WO2020013258A1 - Feuille absorbant les chocs - Google Patents

Feuille absorbant les chocs Download PDF

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Publication number
WO2020013258A1
WO2020013258A1 PCT/JP2019/027438 JP2019027438W WO2020013258A1 WO 2020013258 A1 WO2020013258 A1 WO 2020013258A1 JP 2019027438 W JP2019027438 W JP 2019027438W WO 2020013258 A1 WO2020013258 A1 WO 2020013258A1
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WO
WIPO (PCT)
Prior art keywords
absorbing sheet
impact
resin layer
meth
foamed resin
Prior art date
Application number
PCT/JP2019/027438
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English (en)
Japanese (ja)
Inventor
彩葉 小栗
康司 谷内
平池　宏至
莉紗 山▲崎▼
篤志 半田
上田　雄大
康晴 永井
Original Assignee
積水化学工業株式会社
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 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to KR1020217000363A priority Critical patent/KR20210031683A/ko
Priority to CN201980045839.8A priority patent/CN112384559A/zh
Priority to JP2019543392A priority patent/JP6917468B2/ja
Publication of WO2020013258A1 publication Critical patent/WO2020013258A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • 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
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to a shock-absorbing sheet, for example, a thin shock-absorbing sheet used for electronic equipment and the like.
  • a display device used for various electronic devices such as a personal computer, a mobile phone, and electronic paper
  • a display device is provided between a glass plate and a display portion forming the surface of the device, and a housing body and a display portion to which the display portion is attached.
  • a shock absorber for absorbing shock and vibration is provided therebetween.
  • electronic devices provided with a display device particularly portable electronic devices, are required to be thin due to space restrictions, and accordingly, it is also required that the shock absorbing material be formed into a thin sheet.
  • a polyolefin resin foam made of a polyolefin resin represented by polyethylene is widely known. It is known that in a polyolefin-based resin foam, shock absorption performance is improved by controlling the flexibility of a foam by controlling the shape of cells to be constant (for example, see Patent Document 1).
  • the impact absorption performance may not be sufficiently improved.
  • the glass constituting the surface of a display may be broken when a relatively large impact force of about several tens to hundreds of MPa is locally applied, but the flexibility of a foam sheet made of a polyolefin resin is controlled.
  • the impact absorbing performance may be reduced.
  • the present invention has excellent shock absorption performance, for example, makes it possible to improve the absorption performance for a relatively large impact force applied locally, and to improve the absorption performance even after repeated impacts are applied. It is an object to provide a shock absorbing sheet.
  • the present inventors have found that the above problem can be solved by increasing the value of tan ⁇ at 13 ° C. of the shock absorbing sheet, and have completed the present invention described below. That is, the present invention provides the following [1] to [13].
  • the porosity (P 0.1 ) of the cross section in the plane direction at a thickness of 0.1 T from one surface of the foamed resin layer is 10 area% or more and 60 area% or less, respectively.
  • the porosity (P 0.1 ), the porosity (P 0.5 ), and the standard deviation (P ⁇ ) with respect to the average porosity obtained from the porosity (P 0.9 ) are from 1.0 to 20;
  • the impact absorbing sheet according to any one of the above [1] to [8].
  • An adhesive tape comprising: the impact absorbing sheet according to any one of [1] to [11]; and an adhesive material provided on at least one surface of the impact absorbing sheet.
  • a display device comprising the impact-absorbing sheet according to any one of [1] to [11] or the adhesive tape according to [12].
  • a shock absorbing sheet having excellent shock absorbing performance can be provided.
  • the shock absorbing sheet of the present invention is a shock absorbing sheet including a foamed resin layer, and has a loss coefficient (tan ⁇ ) at 13 ° C. of 0.5 or more.
  • tan ⁇ loss coefficient
  • the shock absorbing sheet containing the foamed resin layer it is effective to increase the loss coefficient (tan ⁇ ) at 13 ° C. in the evaluation method in Examples in order to enhance the impact-absorbing performance near normal temperature.
  • tan ⁇ at 13 ° C. to 0.5 or more, the impact absorbing performance of the impact absorbing sheet becomes excellent.
  • the shock absorbing sheet is made thinner at a room temperature or inside an electronic device slightly higher than the room temperature due to heat generation of the electronic device or the like, a local shock can be sufficiently absorbed. Further, even after repeated impacts are applied, it becomes easy to maintain good impact absorption performance. On the other hand, if the loss coefficient at 13 ° C. is less than 0.5, the shock absorbing performance becomes insufficient, and it becomes impossible to sufficiently absorb external shocks.
  • the loss coefficient (tan ⁇ ) at 13 ° C. is preferably 0.8 or more, more preferably 1.2 or more, and particularly preferably 1.6 or more, from the viewpoint of further improving the impact absorption performance.
  • the upper limit of the loss coefficient (tan ⁇ ) at 13 ° C. is not particularly limited, but is, for example, 4 and preferably 3.5 from the viewpoint of practicality.
  • the glass transition temperature (Tg), which is the peak temperature of tan ⁇ , is preferably 5 ° C or more and 25 ° C or less.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) is more preferably 7 ° C. or more and 24 ° C. or less, and still more preferably 9 ° C. or more and 18 ° C. or less, from the viewpoint of further improving impact absorption performance.
  • the ratio represented by (tan ⁇ at 13 ° C.) / (Half value width of tan ⁇ [° C.]) (hereinafter, also referred to as “tan ⁇ width ratio”) is preferably 0.03 or more, and 0.05 or more. Is more preferable, and 0.09 or more is further preferable.
  • the upper limit of the tan ⁇ width ratio is not particularly limited, but is usually 0.5, preferably 0.3.
  • the tan ⁇ at 13 ° C., the glass transition temperature (Tg), and the half width of tan ⁇ in the present invention can be adjusted by appropriately changing the resin component constituting the foamed resin layer, for example, as described later.
  • the resin component constituting the foamed resin layer for example, as described later.
  • Tg glass transition temperature
  • the loss coefficient (tan ⁇ ) at 13 ° C., the glass transition temperature (Tg), and the half width of tan ⁇ of the shock absorbing sheet can be measured by the methods described in Examples described later.
  • the shock absorbing sheet preferably has a thickness of 200 ⁇ m or less.
  • the impact-absorbing performance is improved by setting the above-mentioned tan ⁇ at 13 ° C. within a predetermined range. Further, by setting the thickness to 200 ⁇ m or less, it is possible to contribute to a thin and small electronic device.
  • the thickness of the shock absorbing sheet is more preferably 20 ⁇ m or more and 190 ⁇ m or less, and even more preferably 50 ⁇ m or more and 160 ⁇ m or less. By setting the thickness of the shock absorbing sheet to 20 ⁇ m or more, it is possible to prevent so-called bottoming or the like from occurring when an impact is applied to the shock absorbing sheet.
  • the density of the foamed resin layer is preferably 0.3 g / cm 3 or more and 0.8 g / cm 3 or less.
  • the density of impact-absorbing sheet from the viewpoint of further improving the impact absorption performance, more preferably at most 0.45 g / cm 3 or more 0.8g / cm 3, 0.6g / cm 3 or more 0.79 g / cm More preferably, it is 3 or less.
  • the shock absorbing sheet of the present invention preferably has an initial shock absorption of 45% or more, more preferably 50% or more, and even more preferably 52% or more.
  • the initial shock absorption is the initial shock absorption measured by the method described in Examples described later.
  • the foamed resin layer of the present invention may contain hollow particles, and bubbles may be formed by the space inside the hollow particles. Further, the bubbles of the foamed resin layer may be formed by other means, and for example, are preferably formed by a gas mixed in the resin composition. In this case, the air bubbles are voids directly formed in the resin composition constituting the foamed resin layer, and the inner surface of the air bubbles is made of the resin composition. That is, the bubbles of the foamed resin layer are bubbles whose inner walls do not have a shell structure.
  • the gas mixed in the foamed resin layer may be a gas generated from a foaming agent or the like mixed in the resin composition constituting the foamed resin layer, but may be mixed in from outside the resin composition by a mechanical floss method or the like described below. Preferably it is a gas.
  • the distribution of air bubbles in the foamed resin layer is not particularly limited, but it is better to be uniform, having a sufficient amount of air bubbles in the plane direction, and having a uniform air bubble distribution in the thickness direction. Is preferred. If the distribution of bubbles is uniform, external impacts, particularly local impacts, can be sufficiently absorbed.
  • the porosity (P 0.1 ) and the thickness of the cross section in the plane direction at a thickness of 0.1 T from one surface of the foamed resin layer The porosity of the cross section in the plane direction at 0.5T (P 0.5 ) and the porosity of the cross section in the plane direction at 0.9T thickness (P 0.9 ) are respectively 10% by area or more and 60% by area or less. Preferably. When the porosity (P 0.1 ), the porosity (P 0.5 ), and the porosity (P 0.9 ) are within these ranges, sufficient porosity in the plane direction can be obtained at any position in the thickness direction. There will be an amount of air bubbles.
  • the standard deviation (P ⁇ ) with respect to the average porosity obtained from the porosity (P 0.1 ), the porosity (P 0.5 ), and the porosity (P 0.9 ) is 1.0 or more and 20 or less. Is preferred.
  • This standard deviation (P ⁇ ) is an index of the bubble distribution in the thickness direction. When the standard deviation (P ⁇ ) is within the above range, it indicates that the bubble distribution in the thickness direction is uniform.
  • Each of P 0.1 , P 0.5 and P 0.9 is more preferably 15 area% or more and 55 area% or less, and the standard deviation (P ⁇ ) is 2.0 or more. More preferably, it is 15.
  • the porosity and the standard deviation can be determined by the methods described in Examples described later.
  • the resin foam layer may have closed cells, may have open cells, or may have both closed cells and open cells.
  • the hollow particles contained in the foamed resin layer are not particularly limited, and may be hollow inorganic microspheres, may be hollow organic microspheres, and may be hollow organic-inorganic composites. It may be a microsphere.
  • the hollow inorganic microspheres include a glass hollow balloon such as a hollow glass balloon, a metal compound hollow balloon such as a hollow silica balloon and a hollow alumina balloon, and a porcelain hollow balloon such as a hollow ceramic balloon.
  • the hollow organic microsphere include resin hollow balloons such as a hollow acrylic balloon, a hollow vinylidene chloride balloon, a phenol balloon, and an epoxy balloon.
  • the average particle diameter of the hollow particles is not particularly limited as long as it is equal to or less than the thickness of the foamed resin layer, but is preferably 10 ⁇ m to 150 ⁇ m, more preferably 20 ⁇ m to 130 ⁇ m, and more preferably 30 ⁇ m to 100 ⁇ m. Is more preferred. When the average particle diameter of the hollow particles is 10 ⁇ m or more and 150 ⁇ m or less, sufficient impact absorption can be obtained.
  • the average particle size of the hollow particles can be measured, for example, by a laser diffraction method or a low-angle laser light scattering method.
  • the ratio of the average particle diameter of the hollow particles to the thickness of the foamed resin layer is preferably from 0.1 to 0.9, and more preferably from 0.2 to 0.85. preferable.
  • the average particle diameter / thickness is within the above range and the viscosity as described below is within a predetermined range, a part of the hollow particles rises when the foamed resin layer is formed, and the final porosity distribution Can be prevented from becoming non-uniform.
  • the density of the hollow particles is not particularly limited, but is preferably 0.01 g / cm 3 or more and 0.4 g / cm 3 or less, and is preferably 0.02 g / cm 3 or more and 0.3 g / cm 3 or less. More preferred. By setting the density of the hollow particles to be 0.01 g / cm 3 or more and 0.4 g / cm 3 or less, it is possible to prevent the hollow particles from being lifted up when forming a foamed resin layer and to uniformly disperse the particles.
  • the resin constituting the foamed resin layer in the impact absorbing sheet of the present invention examples include an acrylic resin and a thermoplastic elastomer.
  • the resin constituting the foamed resin layer is an acrylic resin
  • the foamed resin layer is an acrylic foamed resin layer.
  • the acrylic resin is a main component of the resin component in the foamed resin layer, and its content is preferably 70% by mass or more based on the total amount of the resin component in the foamed resin layer. It is more preferably at least 90% by mass, most preferably 100% by mass.
  • the impact-absorbing sheet of the present invention is preferably composed of a foamed resin layer alone, but layers other than the foamed resin layer may be provided as long as the effects of the present invention are not impaired.
  • layers other than the foamed resin layer By providing a layer other than the foamed resin layer, light-shielding properties can be imparted, and workability and handleability can be improved.
  • a skin layer may be provided on one side or both sides of the foamed resin layer.
  • the skin layer is, for example, a non-foamed resin layer composed of various resins.
  • the skin layer may be formed of the same type of resin as the resin constituting the foamed resin layer, or may be formed of another resin.
  • the resin forming the skin layer may be a polyolefin resin, a polyester resin, a urethane resin, a polyimide, a polyethylene naphthalate, or the like, other than the acrylic resin and the thermoplastic elastomer, but may be a rubber resin.
  • the skin layer may be a metal foil, a nonwoven fabric, or the like.
  • the thickness of the foamed resin layer is not particularly limited as long as the impact absorbing sheet can exhibit appropriate impact absorbing performance, and is preferably 200 ⁇ m or less, more preferably 20 ⁇ m or more and 180 ⁇ m or less, and 50 ⁇ m or more and 150 ⁇ m or less. Is more preferred.
  • the skin layers only need to have a thickness that does not impair the function of the foamed resin layer, and the thickness of each skin layer may be less than the thickness of the foamed resin layer.
  • the thickness of each skin layer is, for example, about 1 ⁇ m or more and 50 ⁇ m or less.
  • the acrylic resin is an acrylic polymer obtained by polymerizing a monomer component (a) containing an acrylic monomer component.
  • the monomer component (a) may be appropriately adjusted so that the tan ⁇ at 13 ° C. of the impact-absorbing sheet falls within the above range.
  • the monomer component (a) is a monomer component having one vinyl group.
  • the monomer component (a) is not particularly limited, but preferably contains an alkyl (meth) acrylate as an acrylic monomer component. In the present specification, (meth) acrylate represents acrylate or methacrylate, and the same applies to other similar terms.
  • alkyl (meth) acrylate examples include an alkyl (meth) acrylate having a linear or branched alkyl group, and the alkyl group has, for example, 1 to 18, preferably 1 to 14, more preferably 1 to 14 carbon atoms. 1 to 10.
  • alkyl (meth) acrylate monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (
  • the alkyl (meth) acrylate is preferably contained in the monomer component (a) constituting the acrylic polymer in an amount of 45% by mass or more, more preferably 55% by mass or more and 100% by mass or less, More preferably, the content is 65% by mass or more and 100% by mass or less.
  • the monomer component (a) may contain a vinyl-based monomer other than the alkyl (meth) acrylate in addition to the alkyl (meth) acrylate.
  • a vinyl-based monomer other than the alkyl (meth) acrylate examples include a carboxyl group-containing monomer or an anhydride thereof, a hydroxyl group-containing (meth) acryl monomer, a nitrogen-containing vinyl monomer, and a styrene monomer.
  • carboxyl group-containing monomer examples include carboxylic acids having a vinyl group such as (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, and citraconic acid.
  • carboxylic acids having a vinyl group such as (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, and citraconic acid.
  • hydroxyl group-containing (meth) acrylic monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified (meth) acrylate, and polyoxyethylene (meth) acrylate.
  • A) acrylates and hydroxyl-containing (meth) acrylates such as polyoxypropylene (meth) acrylate.
  • nitrogen-containing vinyl monomer examples include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- Propyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dibutyl (meth) Acrylamides such as acrylamide; amino group-containing (meth) acrylic monomers such as aminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; (meth) acrylonitrile; N-vinylpyrrolidone; N-vinylcaprolactam; vinyl Urirora
  • styrene-based monomer examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene and the like.
  • the vinyl monomers other than the alkyl (meth) acrylate may be used alone or in combination of two or more.
  • the vinyl monomer other than the alkyl (meth) acrylate is preferably contained in an amount of 55% by mass or less in the monomer component (a) constituting the acrylic polymer, and is contained in an amount of 0% by mass or more and 45% by mass or less. More preferably, the content is more preferably 0% by mass or more and 35% by mass or less.
  • the monomer component (a) constituting the acrylic polymer preferably contains a monomer (a1) whose homopolymer has a glass transition temperature lower than the glass transition temperature (Tg) of the above-described impact-absorbing sheet.
  • the glass transition temperature of the monomer (a1) is, for example, less than 0 ° C., preferably ⁇ 10 ° C. or lower and ⁇ 80 ° C. or higher.
  • an alkyl (meth) acrylate is preferable.
  • an alkyl (meth) acrylate having a low glass transition temperature of a homopolymer tan ⁇ at 13 ° C.
  • the alkyl (meth) acrylate as the monomer (a1) is more preferably an alkyl acrylate having an alkyl group having 2 to 10 carbon atoms. Specific examples of preferred compounds include ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. And the like.
  • the glass transition temperature of a homopolymer is known, Brand Wrap and E. H. See “Polymer Handbook” edited by Interscience Publishers by Inmargut.
  • the monomer component (a) constituting the acrylic polymer contains, in addition to the monomer (a1), a monomer (a2) having a glass transition temperature of a homopolymer higher than that of the monomer (a1). Is preferred.
  • the glass transition temperature of the monomer (a2) is, for example, 0 ° C or higher, preferably 5 ° C or higher and 145 ° C or lower.
  • an alkyl (meth) acrylate, a carboxyl group-containing monomer or its anhydride, a hydroxyl group-containing (meth) acryl monomer, a nitrogen-containing vinyl monomer, a styrene-based monomer, or the like may be used.
  • alkyl (meth) acrylates, styrene monomers, acrylamides, carboxyl group-containing monomers or anhydrides thereof are more preferred.
  • Preferred specific examples of the monomer (a2) include methyl (meth) acrylate, styrene, isopropyl (meth) acrylamide, and acrylic acid, and more preferably, methyl acrylate and styrene.
  • the amounts of the monomers (a1) and (a2) may be adjusted so that the glass transition temperature of the acrylic polymer is close to 13 ° C.
  • (A1) is contained in an amount of from 20% by mass to 90% by mass
  • the monomer (a2) is contained in an amount of from 10% by mass to 80% by mass. More preferably, the content of the monomer (a1) is 23% by mass to 87% by mass, and the content of the monomer (a2) is 13% by mass to 77% by mass.
  • the acrylic foamed resin layer is made of an acrylic resin composition containing at least one of the monomer component (a) and an acrylic polymer obtained by partially or completely polymerizing the monomer component (a). It is formed.
  • the monomer component (a) is 100 parts by mass
  • the content of the monomer component (a) and the content of the structural unit derived from the monomer component (a) are determined. Means the total amount of
  • the acrylic resin composition includes the hollow particles described above.
  • the hollow particles are as described above, and the content of the hollow particles is preferably 0.5 parts by mass or more and 5 parts by mass or less, more preferably 1 part by mass, per 100 parts by mass of the monomer component (a). It is not less than 3 parts by mass and not more than 3 parts by mass.
  • the acrylic polymer may be crosslinked by a crosslinking agent to have a crosslinked structure.
  • a crosslinker may be blended into the acrylic resin composition.
  • the crosslinking agent include those having two or more vinyl groups, and preferably polyfunctional (meth) acrylates having two or more (meth) acryloyl groups.
  • Such a crosslinking agent is incorporated into the main chain constituted by the monomer component (a), and crosslinks the main chains to form a network.
  • crosslinking agents include hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and tris (2-hydroxyethyl) isocyanate.
  • the content of the crosslinking agent in the acrylic resin composition is not particularly limited, but is preferably 0.1 parts by mass or more and 7 parts by mass or less, and more preferably 0.2 parts by mass with respect to 100 parts by mass of the monomer component (a). It is more preferably at least 5 parts by mass.
  • a photopolymerization initiator is preferably compounded.
  • the acrylic resin composition forms bubbles from hollow particles, it is preferable to form the acrylic resin foam layer by photopolymerization. Therefore, in such a case, the acrylic resin composition may contain a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited.
  • a ketal-based photopolymerization initiator for example, a ketal-based photopolymerization initiator, an ⁇ -hydroxyketone-based photopolymerization initiator, an ⁇ -aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, benzoin Ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, alkylphenone-based photopolymerization initiator, aromatic sulfonyl chloride-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzyl-based Examples thereof include a photopolymerization initiator, a benzophenone-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator.
  • the polymerization initiator can be used alone or in combination of two or more.
  • the use amount of these photopolymerization initiators is not particularly limited, but is preferably from 0.03 to 3 parts by mass, and more preferably from 0.05 to 1 part by mass, per 100 parts by mass of the monomer component (a). More preferably, it is not more than 0.5 parts by mass.
  • a surfactant in addition to the above, a surfactant, a metal harm inhibitor, an antistatic agent, a stabilizer, a nucleating agent, a crosslinking aid, a pigment, a dye, a halogen-based, a phosphorus-based flame retardant, etc.
  • other additives such as fillers may be contained within a range not to impair the object of the present invention.
  • the foamed resin layer may be formed from a resin composition containing a resin component, or a precursor of a resin component that becomes a resin component by curing or the like, hollow particles, and other optional additives.
  • the acrylic foamed resin layer is not particularly limited, but is formed on a suitable support such as a release film or a base material, the monomer component (a) and the hollow particles described above, and optionally, a cross-linking agent.
  • the release film (separator) used for forming the acrylic foamed resin layer may be appropriately peeled off before using the manufactured shock absorbing sheet.
  • the monomer component (a) contained in the acrylic resin composition is preferably partially polymerized.
  • the monomer component (a) generally has a very low viscosity. Therefore, the impact-absorbing sheet of the present invention can be manufactured more efficiently by using an acrylic resin composition which has been partially polymerized (partially polymerized).
  • the acrylic resin composition in which the monomer component (a) is partially polymerized can be produced, for example, as follows. First, the composition containing the monomer component (a) while not containing the hollow particles and the cross-linking agent is partially polymerized by polymerization using active energy rays, whereby a so-called syrup-like curable acrylic is obtained. Prepare a resin material.
  • the viscosity is preferably adjusted to 200 mPa ⁇ s or more and 5000 mPa ⁇ s or less, and more preferably 300 mPa ⁇ s or more and 4000 mPa ⁇ s or less.
  • the viscosity is a viscosity measured at a measuring temperature of 23 ° C. and 100 rpm in a viscosity measurement using a B-type viscometer.
  • the curable acrylic resin material, the hollow particles, the cross-linking agent, and the like are stirred and mixed to prepare an acrylic resin composition in which the hollow particles are dispersed in the curable acrylic resin material.
  • the coating method used when applying the acrylic resin composition is not particularly limited, and an ordinary method can be employed.
  • a coating method include a slot die method, a reverse gravure coating method, a microgravure method, a dip method, a spin coating method, a brush coating method, a roll coating method, and a flexographic printing method.
  • the active energy rays include ⁇ -rays, ⁇ -rays, ⁇ -rays, ionizing radiation such as neutron rays and electron beams, and ultraviolet rays. In particular, ultraviolet rays are preferably used.
  • the irradiation energy of the active energy ray and the irradiation time are not particularly limited as long as the monomer component (a) can be appropriately polymerized.
  • the foamed resin layer may be manufactured using, for example, a resin emulsion as a raw material.
  • the resin emulsion is an aqueous dispersion of various resins.
  • the foamed resin layer is preferably made of an acrylic foamed resin layer as described above, and therefore, the resin emulsion is preferably an acrylic emulsion.
  • the volume average particle size of the acrylic polymer must be smaller than the sheet thickness, and is preferably 100 ⁇ m or less.
  • the average particle size is preferably 5 ⁇ m or less. Furthermore, in order to improve the stability of the foam, the average particle size is preferably 500 nm or less. In addition, the average particle diameter of the resin is preferably 1 ⁇ m or less, and more preferably 300 nm or less, since the foam can be stabilized.
  • the particle size of the resin can be measured as a volume average particle size measured by a particle size distribution analyzer (Nanotrac # 150, manufactured by Microtrac).
  • the acrylic emulsion is an aqueous dispersion of an acrylic resin, and a known one can be used.
  • the acrylic emulsion is prepared by, for example, subjecting the monomer component (a) to emulsion polymerization, suspension polymerization, dispersion polymerization, or the like in the presence of a polymerization initiator, an emulsifier, a dispersion stabilizer, or the like, which is blended as necessary.
  • a polymerization initiator an emulsifier, a dispersion stabilizer, or the like
  • the foamed resin layer can be manufactured by a method described later using an emulsion composition (acrylic resin composition) containing an emulsion such as an acrylic emulsion as a raw material.
  • the emulsion composition contains water as a dispersion medium.
  • a polar solvent such as methyl alcohol, ethyl alcohol, and isopropyl alcohol may be contained.
  • the emulsion composition may contain a foaming agent comprising a surfactant or the like, a crosslinking agent, and the like, if necessary.
  • the solid content of the emulsion composition is, for example, 30% by mass or more and 70% by mass or less, and more preferably 35% by mass or more and 60% by mass or less.
  • bubbles are formed by mixing a gas, and a foamed resin layer can be produced by forming the emulsion composition in which the bubbles are formed into a layer.
  • the gas is preferably mixed into the emulsion composition by a mechanical floss method.
  • the emulsion composition is stirred by a stirring blade or the like to mix air or gas in the atmosphere, and the supply may be a continuous type or a batch type.
  • nitrogen, air, carbon dioxide, argon, or the like can be used.
  • the mixing amount of the gas may be appropriately adjusted so that the obtained foamed resin layer has the above-described density. Specifically, it is preferable to adjust the stirring time and the mixing ratio with air or gas.
  • the emulsion composition in which the bubbles are formed is then coated on a suitable support such as a release film or a substrate to form a coating layer, and the layer is heated and dried to form a foamed resin layer.
  • a suitable support such as a release film or a substrate
  • the heating temperature is not particularly limited, but is preferably 45 to 155 ° C, more preferably 50 to 150 ° C.
  • the viscosity of the emulsion composition in which bubbles are formed is preferably adjusted to 1000 mPa ⁇ s or more and 50000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or more to 45000 mPa ⁇ s or less.
  • the viscosity of the emulsion composition can be adjusted by the stirring time when mixing the gas, the mixing amount of the gas, the solid content of the emulsion composition, and the like. Specifically, it is possible to increase the viscosity by extending the stirring time, increasing the amount of mixing, increasing the amount of solid content, and the like.
  • the skin layer is formed by applying a resin material for forming the skin layer to the foamed resin layer and drying it as necessary. Good to do. Further, the skin layer may be formed by laminating a resin layer on one side or both sides of the foamed resin layer.
  • the impact-absorbing sheet of the present invention is used, for example, for various electronic devices, preferably portable electronic devices such as notebook personal computers, mobile phones, electronic paper, digital cameras, and video cameras. More specifically, it is used as a shock absorbing sheet for a display device (display) provided in these electronic devices.
  • the display device include an organic EL display device and a liquid crystal display device, and an organic EL display device is preferable.
  • the display device in particular, the organic EL display device is a flexible display.
  • the organic EL display device is flexible by forming an organic EL element including both electrodes, a light emitting layer formed between the two electrodes, and a sealing material for sealing the light emitting layer on a film substrate. It can be a display.
  • the shock absorbing sheet When used in a display device, the shock absorbing sheet is disposed on the back side of various display devices to absorb a shock applied to the display device.
  • the back surface of the display device is a surface opposite to a surface on which an image of the display device is displayed. More specifically, the shock absorbing sheet is placed, for example, on a housing of an electronic device, and is disposed between the housing and the display device.
  • the shock absorbing sheet is usually arranged in a compressed state between components constituting an electronic device such as a housing and the display device. Since the shock absorbing sheet of the present invention has high shock absorbing performance even when it is thin, it is possible to appropriately prevent breakage of the display device while reducing the thickness of the electronic device. In addition, even when a relatively large impact is locally applied, the impact absorbing sheet can appropriately absorb the impact, so that a display defect or the like generated in a flexible display is appropriately prevented. Becomes possible.
  • the shock absorbing sheet may be provided with an adhesive material on one surface or both surfaces and used as an adhesive tape.
  • the pressure-sensitive adhesive tape includes a shock-absorbing sheet and a pressure-sensitive adhesive provided on at least one surface of the shock-absorbing sheet.
  • the pressure-sensitive adhesive may be at least provided with a pressure-sensitive adhesive layer, and may be composed of a single pressure-sensitive adhesive layer laminated on the surface of the shock-absorbing sheet, or may be a double-sided pressure-sensitive adhesive stuck to the surface of the shock-absorbing sheet It may be a sheet, but is preferably a single pressure-sensitive adhesive layer.
  • the double-sided pressure-sensitive adhesive sheet includes a substrate and pressure-sensitive adhesive layers provided on both sides of the substrate.
  • the double-sided pressure-sensitive adhesive sheet is used for bonding one pressure-sensitive adhesive layer to the shock absorbing sheet and bonding the other pressure-sensitive adhesive layer to another component.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or the like can be used.
  • the thickness of the adhesive is preferably 5 to 200 ⁇ m, more preferably 7 to 150 ⁇ m.
  • a release sheet such as release paper may be further adhered on the adhesive, and the adhesive layer may be protected by the release paper before use.
  • the shock absorbing sheet was affixed to a PET film having a thickness of 50 ⁇ m, cut out in a size of 3 mm in width and 15 mm in length, and three-dimensionally measured by an X-ray CT apparatus.
  • the X-ray CT apparatus is not particularly limited, but in this example, TDM1000H-II (2K) manufactured by Yamato Scientific Co., Ltd. was used. The resolution is about 1.5 ⁇ m / 1 pixel.
  • a reference plane of the PET film and the boundary surface of the impact-absorbing sheet was counted total number S T of the cross-sectional image that exists in a direction perpendicular (thickness direction) to the surface.
  • the cross-sectional images existing in the thickness direction were from the image of the boundary surface (reference surface) between the PET film and the shock absorbing sheet to the last image of the opposite surface of the shock absorbing sheet.
  • S T th cross-sectional image performs binarization processing using an image processing software "Avizo9.2.0" (FEI Co.) to separate the gap portion and the resin portion.
  • the ratio of the area of the void portion to the entire area of the image was calculated and defined as the void ratio (P 0.1 ) of the cross section in the plane direction at a thickness of 0.1T.
  • 0.1 S T is not an integer obtained by rounding off the first decimal place.
  • the same operation was performed for the porosity of the cross section in the plane direction (P 0.5 ) at the thickness of 0.5 T and the porosity of the cross section in the plane direction at the thickness of 0.9 T (P 0.9 ).
  • the average porosity was calculated from the calculated porosity (P 0.1 ), the porosity (P 0.5 ), and the porosity (P 0.9 ), and the standard deviation (P ⁇ ) was calculated. .
  • Measuring apparatus Using DVA-200 (manufactured by IT Measurement Control Co., Ltd.), shear mode: 1 Hz, strain: 0.08%, temperature range: -50 ° C to 100 ° C, heating rate: 5 ° C / min.
  • tan ⁇ at 13 ° C. and the temperature at which tan ⁇ reached a peak value were determined.
  • the temperature at which tan ⁇ reached the peak value was defined as the glass transition temperature Tg.
  • the value of tan ⁇ was plotted, and the temperature width of the peak at half the height of the peak value of tan ⁇ was defined as the half value width of tan ⁇ .
  • the sample size was 10 mm in length, 5 mm in width, and 1 mm in thickness. In each of the examples and comparative examples, the samples were overlapped to have a thickness of about 1 mm.
  • a shock absorbing sheet (50 mm square) was placed on the center of an acrylic plate (100 mm square, 10 mm thick), and an acceleration sensor was attached to the surface on the opposite side of the acrylic plate on which the shock absorbing sheet was placed.
  • the acrylic plate has four corners fixed to the pedestal with bolts having a length of 35 mm, and the acrylic plate is held so that the upper surface of the acrylic plate is at a position 25 mm from the pedestal surface.
  • An iron ball of 13.8 g (diameter 15 mm) was dropped from a height of 100 mm with respect to the center position of the shock absorbing sheet, and the acceleration at the time of collision with the shock absorbing sheet was measured.
  • the same shock-absorbing sheet was not replaced and the same iron ball drop and acceleration measurement were repeated six times, and the average value of the accelerations for all seven times was taken as the acceleration (L 1a ).
  • the average value of the accelerations for all seven times of performing the same iron ball drop and acceleration measurement without placing the shock absorbing sheet on the acrylic plate is defined as acceleration (L 0a ), and the obtained acceleration (L 1a ) and acceleration (L 1a ) are obtained. From L 0a ), the average shock absorption rate of 7 times was calculated by the following equation. The test was performed under the conditions of a temperature of 23 ° C. and a humidity of 50 RH%.
  • Tg represents the glass transition temperature of the homopolymer of each monomer component.
  • 2EHA 2-ethylhexyl acrylate
  • BA n-butyl acrylate
  • EA ethyl acrylate
  • MA methyl acrylate
  • AN acrylonitrile
  • Tg 125 ° C.
  • NIPAM N-isopropylacrylamide
  • AAC acrylic acid
  • MAA methacrylic acid
  • St styrene
  • Tg 100 ° C
  • the components used in the resin compositions of the examples are as follows.
  • Bifunctional crosslinking agent (trade name “NK Ester APG-400”, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Trifunctional cross-linking agent (trade name “NK Ester A-9300-3CL”, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Photoinitiator (trade name "Irgacure 184”, manufactured by BASF Japan Ltd.)
  • Hollow particles A (trade name “EXPANCEL 920DE80d30”, manufactured by Nippon Philite Co., Ltd.), average particle size: 80 ⁇ m
  • Example 1 An aqueous dispersion of an acrylic polymer (average particle size: 120 nm) comprising the monomer component (a) shown in Table 1 and obtained by emulsion polymerization and having a solid content of 50% by mass was prepared.
  • the emulsion composition was stirred for 1.0 minute at a second stage of speed at room temperature using a stirrer (TESCOM 1200), and air was mixed in by a mechanical floss method to form air bubbles.
  • the emulsion composition in which bubbles were formed was applied on release paper, and then heated and dried at 100 ° C. for 5 minutes to obtain an impact-absorbing sheet comprising a foamed resin layer.
  • Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 2 The procedure was performed in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 0.5 minute. Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 3 The procedure was performed in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 1.5 minutes. Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 4 Example 1 was carried out in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 1.0 minute. Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 5 The procedure was performed in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 0.5 minute. Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 6 The procedure was performed in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 1.5 minutes. Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 7 25 parts by mass of butyl acrylate, 75 parts by mass of methyl acrylate, and 0.5 parts by mass of a photoinitiator are mixed, and the mixture is partially polymerized by polymerization using ultraviolet rays to cure a syrup having a viscosity of 2000 mPa ⁇ s.
  • An acrylic resin material was obtained.
  • 2 parts by mass of a bifunctional crosslinking agent, 1 part by mass of a trifunctional crosslinking agent, and 2 parts by mass of hollow particles A were added and mixed to prepare an acrylic resin composition.
  • the obtained acrylic resin composition was applied on release paper, and irradiated with ultraviolet light under the conditions of illuminance: 4 mW / cm 2 and light amount: 720 mJ / cm 2 to obtain a shock absorbing sheet.
  • Table 1 shows the evaluation results of the shock absorbing sheet.
  • the porosity (P 0.1 ), the porosity (P 0.5 ), and the porosity (P 0.9 ) were 22.4%, 50.4%, and 25.25, respectively. 3%, and the standard deviation (P ⁇ ) with respect to the average porosity was 12.6.
  • Example 1 The procedure was performed in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 1.5 minutes. Table 1 shows the evaluation results of the shock absorbing sheet.
  • Example 2 The procedure was performed in the same manner as in Example 1 except that the composition of the monomer component (a) was changed as shown in Table 1 and the stirring time was changed to 1.5 minutes. Table 1 shows the evaluation results of the shock absorbing sheet.
  • the shock absorbing sheets of the examples had higher shock absorbing rates in both the first time and the average of 7 times, and were excellent in the shock absorbing performance, as compared with the comparative examples.

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

Abstract

Cette feuille absorbant les chocs comprend une couche de mousse de résine, et a un coefficient de perte (tanδ) à 13 °C de 0,5 ou plus.
PCT/JP2019/027438 2018-07-11 2019-07-11 Feuille absorbant les chocs WO2020013258A1 (fr)

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JP2020015799A (ja) * 2018-07-24 2020-01-30 株式会社イノアック技術研究所 発泡シート
JPWO2020137576A1 (ja) * 2018-12-26 2021-06-03 Dic株式会社 フレキシブルディスプレイ用発泡体粘着テープ及びフレキシブルディスプレイ積層物
JP2021088685A (ja) * 2019-12-06 2021-06-10 積水化学工業株式会社 衝撃吸収シート
WO2021209833A1 (fr) * 2020-04-17 2021-10-21 3M Innovative Properties Company Feuilles de mousse unitaires antireflet
WO2022130837A1 (fr) * 2020-12-17 2022-06-23 Ａｇｃ株式会社 Feuille absorbant les chocs

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CN113527758A (zh) * 2021-07-20 2021-10-22 湖北祥源新材科技股份有限公司 一种耐冲击泡棉、制备方法以及应用

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WO2021209833A1 (fr) * 2020-04-17 2021-10-21 3M Innovative Properties Company Feuilles de mousse unitaires antireflet
WO2022130837A1 (fr) * 2020-12-17 2022-06-23 Ａｇｃ株式会社 Feuille absorbant les chocs
KR20230121725A (ko) 2020-12-17 2023-08-21 에이지씨 가부시키가이샤 충격 흡수 시트

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CN112384559A (zh) 2021-02-19
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