer (B) include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. These carboxyl group-containing monomers (B) may be used alone or in combination of two or more. Among them, (meth) acrylic acid is preferable, and acrylic acid is more preferable.
- the monomer mixture used as the raw material of the said acryl-type polymer (X) may further contain other monomers other than the said (meth) acrylic-acid alkylester monomer (A) and a carboxyl group-containing monomer (B).
- the other monomers include monomers containing polar groups other than carboxyl groups, and styrene-based monomers such as styrene, ⁇ -methylstyrene, o-methylstyrene, and p-methylstyrene.
- the preferable lower limit of the content of the carboxyl group-containing monomer (B) is 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid alkyl ester monomer (A) in the monomer mixture which is a raw material of the acrylic polymer (X)
- the preferred upper limit is 18 parts by weight.
- the lower limit of the content of the carboxyl group-containing monomer (B) is preferably 6 parts by weight, more preferably 17 parts by weight, still more preferably 10 parts by weight, and still more preferably 15 parts by weight.
- the preferable lower limit of the weight average molecular weight of the acrylic polymer (X) is 550,000, and the preferable upper limit is 1,000,000.
- the weight average molecular weight is 550,000 or more, the plasticizer resistance of the obtained pressure-sensitive adhesive layer is increased.
- the weight average molecular weight is 1,000,000 or less, it can be suppressed that the pressure-sensitive adhesive layer is too hard, and the adhesive force to an adherend having a complicated shape can be exhibited.
- a more preferable lower limit of the weight average molecular weight is 600,000, a more preferable upper limit is 800,000, a still more preferable lower limit is 650,000, and a further preferable upper limit is 750,000.
- the acrylic polymer (X) is obtained by polymerizing the above-mentioned monomer mixture.
- the said polymerization method is not specifically limited, For example, the method etc. which radically polymerize the said monomer mixture in presence of a polymerization initiator are mentioned. More specifically, conventionally known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization can be adopted.
- an organic peroxide type polymerization initiator for example, an organic peroxide type polymerization initiator, an azo type polymerization initiator, etc. are mentioned.
- the organic peroxide-based polymerization initiator include cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, stearoyl peroxide, o-chlorobenzoyl peroxide, acetyl peroxide, and t-butyl.
- azo polymerization initiator for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanopentane) Acid), 2,2′-azobis (2-methylbutyronitrile) and the like.
- azo polymerization initiators may be used alone or in combination of two or more.
- lauroyl peroxide, octanoyl peroxide, stearoyl peroxide and 3,5,5-trimethylhexanoyl peroxide are preferable from the viewpoint of reducing the odor of the resulting acrylic polymer (X).
- the amount of the polymerization initiator is not particularly limited, but preferably about 0.01 to 10 parts by weight, more preferably about 0.05 to 2 parts by weight, with respect to 100 parts by weight of the monomer mixture.
- the preferable lower limit of the softening point of the tackifying resin (Y) is 140 ° C., and the preferable upper limit is 160 ° C. If the softening point is within the above range, it is possible to suppress the decrease in the adhesive strength of the obtained pressure-sensitive adhesive layer with time.
- the more preferable upper limit of the softening point is 150 ° C. from the viewpoint of further suppressing the decrease in adhesive strength with time.
- the softening point of the tackifying resin (Y) can be measured in accordance with JIS K2207.
- tackifying resin (Y) for example, rosin-based resins such as petroleum resin-based tackifying resins, hydrogenated petroleum resin-based tackifying resins, rosin diol-based tackifying resins, rosin ester-based tackifying resins, terpene resins, A phenol resin, a xylene resin, a coumarone resin, a ketone resin, and these modified resin etc. are mentioned. These tackifying resins may be used alone or in combination of two or more.
- a rosin-based tackifying resin is preferable, and a rosin ester-based tackifying resin is more preferable.
- the rosin ester-based tackifying resin include disproportionated rosin ester, polymerized rosin ester, hydrogenated rosin ester, rosin phenol-based resin and the like.
- the content of the component having a molecular weight of 600 or less is preferably 13% by weight or less in the tackifier resin (Y). If such a tackifying resin is used, the volatile component generated from the tackifying resin can be suppressed low while maintaining the adhesiveness. Furthermore, the viscosity of the pressure-sensitive adhesive layer can be made relatively high by reducing the amount of low molecular weight components, and the migration of the plasticizer to the pressure-sensitive adhesive layer is likely to be inhibited, and the decrease in adhesion with time is less likely to occur.
- Examples of the method for removing the component having a molecular weight of 600 or less from the tackifying resin include a method of heating and melting the tackifying resin to a temperature higher than the softening point, a method of blowing steam, and the like.
- the molecular weight of the said tackifying resin and its content are measured by gel permeation chromatography (GPC), and can be calculated by a polystyrene conversion value and an area ratio.
- the compounding quantity of tackifying resin (Y) in the said adhesive composition is 3 weight part with a preferable minimum with respect to 100 weight part of acrylic polymer (X), and a preferable upper limit is 9 weight part.
- a preferable upper limit is 9 weight part.
- the lower limit of the compounding amount of the tackifier resin (Y) is preferably 4 parts by weight, and more preferably 8 parts by weight.
- the preferred upper limit is 7 parts by weight.
- the said crosslinking agent (Z) has a role which improves the cohesion force of the adhesive layer obtained, and improves the physical property as an adhesive tape.
- said crosslinking agent (Z) For example, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. Among these, isocyanate crosslinking agents or metal chelate crosslinking agents are preferable.
- the isocyanate-based crosslinking agent examples include tolylene diisocyanate, naphthylene-1,5-diisocyanate and diphenylmethane diisocyanate.
- Coronate L by Nippon Polyurethane Co., Ltd. etc. are mentioned, for example.
- the metal chelate type crosslinking agent the chelate compound whose metal atom is aluminum, a zirconium, titanium, zinc, iron, tin etc. is mentioned.
- aluminum chelates in which the central metal is aluminum are preferable.
- Examples of commercially available products include Aluminum Chelate A and Aluminum Chelate M manufactured by Kawaken Fine Chemical Co., Ltd.
- the content of the crosslinking agent (Z) in the pressure-sensitive adhesive composition is not particularly limited, but a preferable lower limit is 0.005 parts by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the acrylic polymer (X).
- a more preferable lower limit is 0.01 parts by weight, a more preferable upper limit is 1 part by weight, a still more preferable lower limit is 0.02 parts by weight, and a still more preferable upper limit is 0.1 parts by weight.
- the pressure-sensitive adhesive composition contains, in addition to the acrylic polymer (X), the tackifying resin (Y), and the crosslinking agent (Z), a solvent such as ethyl acetate, dimethyl sulfoxide, ethanol, acetone, diethyl ether, etc. May be. Among them, ethyl acetate is preferable from the viewpoint of reducing the volatile component.
- the above-mentioned pressure-sensitive adhesive composition may further contain additives such as a filler, a pigment, a dye, an antioxidant and the like, if necessary.
- the preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m, and the preferable upper limit is 200 ⁇ m. Sufficient adhesiveness can be exhibited as the thickness of an adhesive layer is in this range.
- a more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 7 ⁇ m, a more preferable upper limit is 150 ⁇ m, a still more preferable lower limit is 10 ⁇ m, and a still more preferable upper limit is 100 ⁇ m.
- the method for producing the pressure-sensitive adhesive tape of the present invention by forming the pressure-sensitive adhesive layer on at least one surface of the resin foam sheet of the present invention is not particularly limited.
- coating an adhesive using coating machines such as, the method of spraying and apply
- the resin foam, the resin foam sheet, and the adhesive tape of the present invention are flexible and excellent in formability, and therefore, the life of a member for vehicles such as automobiles, aircrafts and ships, building members, electronic parts, carpet backings, etc. It can be used in all applications such as components, household and business electrical appliances.
- the living members include members for the purpose of alleviating vibrations, shocks, sounds and the like, such as carpet backings, curtain materials, wallpaper and the like.
- the electric member include electronic components such as mobile phones, tablets and personal computers, audio, headphones, TVs, refrigerators, washing machines, household electric appliances such as cleaners and the like, or vibration for business electronic appliances.
- the member used for the purpose of alleviation of a sound etc. is mentioned.
- matte, a wall, etc. in indoor and outdoor physical exercise facilities, is mentioned, for example.
- the resin foam, the resin foam sheet, and the adhesive tape of the present invention are particularly suitable as a vehicle member and a building member.
- the member for vehicles using the resin foam of the present invention, the resin foam sheet, or the adhesive tape is also one of the present invention.
- An architectural member using the resin foam, the resin foam sheet or the adhesive tape of the present invention is also one of the present invention.
- the member for the purpose of alleviation of vibration, impact, sound, etc. such as a ceiling material of vehicles, such as a car, an aircraft, and a ship, interior materials, interior backing materials, etc. is mentioned, for example. More specifically, for example, a deadning material used by directly affixing to a steel plate member such as a ceiling or door panel or floor plate of a vehicle such as an automobile, or a steel plate member constituting an exterior or casing and a resin member of an interior Damping material, cushion material, etc. to be used are mentioned.
- Examples of the building members include members for the purpose of alleviating vibrations, shocks, sounds, etc., such as floor base materials, materials for sound barriers, ceiling materials, backing materials made of resin and metal tiles, and the like. More specifically, for example, deadning materials that are directly stuck to metallic tiles made of galvary steel plate (registered trademark) as measures against rain noise, and sound insulation mats that are used by being sandwiched between flooring materials and base materials of housing floors are listed.
- a resin foam which is flexible and excellent in formability
- a resin foam sheet made of the resin foam
- an adhesive tape a member for vehicles and a building member.
- Example 1 Production of resin foam 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer and 100 parts by weight of polyvinyl butyral 1 (PVB1), and vinylol as a thermal decomposition type foaming agent
- a resin composition was obtained by adding 8 parts by weight of AC # 3 (manufactured by Eiwa Chemical Industry Co., Ltd., decomposition temperature: 208 ° C.) and 0.8 parts by weight of carbon black (manufactured by Tokai Carbon Co., Ltd., Siest SP).
- the obtained resin composition was sufficiently kneaded with a mixing roll at 110 ° C., and then extruded with an extruder to obtain a sheet-like body.
- the PVB 1 has a hydroxyl group content of 31 mol%, an acetylation degree of 0.7 mol%, a butyralization degree of 68.3 mol%, and an average polymerization degree of 1,800.
- a sheet-like resin foam (resin foam sheet) was obtained by decomposing a thermal decomposition-type foaming agent at a foaming temperature of 230 ° C. in an oven.
- the open cell rate of the obtained resin foam was measured by the picnometer method according to JIS K7138.
- the apparent density was also measured by a method calculated from the measured weight and the apparent volume obtained by dimensional measurement.
- the resin foam sample for measurement is cut into 50 mm long, 50 mm wide and 4 mm thick and immersed in liquid nitrogen for 1 minute, and then the thickness direction is measured with a razor blade. Cut along a plane parallel to. After that, using a digital microscope (manufactured by Keyence Corporation, product name VHX-900), a 200 ⁇ magnified photograph was taken, and the bubble diameter was measured for all the bubbles present on the cut surface for 2 mm in length in the thickness direction. . The operation was repeated five times while changing the measurement point, and the average value of all observed cell diameters was taken as the average cell diameter.
- the bubble diameter of each bubble was made into the diameter of the inscribed circle where the diameter when drawing the inscribed circle inscribed with respect to the observed bubble is the largest. Also, when measuring the average cell diameter, measure the major axis and minor axis when drawing the inscribed ellipse with respect to each observed cell, and divide the length of the major axis by the length of the minor axis to obtain an aspect The ratio was determined. The aspect ratio was determined for all the observed bubbles, and the average value of the obtained aspect ratios was determined.
- the elongation strain and 50% compressive stress were measured by the method according to JIS K 6767. Specifically, using a sample punched into a dumbbell shape No. 1 specified in JIS K 6251, the elongation strain was measured by a method of drawing at a tensile speed of 500 mm / min with a universal testing machine. Moreover, 50% compressive stress was measured by the method of compressing the lamination
- Example 2 A resin foam was produced in the same manner as in Example 1 except that the compounding amount of the thermal decomposition type foaming agent was as shown in Table 1, and elongation strain, 50% compressive stress and the like were measured.
- Example 5 A resin foam is produced in the same manner as in Example 1 except that polyvinyl butyral 2 (PVB 2) is used instead of polyvinyl butyral 1 and the blending amount of the thermal decomposition type foaming agent is as shown in Table 1, and elongation strain And 50% compressive stress etc. were measured.
- the PVB 2 has a hydroxyl content of 22.0 mol%, an acetylation degree of 4.0 mol%, a butyralization degree of 74.0 mol%, and an average polymerization degree of 550.
- Comparative example 1 As a comparative example, a commercially available polyethylene foam (manufactured by Sekisui Chemical Co., Ltd., Softlon S, foaming ratio 5 times) was prepared. With respect to the polyethylene foam, the elongation strain, 50% compression stress and the like were measured in the same manner as in Example 1.
- Comparative example 2 As a comparative example, a commercially available polyethylene foam (manufactured by Sekisui Chemical Co., Ltd., Softlon S, expansion ratio 10 times) was prepared. With respect to the polyethylene foam, the elongation strain, 50% compression stress and the like were measured in the same manner as in Example 1.
- Comparative example 3 As a comparative example, a commercially available polyethylene foam (manufactured by Sekisui Chemical Co., Ltd., Softlon S, expansion ratio 15 times) was prepared. About this polypropylene foam, it carried out similarly to Example 1, and measured elongation strain, 50% compression stress, etc.
- Comparative example 4 As a comparative example, a commercially available polyurethane foam (Super sheet SS-H6, manufactured by Nippon Shojo Co., Ltd., expansion ratio 15 times) was prepared. About this polyurethane foam, it carried out similarly to Example 1, and measured elongation strain, 50% compression stress, etc.
- Example 8 As a pressure-sensitive adhesive layer, a double-sided adhesive tape for fixing an interior member (manufactured by Sekisui Chemical Co., Ltd., # 5782) was attached to one surface of the resin foam sheet obtained in Example 1 to obtain a single-sided adhesive tape. The obtained single-sided pressure-sensitive adhesive tape was able to exhibit tackiness while maintaining the flexibility and sound insulation of the resin foam sheet described in Example 1.
- Example 9 (1) Production of Acrylic Polymer Into a reaction vessel, 100 parts by weight of n-butyl acrylate and 11 parts by weight of acrylic acid were introduced to obtain a monomer component. The monomer component is dissolved in ethyl acetate, and 0.1 part by weight of lauroyl peroxide is added as a polymerization initiator at the reflux point, and the mixture is refluxed at 70 ° C. for 5 hours to obtain an acrylic weight having a weight average molecular weight of 720,000. A combined solution was obtained.
- the obtained acrylic polymer solution contains a component having a molecular weight of 600 or less with respect to 100 parts by weight of the acrylic polymer which is a non-volatile component of the acrylic polymer solution. 6.3 parts by weight of a polymerized rosin ester-based tackifying resin (softening point 140 ° C.) having a content of 13%, and 0.054 parts by weight of aluminum chelate which is a metal chelate-based crosslinking agent as a crosslinking agent added. Thereafter, they were uniformly mixed to obtain a pressure-sensitive adhesive composition.
- the obtained pressure-sensitive adhesive composition is applied to one side of the resin foam sheet obtained in Example 1, and then dried at 120 ° C. for 5 minutes to form a 60 ⁇ m thick adhesive on one side of the resin foam sheet.
- the single-sided adhesive tape on which the agent layer was laminated was obtained.
- the obtained single-sided pressure-sensitive adhesive tape was able to exhibit tackiness while maintaining the flexibility and sound insulation of the resin foam sheet described in Example 1.
- Adhesive strength retention rate (%) 100 ⁇ (adhesive strength over time / initial adhesive strength)
- the adhesion retention ratio of the single-sided adhesive tape obtained in Example 9 was significantly improved as compared to the adhesion retention ratio of the single-sided adhesive tape obtained in Example 8.
- a resin foam which is flexible and excellent in formability
- a resin foam sheet made of the resin foam
- an adhesive tape a member for vehicles and a building member.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Building Environments (AREA)
Abstract
Description
しかしながら、従来の樹脂発泡体は、必要形状に賦型しようとすると破断しやすく、賦形性に劣るという問題点があった。例えば、従来の樹脂発泡体を板形状に賦型しようとすると、延展により樹脂発泡体に破れ等が発生することがあった。
以下に本発明を詳述する。
上記ポリビニルアセタールは、ポリビニルアルコールをアルデヒドでアセタール化して得られるポリビニルアセタールであれば特に限定されないが、ポリビニルブチラールが好適である。また、必要に応じて2種以上のポリビニルアセタールを併用してもよい。
上記ポリビニルアセタールは、水酸基量の好ましい下限が15モル%、好ましい上限が40モル%である。水酸基量がこの範囲内であると、可塑剤との相溶性が高くなる。
なお、上記アセタール化度及び水酸基量は、例えば、JIS K6728「ポリビニルブチラール試験方法」に準拠して測定できる。
上記ポリビニルアルコールは、通常、ポリ酢酸ビニルを鹸化することにより得られ、鹸化度70~99.8モル%のポリビニルアルコールが一般的に用いられる。上記ポリビニルアルコールの鹸化度は、80~99.8モル%であることが好ましい。
上記ポリビニルアルコールの重合度の好ましい下限は500、好ましい上限は4000である。上記ポリビニルアルコールの重合度が500以上であると、得られる樹脂発泡体の取り扱い性が優れるものとなる。上記ポリビニルアルコールの重合度が4000以下であると、樹脂発泡体の成形が容易になる。上記ポリビニルアルコールの重合度のより好ましい下限は1000、より好ましい上限は3600である。
上記グリコールとしては、例えば、トリエチレングリコール、テトラエチレングリコール、トリプロピレングリコール等が挙げられる。上記一塩基性有機酸としては、例えば、酪酸、イソ酪酸、カプロン酸、2-エチル酪酸、ヘプチル酸、n-オクチル酸、2-エチルヘキシル酸、ペラルゴン酸(n-ノニル酸)、デシル酸等が挙げられる。なかでも、トリエチレングリコールジカプロン酸エステル、トリエチレングリコールジ-2-エチル酪酸エステル、トリエチレングリコールジ-n-オクチル酸エステル、トリエチレングリコールジ-2-エチルヘキシル酸エステル等が好適である。
上記粘着剤としては特に限定されず、例えば、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤等の公知の粘着剤が挙げられる。
本明細書において伸長ひずみとは、シート状に成形した樹脂発泡体に対して、1軸方向に伸長変形を加えたときに、樹脂発泡体に加わった変形の程度を示す値を意味する。上記伸長ひずみが300%以上であることにより、本発明の樹脂発泡体は、優れた耐衝撃性を発揮することができる。上記伸長ひずみは400%以上であることが好ましく、500%以上であることがより好ましい。上記伸長ひずみの上限は特に限定されないが、実質的には800%程度が上限である。
本明細書において50%圧縮応力とは、シート状に成形した樹脂発泡体の厚み方向に50%圧縮したときに、樹脂発泡体にかかる応力を示す値を意味する。50%圧縮応力が70kPa以下であることにより、本発明の樹脂発泡体は、優れた賦形性を発揮することができる。上記50%圧縮応力は30kPa以下であることが好ましく、20kPa以下であることがより好ましい。上記50%圧縮応力の下限は特に限定されないが、実質的には5kPa程度が下限である。
なお、伸長ひずみ、50%圧縮応力は、JIS K 6767に準じる方法により測定することができる。
具体的には例えば、樹脂発泡体の連続気泡率を20%以上とすることが好ましい。連続気泡率を20%以上とすることにより、得られる樹脂発泡体の50%圧縮応力を所期の範囲に調整することができ、極めて高い柔軟性を発揮させることができる。上記連続気泡率が30%以上であることがより好ましく、40%以上であることが更に好ましく、50%以上であることが特に好ましい。上記連続気泡率の上限は特に限定されないが、98%程度が実質的な上限である。
なお、本明細書において連続気泡とは、樹脂発泡体を形成する気泡がお互いにつながっているものを意味する。
また、上記連続気泡率は、寸法測定によって得られる樹脂発泡体の見掛け体積に対する、樹脂発泡体の外部にまで連結している気泡の容積割合で定義され、JIS K7138記載のピクノメータ法などにより測定することができる。
なお、上記平均気泡径は、気泡の断面観察写真より気泡壁部と空隙部とを観察して、空隙部のサイズを測定する方法により測定することができる。
なお、上記気泡の平均アスペクト比は、気泡の断面観察写真より空隙部の長径と短径とを測定してその比を計算する方法により測定することができる。
上記発泡温度は、180℃以上であることが好ましい。180℃以上の温度では、発泡時に上記樹脂組成物が充分に軟化して気泡同士が連通しやすくなるため、連続気泡が発生し易くなるものと考えられる。ポリビニルアセタール以外の樹脂からなる樹脂組成物では、発泡温度を高くしてもこのような連続気泡率の上昇は認められないことから、ポリビニルアセタールと可塑剤とを含有する樹脂組成物に独特の現象のようである。
上記熱分解型発泡剤のうち市販のものとしては、例えば、セルマイクシリーズ(三協化成社製)やビニホールシリーズ、セルラーシリーズ、ネオセルボンシリーズ(以上、永和化成工業社製)等が挙げられる。
本発明の樹脂発泡体からなる樹脂発泡体シートもまた、本発明の1つである。
本発明の樹脂発泡体シートと、該樹脂発泡体シートの少なくとも一方の面に形成された粘着剤層とを有する粘着テープもまた、本発明の1つである。
ただし、本発明の樹脂発泡体シートは可塑剤を含有することから、上記粘着剤層へ可塑剤が移行することにより、粘着力の低下が生じる恐れがある。そこで、上記粘着剤層として、可塑剤耐性の高い粘着剤層を用いることが好ましい。
上記可塑剤耐性の高い粘着剤層としては、例えば、アクリル系重合体(X)、軟化点が140~160℃である粘着付与樹脂(Y)、及び、架橋剤(Z)を含む粘着剤組成物により形成された粘着剤層等が挙げられる。このような粘着剤組成物を用いることで、可塑剤の移行に由来する経時的な粘着力の低下が生じにくくなる。
以下、上記粘着剤組成物を構成する各成分について詳しく説明する。
なお、本明細書において、(メタ)アクリル酸はアクリル酸又はメタクリル酸を示し、(メタ)アクリレートはアクリレート又はメタクリレートを示す。
上記(メタ)アクリル酸アルキルエステルモノマー(b)としては、具体的には例えば、2-エチルヘキシル(メタ)アクリレート、イソオクチル(メタ)アクリレート、イソノニル(メタ)アクリレート、ラウリル(メタ)アクリレート等が挙げられる。
上記(メタ)アクリル酸アルキルエステルモノマー(A)が上記(メタ)アクリル酸アルキルエステルモノマー(b)を含む場合の含有量は、好ましくは20重量%以下、より好ましくは10重量%以下である。
上記カルボキシル基含有モノマー(B)としては、具体的には例えば、(メタ)アクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸等が挙げられる。これらのカルボキシル基含有モノマー(B)は単独で用いてもよく、2種以上を併用してもよい。なかでも、(メタ)アクリル酸が好ましく、アクリル酸がより好ましい。
上記その他のモノマーとしては、例えば、カルボキシル基以外の極性基を含有するモノマー、スチレン、α-メチルスチレン、o-メチルスチレン、及びp-メチルスチレン等のスチレン系モノマー等が挙げられる。
上記重合方法は特に限定されないが、例えば、上記モノマー混合物を重合開始剤の存在下にてラジカル重合させる方法等が挙げられる。より具体的には、溶液重合、乳化重合、懸濁重合、塊状重合等の従来公知の重合方法を採用できる。
上記有機過酸化物系重合開始剤としては、例えば、クメンハイドロパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、オクタノイルパーオキサイド、ステアロイルパーオキサイド、o-クロロベンゾイルパーオキサイド、アセチルパーオキサイド、t-ブチルハイドロパーオキサイド、t-ブチルパーオキシアセテート、t-ブチルパーオキシイソブチレート、3,5,5-トリメチルヘキサノイルパーオキサイド、t-ブチルパーオキシ-2-エチルヘキサノエート又はジ-t-ブチルパーオキサイド等が挙げられる。
上記アゾ系重合開始剤としては、例えば、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、4,4’-アゾビス(4-シアノペンタン酸)、2,2’-アゾビス(2-メチルブチロニトリル)等が挙げられる。
これらの重合開始剤は単独で用いてもよく、2種以上を併用してもよい。なかでも、得られるアクリル系重合体(X)の臭気低減の観点から、ラウロイルパーオキサイド、オクタノイルパーオキサイド、ステアロイルパーオキサイド、3,5,5-トリメチルヘキサノイルパーオキサイドが好ましい。
上記重合開始剤の量は特に限定されないが、上記モノマー混合物100重量部に対して、好ましくは0.01~10重量部、より好ましくは0.05~2重量部程度用いる。
なお、上記粘着付与樹脂(Y)の軟化点は、JIS K2207に準拠して測定することができる。
上記ロジンエステル系粘着付与樹脂としては、不均化ロジンエステル、重合ロジンエステル、水添ロジンエステル、ロジンフェノール系等が挙げられる。
粘着付与樹脂から分子量600以下の成分を除去する方法としては、例えば、粘着付与樹脂を軟化点以上に加熱溶融する方法、水蒸気を吹き込む方法等が挙げられる。
なお、上記粘着付与樹脂の分子量及びその含有量はゲルパーミエーションクロマトグラフィー(GPC)により測定し、ポリスチレン換算値及び面積比により算出できる。
上記架橋剤(Z)としては特に限定されないが、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤又は金属キレート系架橋剤が好ましい。
上記金属キレート系架橋剤としては、具体的には例えば、金属原子がアルミニウム、ジルコニウム、チタニウム、亜鉛、鉄、スズ等であるキレート化合物が挙げられる。なかでも、中心金属がアルミニウムであるアルミニウムキレートが好ましい。市販品としては、川研ファインケミカル株式会社製のアルミキレートA、アルミキレートM等が挙げられる。
上記粘着剤組成物中の架橋剤(Z)の含有量は特に限定されないが、上記アクリル系重合体(X)100重量部に対する好ましい下限は0.005重量部、好ましい上限は5重量部であり、より好ましい下限は0.01重量部、より好ましい上限は1重量部であり、更に好ましい下限は0.02重量部、更に好ましい上限は0.1重量部である。
上記粘着剤組成物には、更に必要に応じて、充填剤、顔料、染料、酸化防止剤等の添加剤を含有してもよい。
上記生活部材としては、例えば、カーペット裏材、カーテン素材、壁紙等の、振動、衝撃、音等の緩和を目的とした部材が挙げられる。
上記電気部材としては、例えば、携帯電話、タブレット、パソコン等の電子部品や、オーディオ、ヘッドフォン、テレビ、冷蔵庫、洗濯機、掃除機等の家電製品等、或いは業務用電気製品において、振動、衝撃、音等の緩和を目的として用いられる部材が挙げられる。
上記その他の用途の部材としては、例えば、室内外運動施設における床、マット、壁等の、追突時の衝撃緩和を目的として用いられる部材が挙げられる。
本発明の樹脂発泡体、樹脂発泡体シート又は粘着テープを用いた車両用部材もまた、本発明の1つである。
本発明の樹脂発泡体、樹脂発泡体シート又は粘着テープを用いた建築部材もまた、本発明の1つである。
より具体的には例えば、自動車等の車両の天井やドアパネル、床板等の鋼板部材に直接貼り付けて用いるデッドニング材や、外装や躯体を構成する鋼板部材と内装の樹脂部材との間に挟んで用いるダンピング材、クッション材等が挙げられる。
より具体的には例えば、ガルバリウム鋼板(登録商標)からなる金属瓦に雨音対策として直接貼り付けるデッドニング材や、住宅床のフローリング材と下地材との間に挟み込んで使用する遮音マット等が挙げられる。
(1)樹脂発泡体の製造
ポリビニルブチラール1(PVB1)100重量部に対して、可塑剤としてトリエチレングリコールジ-2-エチルヘキサノエート(3GO)を40重量部、熱分解型発泡剤としてビニホールAC#3(永和化成工業社製、分解温度208℃)を8重量部、カーボンブラック(東海カーボン社製、シーストSP)を0.8重量部加えて樹脂組成物を得た。得られた樹脂組成物を110℃にてミキシングロールで充分に混練した後、押出機により押出して、シート状体を得た。なお、PVB1は、水酸基の含有率31モル%、アセチル化度0.7モル%、ブチラール化度68.3モル%、平均重合度1800である。
得られたシート状体を、オーブン中、230℃の発泡温度にて熱分解型発泡剤を分解させることにより、シート状の樹脂発泡体(樹脂発泡体シート)を得た。
得られた樹脂発泡体について、JIS K7138に準拠してピクノメータ法により連続気泡率を測定した。また、測定重量と寸法測定によって得られる見掛け体積とから計算する方法により見掛け密度を測定した。
測定用の樹脂発泡体サンプルは縦50mm、横50mm、厚さ4mmにカットして液体窒素に1分間浸した後、カミソリ刃で厚さ方向に平行な面に沿って切断した。
その後、デジタルマイクロスコープ(キーエンス社製、製品名VHX-900)を用いて200倍の拡大写真を撮り、厚さ方向における長さ2mm分の切断面に存在する全ての気泡について気泡径を測定した。
その操作を測定箇所を変えて5回繰り返し、観察された全ての気泡径の平均値を平均気泡径とした。なお、各気泡の気泡径は、観察された気泡に対して内接する内接円を描いた時の直径が最大となる内接円の直径とした。
また、平均気泡径を測定する際に、観察された各気泡に対して内接する楕円を描いた時の長径と短径を測定し、長径の長さを短径の長さで除してアスペクト比を求めた。観察された全ての気泡に対してアスペクト比を求め、得られたアスペクト比の平均値を求めた。
JIS K 6767に準じる方法により、伸長ひずみ及び50%圧縮応力を測定した。
具体的には、JIS K 6251に規定するダンベル状1号形に打ち抜いたサンプルを用いて、万能試験機にて引張速度500mm/分で引張する方法により伸長ひずみを測定した。
また、一辺が50mmの正方形状に切り出したサンプルを積層厚さが25mm以上になるまで積層した積層サンプルを万能試験機にて圧縮速度10mm/分で圧縮する方法により50%圧縮応力を測定した。
熱分解型発泡剤の配合量を表1に示したようにした以外は実施例1と同様にして樹脂発泡体を製造し、伸長ひずみや50%圧縮応力等を測定した。
ポリビニルブチラール1に代えてポリビニルブチラール2(PVB2)を用い、熱分解型発泡剤の配合量を表1に示したようにした以外は実施例1と同様にして樹脂発泡体を製造し、伸長ひずみや50%圧縮応力等を測定した。なお、PVB2は、水酸基の含有率22.0モル%、アセチル化度4.0モル%、ブチラール化度74.0モル%、平均重合度550である。
比較例として市販のポリエチレン発泡体(積水化学工業社製、ソフトロンS、発泡倍率5倍)を準備した。該ポリエチレン発泡体について、実施例1と同様にして伸長ひずみや50%圧縮応力等を測定した。
比較例として市販のポリエチレン発泡体(積水化学工業社製、ソフトロンS、発泡倍率10倍)を準備した。該ポリエチレン発泡体について、実施例1と同様にして伸長ひずみや50%圧縮応力等を測定した。
比較例として市販のポリエチレン発泡体(積水化学工業社製、ソフトロンS、発泡倍率15倍)を準備した。該ポリプロピレン発泡体について、実施例1と同様にして伸長ひずみや50%圧縮応力等を測定した。
比較例として市販のポリウレタン発泡体(日本発条社製、スーパーシートSS-H6、発泡倍率15倍)を準備した。該ポリウレタン発泡体について、実施例1と同様にして伸長ひずみや50%圧縮応力等を測定した。
実施例1~7及び比較例1~4で得た樹脂発泡体について、以下の方法により評価を行った。
結果を表1に示した。
片面に粘着材を塗布した発泡体を、ピッチ32mm、谷深さ9mmのポリカ製波板に波板の山部のみ接触するように乗せ、発泡体の接触していない部分を谷部に押し付けるように延伸して貼り付けた。このとき発泡体に生じるヤブレや局所的な薄肉化の有無を観察した。樹脂発泡体の賦形性について、以下の基準により評価した。
○:ヤブレや薄肉化が見られない
×:ヤブレ、もしくは薄肉化がみられた
波板形状に賦型した発泡体の谷部に、直径1/2インチのSUS玉を1分間静置した。SUS玉を取り除いたときにSUS玉が沈み込んだ痕跡があるか否かを観察した。樹脂発泡体の柔軟性について、以下の基準により評価した。
○:SUS玉の沈み込んだ痕跡が見られた
×:痕跡が確認できなかった
実施例1で得られた樹脂発泡体シートの片面に粘着剤層として、内装部材固定用両面テープ(積水化学工業社製、#5782)を貼り付けて片面粘着テープを得た。
得られた片面粘着テープは、実施例1記載の樹脂発泡体シートの柔軟性と遮音性を維持したまま粘着性を発揮することができた。
(1)アクリル系重合体の製造
反応容器の内に、n-ブチルアクリレート100重量部及びアクリル酸11重量部を導入しモノマー成分を得た。該モノマー成分を酢酸エチルに溶解して、還流点において、重合開始剤としてラウロイルパーオキサイド0.1重量部を添加し、70℃で5時間還流させて、重量平均分子量が72万のアクリル系重合体の溶液を得た。
得られたアクリル系重合体溶液に、アクリル系重合体溶液の不揮発分であるアクリル系重合体100重量部に対して、分子量600以下の成分の含有量が13%である重合ロジンエステル系粘着付与樹脂(軟化点140℃)を6.3重量部、及び、架橋剤として金属キレート系架橋剤であるアルミニウムキレートを0.054重量部となるように加えた。その後、均一に混合して粘着剤組成物を得た。
次いで、得られた該粘着剤組成物を、実施例1で得られた樹脂発泡体シートの片面に塗布した後、120℃で5分乾燥させ、樹脂発泡体シートの片面に厚さ60μmの粘着剤層が積層された片面粘着テープを得た。
得られた片面粘着テープは、実施例1記載の樹脂発泡体シートの柔軟性と遮音性を維持したまま粘着性を発揮することができた。
実施例8、9で得た片面粘着テープについて、以下の方法により評価を行った。
(1)試験体準備
実施例8、9で得られた片面粘着テープを、幅25mm×長さ150mmに切り出し、JIS G4305に規定するSUS304(表面BA仕上げ)に、JIS Z0237に準じて2kgゴムローラーを10mm/秒の速度で1往復させ圧着した。
上記試験体準備で得た片面粘着テープを、23℃、50%RHにて圧着から20分間放置した後、JIS Z0237に準じて、90度剥離試験を試験数3にて実施し、平均値を初期粘着力(N/25mm)とした。なお、剥離速度は300mm/分であった。
上記試験体準備で得た試験体を60℃の雰囲気下で72時間放置し、ついで23℃、50%RHにて30分間放置した後、JIS Z0237に準じ、90度剥離試験を試験数3にて実施し、平均値を経時粘着力(N/25mm)とした。
上記で得られた初期粘着力及び経時粘着力を用いて、以下の式により粘着力維持率(%)を算出した。
粘着力維持率(%)=100×(経時粘着力/初期粘着力)
実施例9で得られた片面粘着テープの粘着力維持率は、実施例8で得られた片面粘着テープの粘着力維持率に比較して、大幅に改善されていた。
Claims (7)
- 多数の気泡を有する樹脂発泡体であって、
ポリビニルアセタールと可塑剤を含有し、伸長ひずみが300%以上、かつ、50%圧縮応力が70kPa以下である
ことを特徴とする樹脂発泡体。 - 伸長ひずみが400%以上、かつ、50%圧縮応力が30kPa以下であることを特徴とする請求項1記載の樹脂発泡体。
- 粘着剤を含有することを特徴とする請求項1又は2記載の樹脂発泡体。
- 請求項1、2又は3記載の樹脂発泡体からなることを特徴とする樹脂発泡体シート。
- 請求項4記載の樹脂発泡体シートと、該樹脂発泡体シートの少なくとも一方の面に形成された粘着剤層とを有することを特徴とする粘着テープ。
- 請求項1、2若しくは3記載の樹脂発泡体、請求項4記載の樹脂発泡体シート、又は、請求項5記載の粘着テープを用いたことを特徴とする車両用部材。
- 請求項1、2若しくは3記載の樹脂発泡体、請求項4記載の樹脂発泡体シート、又は、請求項5記載の粘着テープを用いたことを特徴とする建築部材。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018539162A JP6574907B2 (ja) | 2017-07-07 | 2018-07-05 | 樹脂発泡体、樹脂発泡体シート、粘着テープ、車両用部材及び建築部材 |
US16/628,298 US11414570B2 (en) | 2017-07-07 | 2018-07-05 | Resin foam, resin foam sheet, adhesive tape, vehicle member, and building member |
KR1020197026736A KR20200027460A (ko) | 2017-07-07 | 2018-07-05 | 수지 발포체, 수지 발포체 시트, 점착 테이프, 차량용 부재 및 건축 부재 |
CN201880031753.5A CN110621729A (zh) | 2017-07-07 | 2018-07-05 | 树脂发泡体、树脂发泡体片、粘合带、车辆用构件和建筑构件 |
EP18827512.7A EP3650490A4 (en) | 2017-07-07 | 2018-07-05 | RESIN FOAM, RESIN FOAM FILM, ADHESIVE TAPE, VEHICLE PART AND COMPONENT |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017134168 | 2017-07-07 | ||
JP2017-134168 | 2017-07-07 | ||
JP2017-217412 | 2017-11-10 | ||
JP2017217412 | 2017-11-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019009351A1 true WO2019009351A1 (ja) | 2019-01-10 |
Family
ID=64951002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/025473 WO2019009351A1 (ja) | 2017-07-07 | 2018-07-05 | 樹脂発泡体、樹脂発泡体シート、粘着テープ、車両用部材及び建築部材 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11414570B2 (ja) |
EP (1) | EP3650490A4 (ja) |
JP (2) | JP6574907B2 (ja) |
KR (1) | KR20200027460A (ja) |
CN (1) | CN110621729A (ja) |
TW (1) | TWI763880B (ja) |
WO (1) | WO2019009351A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022172835A1 (ja) * | 2021-02-10 | 2022-08-18 | 積水化学工業株式会社 | 発泡体、積層発泡体、積層体及び住宅用建材 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023111958A1 (en) * | 2021-12-16 | 2023-06-22 | 3M Innovative Properties Company | Adhesive system including a tape with a foam support layer |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6259640A (ja) * | 1985-09-09 | 1987-03-16 | Sekisui Chem Co Ltd | ブチラ−ル樹脂組成物の発泡方法 |
JPH1052268A (ja) * | 1996-05-01 | 1998-02-24 | Kanebo Ltd | 微生物担持体及びその製造方法 |
JP2007536440A (ja) * | 2004-05-06 | 2007-12-13 | コリンズ アンド エイクマン フロアーカバーリングス, インコーポレイテッド | ポリビニルブチラールを含む床の敷物およびそれを作製する方法 |
JP2010100778A (ja) * | 2008-10-27 | 2010-05-06 | Denki Kagaku Kogyo Kk | シート及びその製造方法 |
CN102382406A (zh) * | 2011-11-23 | 2012-03-21 | 郑州大学 | 聚乙烯醇缩丁醛发泡材料 |
WO2013100015A1 (ja) * | 2011-12-28 | 2013-07-04 | 積水化成品工業株式会社 | ポリオレフィン系樹脂発泡シート、その製造方法、及びその用途 |
JP2015052726A (ja) | 2013-09-09 | 2015-03-19 | 東洋ゴム工業株式会社 | 遮音材 |
JP2016079361A (ja) * | 2014-10-22 | 2016-05-16 | Dic株式会社 | 粘着テープ、粘着テープを用いて得られる物品及び物品の解体方法 |
JP2017133002A (ja) * | 2016-01-29 | 2017-08-03 | 日東電工株式会社 | 両面粘着シートおよびその利用 |
WO2018016536A1 (ja) * | 2016-07-20 | 2018-01-25 | 積水化学工業株式会社 | ポリビニルアセタール多孔質体及びポリビニルアセタール不織布 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050249911A1 (en) | 2004-05-06 | 2005-11-10 | C&A Floorcoverings, Inc. | Polyvinyl butyral backed floor covering |
US20080135159A1 (en) * | 2006-12-12 | 2008-06-12 | 3M Innovative Properties Company | Stretch releasing pressure-sensitive adhesive articles and methods of using the same |
JP2015044887A (ja) | 2011-12-28 | 2015-03-12 | 積水化成品工業株式会社 | ポリオレフィン系樹脂発泡シートの製造方法 |
US10626268B2 (en) * | 2012-04-13 | 2020-04-21 | 3M Innovative Properties Company | Pressure sensitive adhesive foams and articles therefrom |
US10344188B2 (en) * | 2015-12-22 | 2019-07-09 | 3M Innovative Properties Company | Acrylic polyvinyl acetal films comprising an adhesive layer |
-
2018
- 2018-07-05 JP JP2018539162A patent/JP6574907B2/ja active Active
- 2018-07-05 WO PCT/JP2018/025473 patent/WO2019009351A1/ja unknown
- 2018-07-05 CN CN201880031753.5A patent/CN110621729A/zh active Pending
- 2018-07-05 EP EP18827512.7A patent/EP3650490A4/en active Pending
- 2018-07-05 KR KR1020197026736A patent/KR20200027460A/ko not_active Application Discontinuation
- 2018-07-05 US US16/628,298 patent/US11414570B2/en active Active
- 2018-07-06 TW TW107123510A patent/TWI763880B/zh active
-
2019
- 2019-08-19 JP JP2019149831A patent/JP2020012112A/ja active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6259640A (ja) * | 1985-09-09 | 1987-03-16 | Sekisui Chem Co Ltd | ブチラ−ル樹脂組成物の発泡方法 |
JPH1052268A (ja) * | 1996-05-01 | 1998-02-24 | Kanebo Ltd | 微生物担持体及びその製造方法 |
JP2007536440A (ja) * | 2004-05-06 | 2007-12-13 | コリンズ アンド エイクマン フロアーカバーリングス, インコーポレイテッド | ポリビニルブチラールを含む床の敷物およびそれを作製する方法 |
JP2010100778A (ja) * | 2008-10-27 | 2010-05-06 | Denki Kagaku Kogyo Kk | シート及びその製造方法 |
CN102382406A (zh) * | 2011-11-23 | 2012-03-21 | 郑州大学 | 聚乙烯醇缩丁醛发泡材料 |
WO2013100015A1 (ja) * | 2011-12-28 | 2013-07-04 | 積水化成品工業株式会社 | ポリオレフィン系樹脂発泡シート、その製造方法、及びその用途 |
JP2015052726A (ja) | 2013-09-09 | 2015-03-19 | 東洋ゴム工業株式会社 | 遮音材 |
JP2016079361A (ja) * | 2014-10-22 | 2016-05-16 | Dic株式会社 | 粘着テープ、粘着テープを用いて得られる物品及び物品の解体方法 |
JP2017133002A (ja) * | 2016-01-29 | 2017-08-03 | 日東電工株式会社 | 両面粘着シートおよびその利用 |
WO2018016536A1 (ja) * | 2016-07-20 | 2018-01-25 | 積水化学工業株式会社 | ポリビニルアセタール多孔質体及びポリビニルアセタール不織布 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3650490A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022172835A1 (ja) * | 2021-02-10 | 2022-08-18 | 積水化学工業株式会社 | 発泡体、積層発泡体、積層体及び住宅用建材 |
Also Published As
Publication number | Publication date |
---|---|
JP2020012112A (ja) | 2020-01-23 |
KR20200027460A (ko) | 2020-03-12 |
EP3650490A4 (en) | 2021-03-17 |
CN110621729A (zh) | 2019-12-27 |
EP3650490A1 (en) | 2020-05-13 |
TW201908382A (zh) | 2019-03-01 |
US20200216719A1 (en) | 2020-07-09 |
TWI763880B (zh) | 2022-05-11 |
JP6574907B2 (ja) | 2019-09-11 |
US11414570B2 (en) | 2022-08-16 |
JPWO2019009351A1 (ja) | 2019-07-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10106708B2 (en) | Rubber-based pressure sensitive adhesive foam | |
KR101947591B1 (ko) | 에폭시화 식물성유를 포함하는 폴리머 중간층 | |
CN103029394A (zh) | 具有含增塑剂的聚乙烯醇缩(正)醛层和含增塑剂聚乙烯醇缩(异)醛层的高强度膜层压体 | |
JP2017501963A (ja) | 合わせガラスのための高流動性ポリマー中間層 | |
JP2016524633A (ja) | アクリルフォーム粘着テープおよびこれを適用したフラットパネルディスプレイ | |
JP6574907B2 (ja) | 樹脂発泡体、樹脂発泡体シート、粘着テープ、車両用部材及び建築部材 | |
WO2009144889A1 (ja) | アクリル系感圧接着テープ又はシート | |
JP2023041841A (ja) | 粘着剤組成物、及び粘着テープ | |
JP6571881B2 (ja) | 樹脂発泡体、樹脂発泡体シート、粘着テープ、車両用部材及び建築部材 | |
TWI753185B (zh) | 樹脂發泡體 | |
JP2008115374A (ja) | アクリル系粘着テープ又はシート、およびその製造方法 | |
JP2018138504A (ja) | 合わせガラス用中間膜、及び合わせガラス | |
WO2019124405A1 (ja) | 両面粘着テープ | |
JP2018176543A (ja) | 光学デバイス用保護層付き充填接合材、及び、光学デバイス用保護層付き充填接合材の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018539162 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18827512 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20197026736 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2018827512 Country of ref document: EP Effective date: 20200207 |