WO2021049301A1 - Feuille adhésive thermosensible et procédé de production d'un article obtenu par application d'une feuille adhésive thermosensible - Google Patents

Feuille adhésive thermosensible et procédé de production d'un article obtenu par application d'une feuille adhésive thermosensible Download PDF

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WO2021049301A1
WO2021049301A1 PCT/JP2020/032268 JP2020032268W WO2021049301A1 WO 2021049301 A1 WO2021049301 A1 WO 2021049301A1 JP 2020032268 W JP2020032268 W JP 2020032268W WO 2021049301 A1 WO2021049301 A1 WO 2021049301A1
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Prior art keywords
heat
sensitive adhesive
adhesive layer
adhesive sheet
thermoplastic
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PCT/JP2020/032268
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English (en)
Japanese (ja)
Inventor
澄生 下岡
森野　彰規
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Dic株式会社
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Priority to CN202080059699.2A priority Critical patent/CN114286847A/zh
Priority to JP2021545200A priority patent/JP7111260B2/ja
Publication of WO2021049301A1 publication Critical patent/WO2021049301A1/fr

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    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

Definitions

  • the present invention relates to a heat-sensitive adhesive sheet and a method for manufacturing an article to which the heat-sensitive adhesive sheet is attached.
  • the surface of the molded product such as interior and exterior parts of home appliances, mobile terminals, automobiles, etc. is decorated with a colored paint or metal vapor deposition (hereinafter referred to as "decorative layer").
  • a decorative layer or a functional layer (hereinafter referred to as a functional layer) accompanied by metal wiring such as a touch sensor element and an antenna wire is laminated.
  • thermoplastic bonding materials such as polycarbonate resin and acrylic resin are bonded to the surface layers of these decorative layers and functional layers. Will be done.
  • a hard coat layer, a matte layer, an ultraviolet absorbing layer, an antistatic layer and the like can be laminated on the surface of the thermoplastic bonding material, and these layers may cause scratches, ultraviolet deterioration, disconnection due to charge discharge, etc.
  • the decorative layer and the functional layer can be protected more efficiently from the damage of the above. Further, if the decorative layer and the functional layer are laminated on the back surface side of the thermoplastic bonding material in advance and then bonded to the surface of the molded product, they can be easily laminated as compared with the case where these are directly laminated on the surface of the molded product. It can be performed.
  • thermoplastic laminating material and the molded product for example, only the thermoplastic laminating material is heated at about 90 ° C. to 200 ° C. for about 1 second to 300 seconds to soften it, and then the molding is placed in a reduced pressure space.
  • a pressure molding machine or vacuum forming that strongly presses the surface of an object with compressed air or the like to deform the heated thermoplastic laminating material in a three-dimensional direction and adhere it to the surface of the object so as to follow the shape of the surface of the object.
  • a bonding method using a machine, a TOM molding machine, or the like is used (for example, Patent Document 1).
  • thermoplastic laminating material above the temperature at which the adhesiveness occurs and laminating it on the surface of the molded product
  • the surface of the thermoplastic laminating material is also softened, and appearance defects such as uneven gloss and waviness are likely to occur. .. Therefore, a method is used in which an adhesive layer is sandwiched between the thermoplastic bonding material and the molded product to lower the heating temperature during molding of the thermoplastic bonding material.
  • a liquid adhesive that cures with stimulating energy such as heat, moisture, or ultraviolet rays
  • a liquid adhesive that cures with heat or humidity it takes about 24 hours from the time when the thermoplastic adhesive is attached to the surface of the molded product to the time when the adhesive is cured.
  • a liquid adhesive that cures with ultraviolet rays the light transmission is hindered by a shield such as a decorative layer on the back surface of the thermoplastic bonding material or an ultraviolet absorbing layer, and the ultraviolet curing is hindered, resulting in insufficient curing. It is easy to occur.
  • the surface repulsive force of the thermoplastic adhesive deformed in the three-dimensional direction causes floating or peeling from the end portion.
  • the liquid adhesive flows out, and the thickness of the adhesive layer is easily changed.
  • the liquid adhesive tends to form bubbles due to the gas generated from the thermoplastic adhesive material by heating. ..
  • thermosetting type or ultraviolet curable type adhesive sheet containing a polymerizable monomer or oligomer component may be used instead of a liquid adhesive.
  • these adhesive sheets are unlikely to float or peel off from the edges, protrude from the bonded material due to flow, or change in thickness, but like the above-mentioned liquid adhesives, they are thermoplasticly bonded.
  • the polymerizable monomer or oligomer component significantly softens the adhesive layer, and the gas generated from the thermoplastic bonding material causes the adhesive sheet to form. There was a problem that bubbles were easily formed.
  • Grooves are provided to release the gas generated from the thermoplastic bonding material or the molded product from the interface of the adhesive layer to the surroundings (for example, Patent Document 3), or fine pores are provided on the surface of the thermoplastic bonding material. If this is the case, these grooves and pores will remain even after the heating and bonding, which is inferior in appearance. Further, in order to suppress the generation of gas from the surface of the thermoplastic bonding material or the molded product after application, a step of preheating these adherends to release the gas is required (for example, Patent Document 4). It was inferior in production efficiency.
  • the liquid adhesive or the adhesive sheet when used, it is highly sticky at room temperature, so that it is difficult to correct the position when attaching it to a laminating device such as a pressure molding machine, a vacuum forming machine, or a TOM molding machine. There is also a problem that dirt or foreign matter adheres to the surface of the adhesive and the appearance after bonding is impaired. Further, when the thermoplastic bonding material is first molded so as to follow the shape of the molded product and then bonded to the surface of the molded product with the liquid adhesive or the adhesive sheet, the stickiness is high at room temperature, so that the bonding position is high. There were also problems such as slippage and mixing of air bubbles at the bonding interface.
  • thermoplastic in applications such as automobiles where it is used in a cold environment of 0 ° C or less, or where cold heat is repeated for home appliances and mobile terminals.
  • the adhesive layer cannot completely alleviate the strain generated by the expansion difference between the laminating material and the molded product, and the thermoplastic laminating material and the molded product tend to float or peel off.
  • JP-A-2015-145103 Japanese Unexamined Patent Publication No. 2015-072343 Japanese Unexamined Patent Publication No. 2011-016258 Japanese Unexamined Patent Publication No. 2014-205335
  • thermoplastic laminating material or the like in the step of heating a thermoplastic laminating material or the like to about 90 ° C. to 200 ° C. and laminating it to the surface of a molded product while deforming it in a three-dimensional direction, the thermoplastic laminating material or the like is bonded. It is possible to realize the adhesion between the thermoplastic bonding material and the molded product by suppressing the formation of bubbles due to the gas that can be generated from the above and the peeling due to the repulsion of the curved surface of the thermoplastic bonding material, and further, these bonding products.
  • thermoplastic binder and the molded product Even if it is left in a hot and humid environment, it suppresses the formation and peeling of bubbles due to the gas that can be generated from at least one of the thermoplastic binder and the molded product, and is used in a cold environment or cold.
  • a heat-sensitive adhesive sheet that can suppress floating and peeling between the thermoplastic bonding material and the molded product, and the thermoplastic bonding material and the molded product using the above-mentioned heat-sensitive adhesive sheet, etc. It is to provide a method of manufacturing an article which makes it possible to realize a bonded article with.
  • the present inventor has found that the above-mentioned problems can be solved by a heat-sensitive adhesive sheet having a heat-sensitive adhesive layer having various tensile elastic moduli and a bonding method using the above-mentioned heat-sensitive adhesive sheet. That is, in the present invention, the peak temperature of tensile loss tangent (tan ⁇ ) measured in the range of ⁇ 50 ° C. to 200 ° C. and at a frequency of 3 Hz is at least one or more at 90 ° C. or higher and at least -20 ° C. or lower. It has one or more and has a heat-sensitive adhesive layer (a) having a tensile storage elasticity (E'a100 ) at 100 ° C.
  • the heat-sensitive adhesive sheet of the present invention uses a specific heat-sensitive adhesive sheet as an adhesive layer for adhering a thermoplastic bonding material or the like to a molded product or the like, so that the thermoplastic bonding material or the like can be heated from 90 ° C. to 90 ° C.
  • the formation of bubbles by the gas that can be generated from the thermoplastic bonding material and the curved surface repulsion of the thermoplastic bonding material etc. It is possible to realize adhesion between a thermoplastic bonding material or the like and a molded product or the like, which suppresses peeling due to the above.
  • thermoplastic bonding material or the molded product or the like can be used from at least one of them. Heat that suppresses the formation and peeling of bubbles due to the gas that can be generated, and suppresses the floating and peeling between the thermoplastic binder and the molded product even if it is used in a cold environment or if cold heat is repeated. It is possible to realize a bonded product of a plastic bonded material or the like and a molded product or the like.
  • the heat-sensitive adhesive sheet of the present invention and the method for manufacturing an article using the same greatly contribute to the manufacture of resin molded products used for the exterior of home appliances, the exterior of mobile terminals, the interior and exterior of automobiles, and the like. be able to.
  • the heat-sensitive adhesive sheet of the present invention has a peak temperature of tensile loss tangent (tan ⁇ ) measured in the range of -50 ° C to 200 ° C and at a frequency of 3 Hz to 90 ° C or higher, at least one or more, and -20 ° C or lower.
  • the thermal adhesive layer (a) having at least one and having a tensile storage elasticity ( E'a100 ) at 100 ° C. of 5 ⁇ 10 5 Pa to 1 ⁇ 10 8 Pa is provided. It provides a thermal adhesive sheet (A) used for adhering a thermoplastic adhesive (B) to the surface of a molded product (C) as an adhesive layer.
  • thermoplastic adhesive layer (a) when the thermoplastic adhesive (B) is heated and attached to the surface of the molded product (C) while being deformed in a three-dimensional direction, the thermoplastic adhesive layer (a) is provided.
  • the thermal adhesive sheet (A) can suppress the formation of bubbles due to the generation of gas from the thermoplastic adhesive (B) and the peeling due to the curved surface repulsion of the thermoplastic adhesive (B), which impairs the appearance. It is possible to obtain a bonded product without any need.
  • thermoplastic bonding material (B) and the molded product (C) are bonded to each other by the heat-sensitive adhesive sheet (A) having the heat-sensitive adhesive layer (a). Even if the mixture is left in a hot and humid environment, it is left in a cold environment by suppressing the formation and peeling of bubbles due to the gas that can be generated from at least one of the thermoplastic adhesive (B) and the molded product (C). It is possible to suppress floating and peeling between the thermoplastic bonding material and the molded product even when the material is repeatedly cooled or cooled.
  • the heat-sensitive adhesive sheet of the present invention has low room temperature adhesiveness due to having predetermined physical properties, so that dust does not easily adhere and reattachment can be easily performed.
  • the heat-sensitive adhesive sheet of the present invention since the heat-sensitive adhesive sheet of the present invention has low room temperature adhesiveness, it can be suitably used for bonding the molded thermoplastic bonding material (B) and the molded product (C). More specifically, the thermoplastic laminating material (B) is preliminarily molded according to the shape of the molded product (C), and the molded thermoplastic laminating material (B) and the molded product (C) are bonded to each other.
  • the molded thermoplastic bonding material (B) may be difficult to fit through the adhesive sheet and may not be sufficiently bonded. is there.
  • the heat-sensitive adhesive sheet of the present invention since the adhesiveness at room temperature is low, it is possible to sufficiently fit and join the molded members to each other.
  • the heat-sensitive adhesive layer (a) and the heat-sensitive adhesive sheet (A) are attached to the thermoplastic bonding material (B) or the molded product (C) at a temperature of 23 ° C. and a relative humidity of 50% RH.
  • a temperature of 23 ° C. and a relative humidity of 50% RH Immediately after, it is defined as 1 N / cm or less, and it is defined that the adhesive strength changes to 5 N / cm or more at a temperature of 23 ° C. and a relative humidity of 50% RH by heating at 90 ° C. to 200 ° C. for about 1 second to 300 seconds. ..
  • heat-sensitive adhesive sheet (A) a sheet composed of a single layer or two or more layers of the heat-sensitive adhesive layer (a) can be used.
  • Thermal adhesive sheet In the heat-sensitive adhesive sheet (A) of the present invention, as an adhesive layer, the peak temperature of tensile loss tangent (tan ⁇ ) measured in the range of ⁇ 50 ° C. to 200 ° C. and at a frequency of 3 Hz is at least 90 ° C. or higher.
  • the thermoplastic adhesive (B) is heated to 90 ° C. to 200 ° C. and attached to the surface of the molded product (C).
  • the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A) enables heat-sensitive adhesion, and the formation of bubbles and thermoplasticity due to the gas that can be generated from the thermoplastic bonding material (B). Peeling of the bonded material (B) due to repulsion of the curved surface can be suppressed, and a bonded product can be obtained without impairing the appearance.
  • the heat-sensitive adhesive layer (a) is a thermoplastic bonding material (B) or a molded product (C) even if the bonded product is left in a high-temperature and high-humidity environment, a cold environment, or a cold environment.
  • the formation of bubbles due to the gas that can be generated from at least one of the above can be suppressed, and the peeling due to the strain generated by the difference in thermal expansion can be suppressed.
  • the heat-sensitive adhesive layer (a) is an adhesive layer of the heat-sensitive adhesive sheet (A) having appropriate hardness and adhesive strength.
  • the peak temperature of the loss tangent which is at least one above 90 ° C., is preferably in the range of 100 ° C. to 150 ° C., more preferably in the range of 110 ° C. to 140 ° C., and 110 ° C. to 130 ° C. It is particularly preferable that the temperature is in the range of.
  • the peak temperature of the loss tangent which is at least one above ⁇ 20 ° C., is preferably in the range of ⁇ 60 ° C. to ⁇ 20 ° C., and more preferably in the range of ⁇ 50 ° C. to ⁇ 25 ° C. It is preferably in the range of ⁇ 40 ° C. to ⁇ 25 ° C., particularly preferably in the range of ⁇ 40 ° C. to ⁇ 25 ° C. Due to the peak temperature in the temperature range, the heat-sensitive adhesive even when the bonded product of the thermoplastic bonding material (B) and the molded product (C) is used in a cold environment or the cold heat is repeated.
  • the layer (a) can maintain appropriate flexibility, and the strain generated by the difference in thermal expansion between the thermoplastic bonding material (B) and the molded product (C) constitutes the heat-sensitive adhesive sheet (A).
  • the heat-sensitive adhesive layer (a) is relaxed, and floating or peeling between the thermoplastic bonding material (B) and the molded product (C) can be suppressed.
  • the tensile storage elastic modulus ( E'a100 ) at 100 ° C. is preferably 1 ⁇ 10 6 Pa to 7 ⁇ 10 7 Pa, more preferably 3 ⁇ 10 6 Pa to 5 ⁇ 10 7 Pa. It is particularly preferably ⁇ 10 6 Pa to 3 ⁇ 10 7 Pa.
  • the thermoplastic adhesive bonding material (B) is heated at 90 ° C. to 200 ° C.
  • a molded product When bonded to C), it becomes a heat-sensitive adhesive layer that has appropriate hardness and adhesiveness, and also forms bubbles due to the gas that can be generated from the thermoplastic bonding material (B) and the thermoplastic bonding material (B). ) Can suppress peeling due to curved surface repulsion. Further, even if the bonded product is left in a hot and humid environment, a cold environment, or a cold environment, the heat-sensitive adhesive sheet (A) having appropriate hardness and adhesive strength capable of suppressing the formation and peeling of bubbles can be adhered. It becomes a drug layer.
  • the loss tangent (tan ⁇ ) of the heat-sensitive adhesive layer (a) at a peak temperature of 90 ° C. or higher is preferably 2.0 or less, more preferably 1.5 or less, and the thermoplastic bonding material (B) is suitable.
  • the heat-sensitive adhesive layer (a) When the heat-sensitive adhesive layer (a) is heat-sensitive and bonded to a softened state, the heat-sensitive adhesive layer (a) obtains appropriate flexibility and heat-sensitively adheres, and bubbles due to gas that can be generated from the thermoplastic bonding material (B) It is particularly preferably in the range of 0.3 to 1.0 in order to suppress the formation and peeling of the thermoplastic bonding material (B) due to the repulsion of the curved surface.
  • the loss tangent (tan ⁇ ) of the heat-sensitive adhesive layer (a) at a peak temperature of ⁇ 20 ° C. or lower is preferably 2.0 or less, more preferably 1.5 or less, and the heat-sensitive adhesive layer (a) has.
  • the bonded product bonded with the constructed heat-sensitive adhesive sheet (A) has a difference in thermal expansion between the thermoplastic bonding material (B) and the molded product (C) even if it is left in a cold environment or a cold environment. It is particularly preferably in the range of 0.3 to 1.0 in order to maintain an appropriate hardness and adhesive strength capable of suppressing peeling due to the generated strain in a low temperature environment.
  • the tensile storage elastic modulus (E'a-20 ) of the heat-sensitive adhesive layer (a) at ⁇ 20 ° C. is preferably 5 ⁇ 10 6 Pa to 3 ⁇ 10 9 Pa, and is preferably 1 ⁇ 10 7 Pa to 9. It is more preferably ⁇ 10 8 Pa, and when the bonded product of the thermoplastic bonding material (B) and the molded product (C) is used in a cold environment or when cold heat is repeated, the thermoplastic bonding material is bonded.
  • the heat-sensitive adhesive layer (a) relaxes the strain generated by the difference in thermal expansion between the material (B) and the molded product (C), and the floating between the thermoplastic bonding material (B) and the molded product (C). It is particularly preferably 3 ⁇ 10 7 Pa to 7 ⁇ 10 8 Pa in order to suppress peeling.
  • the tensile storage elastic modulus (E'a25 ) of the heat-sensitive adhesive layer (a) at 25 ° C. is preferably 1 ⁇ 10 6 Pa to 1 ⁇ 10 9 Pa, and is preferably 5 ⁇ 10 6 Pa to 7 ⁇ 10 8. Pa is more preferable, and it is easy to correct the position when the thermoplastic laminating material is attached to the pneumatic molding machine, the vacuum forming machine, the TOM molding machine, etc. at room temperature, and the thermoplastic laminating material (B). ) And the molded product (C) are left at a rapid temperature from room temperature to a cold environment, or when cold heat is repeated, 1 ⁇ 10 7 Pa to 5 ⁇ and more preferably 10 8 Pa.
  • the tensile storage elastic modulus (E'a150 ) of the heat-sensitive adhesive layer (a) at 150 ° C. is preferably 1 ⁇ 10 5 Pa to 1 ⁇ 10 7 Pa, and is preferably 1 ⁇ 10 5 Pa to 7 ⁇ . 10 6 Pa is more preferable, and when the thermoplastic bonding material (B) is heated at 90 ° C. to 200 ° C. for about 1 second to 300 seconds and bonded to the molded product (C), it has appropriate hardness and adhesiveness.
  • tensile storage elastic modulus and loss tangent (tan ⁇ )
  • a viscoelasticity tester manufactured by TA Instruments Japan, trade name: RSA III
  • the tensile storage elastic modulus (E') and the loss tangent (tan ⁇ ) are measured in the temperature range of ⁇ 50 ° C. to 200 ° C. under the conditions of 0 Hz and a heating rate of 5 ° C./min.
  • the test piece used in the above measurement after laminating the heat-sensitive adhesive layer (a) from 400 ⁇ m to 600 ⁇ m, the width is 5 mm and the length of the measuring portion is 20 mm, and the lengths of the handles at both ends are set. Use a rectangular piece cut to 20 mm.
  • the heat-sensitive adhesive layer (a) is formed of an adhesive composition, and for example, a solution of the adhesive composition in which the adhesive composition described later is dissolved in an organic solvent or the like is applied to the surface of a release liner or the like and dried. It can be manufactured by equalizing.
  • the adhesive composition is not particularly limited as long as it can have the above-mentioned physical properties, but for example, a polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower and glass having a glass transition temperature of 90 ° C. or higher.
  • An adhesive composition containing a block copolymer having a polymer block (S2) having a transition temperature can be preferably used. More specifically, a (meth) acrylic triblock copolymer or a vinyl aromatic triblock copolymer represented by the formula: S2-S1-S2 (a single amount of diene conjugated with an aromatic vinyl monomer).
  • a triblock copolymer (triblock copolymer composed of a body) or the like, or a (meth) acrylic diblock copolymer or a vinyl aromatic diblock copolymer (fragrance) represented by the formula: S1-S2.
  • An adhesive composition containing a diblock copolymer (diblock copolymer composed of a group vinyl monomer and a conjugated diene monomer) or the like can be used. Above all, in order to suppress the formation and peeling of bubbles, it is preferable to use an adhesive composition containing a triblock copolymer represented by the formula: S2-S1-S2.
  • the polymer blocks (S1) and the polymer blocks (S2) form a domain.
  • the heat-sensitive adhesive sheet (A) is used as an adhesive layer, and the thermoplastic bonding material (B) is heated and bonded to the surface of the molded product (C) while being deformed in a three-dimensional direction.
  • the domain of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher contained in the heat-sensitive adhesive layer (a) forms bubbles due to the gas that can be generated from the thermoplastic bonding material (B).
  • thermoplastic adhesive (B) is suppressed from peeling due to curved surface repulsion, and even if the adhesive is left in a high temperature and high humidity environment, it can be removed from at least one of the thermoplastic adhesive (B) and the molded product (C). Suppresses the formation and peeling of bubbles due to the gas that can be generated.
  • the domain of the polymer block (S1) contained in the heat-sensitive adhesive layer (a) and having a glass transition temperature of ⁇ 20 ° C. or lower makes the thermoplastic binder (B) 90 ° C. to 200 ° C.
  • the heat-sensitive adhesiveness is enhanced when the bonded product is bonded to the molded product (C) by heating for about 1 to 300 seconds. , The strain due to the difference in thermal expansion between the thermoplastic bonding material (B) and the molded product (C) is alleviated, and the floating and peeling between the thermoplastic bonding material (B) and the molded product (C) are suppressed. ..
  • the glass transition temperature of the polymer block (S1) and the polymer block (S2) of the block copolymer is shown in the curve obtained by analyzing the copolymer resin with a differential scanning calorimeter (DSC). It is the extrapolation start temperature of the transition region of S1) and the polymer block (S2).
  • the polymer block (S2) having a glass transition temperature of 90 ° C. or higher constitutes the copolymer.
  • examples include a polymer block composed of a methacrylic acid ester such as methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and phenyl methacrylate; and an acrylic acid ester such as isobornyl acrylate. These may be used alone or in combination of two or more to form a polymer block (S2).
  • thermoplastic adhesive (B) it is easy to adjust to the predetermined viscoelastic range, suppresses the formation of bubbles and peeling due to the repulsion of the curved surface of the thermoplastic adhesive (B), and the adhesive is left in a high temperature and high humidity environment. Since it is easy to suppress the formation and peeling of bubbles, and the heat-sensitive adhesive layer (a) is excellent in moldability and heat-sensitive adhesiveness, it is more possible to form a polymer block (S2) using methyl methacrylate. preferable.
  • Examples of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or higher, which constitutes the (meth) acrylic block copolymer, include n-lauryl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, and methacrylic acid.
  • Methacrylic acid esters such as stearyl and 2-ethoxyethyl methacrylate; ethylacrylic acid, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, acrylate
  • Examples thereof include polymer blocks such as isoamyl, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, and acrylate esters such as 2-methoxyethyl acrylate.
  • a polymer block (S1) may be used alone or in combination of two or more to form a polymer block (S1). Among these, it is easy to adjust to the predetermined viscoelastic range, it is easy to alleviate the strain due to the difference in thermal expansion when the bonded product is used in a cold environment or when cold heat is repeated, and heat sensitivity. Since the adhesive layer (a) has excellent heat-sensitive adhesiveness, a polymer block (S1) is formed using any one of ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. Is preferable.
  • the glass transition point may be obtained by any method, and a measurement method based on the plastic transition temperature measurement method (JIS K7121-1987) using a differential thermal analysis method or a differential scanning calorimetry method is used. Is preferable.
  • the glass transition temperature of the polymer block (S2) is preferably in the range of 90 ° C. to 150 ° C., more preferably 100 ° C. to 130 ° C., and the formation of bubbles by the gas that can be generated from the thermoplastic bonding material (B). It suppresses peeling due to curved surface repulsion of the thermoplastic bonding material (B), and is generated from at least one of the thermoplastic bonding material (B) and the molded product (C) even if the bonded material is left in a high temperature and high humidity environment.
  • the temperature of 100 ° C. to 120 ° C. is most preferable in order to suppress the formation and peeling of bubbles due to the possible gas.
  • the glass transition temperature of the polymer block (S1) is preferably in the range of ⁇ 90 ° C. to ⁇ 20 ° C., more preferably ⁇ 70 ° C. to ⁇ 30 ° C., and the thermoplastic binder (B) is in the range of 90 ° C. to ⁇ 30 ° C.
  • the bonded product When the bonded product is used in a cold environment or when cold heat is repeated, it enhances the heat-sensitive adhesiveness when the bonded product is bonded to the molded product (C) by heating at 200 ° C. for about 1 to 300 seconds.
  • the temperature is most preferably ⁇ 60 ° C. to ⁇ 40 ° C.
  • the (meth) acrylic block copolymer may have other polymer blocks in addition to the polymer blocks (S1) and (S2).
  • Other polymer blocks include, for example, methacrylic acid, acrylic acid, methacrylonitrile, acrylonitrile, vinyl acetate, styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, ethylene, propylene, butadiene, isobutene, isoprene.
  • an acid group such as methacrylic acid or acrylic acid is used to prevent corrosion or discoloration of the metal layer. It is preferable that the polymer block composed of the contained monomer is not contained in the (meth) acrylic block copolymer.
  • the (meth) acrylic block copolymer has a crosslinkable functional group in order to improve the cohesive force, and may be crosslinked with a crosslinking agent.
  • the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, and the like. If the crosslinkable functional group has a hydroxyl group, a crosslinker such as a polyfunctional isocyanate compound, and if it has a carboxyl group, a crosslinker such as a polyfunctional epoxy compound or a glycidyl group. If it is possessed, a cross-linking agent such as an amine compound, an acid anhydride or a polyfunctional thiol can be used.
  • the content of the crosslinkable functional group is preferably 1,000 equivalents to 100,000 equivalents, preferably 3,000 equivalents to 50,000 equivalents, and 5,000 equivalents to the appropriate viscoelastic range. 20,000 equivalents are particularly preferred.
  • the heat-sensitive adhesive layer (a) comes into contact with a decorative layer on which metal is vapor-deposited or a functional layer accompanied by metal wiring or the like, it has a hydroxyl group as a crosslinkable functional group in order to prevent corrosion or discoloration of the metal layer.
  • the glass transitions to 90 ° C. or higher.
  • the polymer block (S2) having a temperature include a polymer block composed of aromatic vinyl monomer units, and for example, a polymer composed of styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene and the like. Blocks can be mentioned. These may be used alone or in combination of two or more.
  • thermoplastic adhesive (B) it is easy to adjust to the predetermined viscoelastic range, suppresses the formation of bubbles and peeling due to the repulsion of the curved surface of the thermoplastic adhesive (B), and the adhesive is left in a high temperature and high humidity environment. It is preferable to form the polymer block (S2) using styrene because it is easy to suppress the formation and peeling of bubbles and the heat-sensitive adhesive layer (a) is excellent in moldability and heat-sensitive adhesiveness.
  • Examples include polymer blocks composed of body units, and examples thereof include unsaturated hydrocarbons such as butadiene, isobutene, and isoprene, and hydrogenated products thereof.
  • a polymer block (S1) is formed by using a hydrogenated additive of any unsaturated hydrocarbon selected from the group consisting of butadiene, isobutene and isoprene. It is preferable to do so.
  • the weight average molecular weight of the block copolymer is not particularly limited, but is preferably in the range of 10,000 to 500,000, more preferably in the range of 50,000 to 200,000, and is a heat-sensitive adhesive layer (a). ) Is particularly preferably 70,000 to 120,000 in order to obtain transparency and moldability. Within the above range, when the thermoplastic bonding material (B) is heated and bonded to the molded product (C), the heat-sensitive adhesive layer (a) obtains appropriate flexibility and has heat-sensitive adhesiveness.
  • the polymer block (S1) and the polymer block (S2) can be easily domain-formed, and bubbles can be formed by the gas that can be generated from the thermoplastic bonding material (B) and the thermoplastic bonding material (B).
  • the weight average molecular weight indicates a value measured under the following conditions by a gel permeation chromatography (GPC) method.
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40 ° C Eluent: tetrahydrofuran (THF) Flow velocity: 1.0 mL / min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the block copolymer is preferably 29% by mass to 49% by mass, more preferably 33% by mass to 46% by mass, and 36% by mass. % To 42% by mass is particularly preferable.
  • the heat-sensitive adhesive layer (a) softens when the thermoplastic bonding material (B) is heated and bonded to the molded product (C).
  • thermoplastic bonding material (B) Because it is too much, the formation of bubbles due to the gas that can be generated from the thermoplastic bonding material (B) and the peeling due to the curved surface repulsion of the thermoplastic bonding material (B) are likely to occur, and the bonded material is placed in a high temperature and high humidity environment. When left unattended, the formation and peeling of bubbles due to the gas that can be generated from at least one of the thermoplastic bonding material (B) and the molded product (C) are likely to occur. Further, when the polymer block (S2) is more than 49% by mass, the heat-sensitive adhesiveness of the heat-sensitive adhesive layer (a) is insufficient, and the bonded product is used in a cold environment or the cold heat is generated.
  • the content of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower in the block copolymer is preferably 51% by mass to 71% by mass, more preferably 54% by mass to 67% by mass, 58. Mass% to 64% by mass is particularly preferable.
  • the thermal adhesive layer (a) is softened when the thermoplastic adhesive (B) is heated and bonded to the molded product (C). Insufficient, the heat-sensitive adhesiveness of the heat-sensitive adhesive layer (a) is insufficient, and when the bonded product is used in a cold environment or the cold heat is repeated, it becomes insufficient with the thermoplastic bonding material (B).
  • Distortion due to the difference in thermal expansion with the molded product (C) cannot be relaxed, and floating or peeling between the thermoplastic bonding material (B) and the molded product (C) is likely to occur.
  • the polymer block (S1) is more than 71% by mass, bubbles may be formed by the gas generated from the thermoplastic bonding material (B) and the thermoplastic bonding material (B) may be peeled off due to curved surface repulsion. Is likely to occur, and when the bonded product is left in a high temperature and high humidity environment, bubbles may be formed or peeled off due to a gas that may be generated from at least one of the thermoplastic bonded material (B) and the molded product (C). It is more likely to occur.
  • the block copolymer contained in the adhesive composition may be one kind of block copolymer, or a mixture of two or more kinds of block copolymers having different content of polymer blocks. May be good.
  • the content of the polymer block (S1) or (S2) when two or more types of block copolymers are contained is the content of the polymer blocks (S1) or (S2) in each block copolymer.
  • the content of the polymer block (S1) or (S2) of the mixture of two types of block copolymers (F) and the block copolymer (G) is, for example, the block copolymer (F) and the block copolymer (G). It is calculated by the following formula (1) from the content of the polymer blocks (S1) or (S2) of the block copolymers of the polymers (F) and (G), respectively.
  • the absolute value of the content rate difference between the block copolymers (S1) and (S2) determines the formation of domains.
  • it is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
  • the size of the domain of the polymer block (S2) of the block copolymer contained in the adhesive composition formed on the surface or inside of the heat-sensitive adhesive layer (a) is determined by the thermoplastic binder (B). ) Suppresses the formation of bubbles due to the gas that can be generated from) and the peeling of the thermoplastic adhesive (B) due to the repulsion of the curved surface, and even if the adhesive is left in a hot and humid environment, the thermoplastic adhesive (B) ) Or the formation and peeling of bubbles due to the gas that can be generated from at least one of the molded product (C), when used in a cold environment, or when cold heat is repeated, the thermoplastic adhesive (B) In order to suppress floating and peeling due to strain due to the difference in thermal expansion from the molded product (C), it is preferable to form a relatively large domain, and the length of the long side of the domain of the polymer block (S2) is 160 nm or more on average.
  • a strip-shaped structure such as a cylinder or a lamella having a long side length of 160 nm or more on average.
  • the size of the domain is arbitrary for the image of the separated phase obtained by scanning the surface or cross section of the heat-sensitive adhesive layer (a) in the phase mode of a scanning probe microscope (SPM) in a visual field range of 1 ⁇ m. It is an average value obtained by measuring the length of the long side of the polymer block (S2) of the domain of 5 points or more.
  • SPM scanning probe microscope
  • S2 scanning probe microscope
  • “Nano-DST" manufactured by Pacific Nanotechnology can be used for measurement in the close contact mode.
  • the size of the domain of the polymer block (S2) of the block copolymer contained in the adhesive composition is It refers to the size of a domain formed by assembling polymer blocks (S2) of block copolymers forming the above mixture.
  • a block copolymer X in which the adhesive composition has a polymer block (S1x) and a polymer block (S2x) and a block copolymer Y having a polymer block (S1y) and a polymer block (S2y).
  • the polymer block (S2x) of the block copolymer X and the polymer block (S2y) of the block copolymer X are aggregated on the surface or the inside of the heat-sensitive adhesive layer (a). Since the domain of one type of polymer block (S2) is formed, the length of the long side of the above one type of domain is measured.
  • the method for producing the block copolymer is not particularly limited, and examples thereof include living anionic polymerization disclosed in JP-A-04-246488 and JP-A-2014-08434.
  • the block copolymer may be produced in the presence of an organic solvent.
  • organic solvent examples include ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone, and ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
  • ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone
  • ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
  • the adhesive composition may contain other additives, if necessary.
  • additives examples include silane coupling agents, antioxidants, light stabilizers, rust preventives, thioxic imparting agents, leveling agents, tackifiers, antistatic agents, flame retardants, coloring dyes, and coloring. Pigments and the like can be used. These additives may be used alone or in combination of two or more. Among these, when the bonded product manufactured by the method of the present invention is used for outdoor exposure or being left in a high temperature and high humidity environment, high light resistance and yellowing resistance are required, and light It preferably contains a stabilizer, an antioxidant and the like. Further, in order to further enhance the heat-sensitive adhesiveness, it is preferable to contain a tackifier or the like.
  • the light stabilizer captures radicals generated by photodegradation.
  • a radical scavenger such as a thiol compound, a thioether compound or a hindered amine compound
  • an ultraviolet absorber such as a benzophenone compound or a benzoate compound
  • These light stabilizers may be used alone or in combination of two or more. Among these, it is preferable to use a hindered amine compound from the viewpoint of further improving yellowing resistance.
  • the amount used is 0, based on 100 parts by mass of the total amount of the block copolymer of one or more types, from the viewpoint of further improving light resistance and yellowing resistance. It is preferably in the range of 01 parts by mass to 10 parts by mass, and more preferably in the range of 0.05 parts by mass to 3 parts by mass without impairing the heat-sensitive adhesiveness.
  • the antioxidants include hindered phenol compounds (primary antioxidants) that capture radicals generated by thermal deterioration, phosphorus compounds and sulfur compounds (secondary antioxidants) that decompose peroxides generated by thermal deterioration. Agent) and the like can be used.
  • the amount used is 0.01 part by mass with respect to 100 parts by mass of the total amount of the block copolymer of one or more kinds, from the viewpoint of further improving the antioxidant property.
  • the range is preferably from 10 parts by mass, and more preferably from 0.05 parts by mass to 3 parts by mass without impairing the heat-sensitive adhesiveness.
  • any tackifier resin such as a styrene resin, a rosin resin, a terpene resin, or an aliphatic hydrocarbon resin can be used, and it is easy to adjust to the predetermined viscoelastic range. It is preferable to use a rosin-based resin or a terpene-based resin, and since it is excellent in light resistance and yellowing resistance, it is more preferable to use a hydrogenated rosin-based resin or a terpene-based resin. Use is particularly preferred.
  • the amount used is 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer of one kind or two or more kinds from the viewpoint that the heat-sensitive adhesiveness can be further improved.
  • the range is preferably in the range of 5 parts by mass, and more preferably in the range of 5 parts by mass to 20 parts by mass so as not to impair the suppression of bubble formation when heated.
  • thermoplastic resin may be used in combination with the above-mentioned components as long as the properties are not impaired.
  • thermoplastic resin include urethane-based resins, acrylic-based resins, polyester-based resins, and epoxy-based resins.
  • the resin contains a crosslinkable functional group such as a hydroxyl group, a carboxyl group, or a glycidyl group, and is a crosslinking agent. It is more preferable to use a thermoplastic resin that can be crosslinked with the above.
  • the thermoplastic resin is preferably semi-solid or solid in an atmosphere of 25 ° C., and the weight average molecular weight is preferably in the range of 5,000 to 200,000, preferably in the range of 15,000 to 100,000. Is more preferable.
  • the weight average molecular weight of the thermoplastic resin indicates a value obtained by measuring in the same manner as the weight average molecular weight of the block copolymer.
  • the amount of the thermoplastic resin used is preferably 1 part by mass to 50 parts by mass, and 3 parts by mass to 20 parts by mass, based on 100 parts by mass of the total amount of the one or more block copolymers. This is particularly preferable in order not to reduce the cohesive force of the block copolymer contained in the heat-sensitive adhesive layer (a) and to suppress the formation, floating and peeling of bubbles when heated.
  • the polyolefin resin is preferably an olefin resin such as a polyethylene resin or polypropylene resin having a specific dielectric constant of about 2 to 3, a rubber resin such as an isoprene resin or a butadiene resin, and a composition such as the block copolymer.
  • a part of the side chain may be chlorinated or modified with a carboxylic acid to partially improve the polarity.
  • the inorganic filler it is preferable to use an inorganic filler such as boron nitride, forteslite, cordierite, silica, magnesium oxide, and alumina having a dielectric constant contact of about 10 -4 to 10-5, and the block copolymer. It is more preferable to use silica which has excellent compatibility with the adhesive composition such as the above and can enhance the transparency of the heat-sensitive adhesive layer (a).
  • an inorganic filler such as boron nitride, forteslite, cordierite, silica, magnesium oxide, and alumina having a dielectric constant contact of about 10 -4 to 10-5, and the block copolymer.
  • silica which has excellent compatibility with the adhesive composition such as the above and can enhance the transparency of the heat-sensitive adhesive layer (a).
  • the inorganic filler an arbitrary shape such as spherical or crushed can be used, and in order to enhance compatibility with an adhesive composition such as the block copolymer, a titanate coupling or aluminum is used on the surface.
  • Surface-treated materials such as nate couplings and silane couplings may be used.
  • the particle size of the inorganic filler it is preferable to use one having a 50% particle size distributed under the integrated sieve of less than 10 nm to 50 ⁇ m, more preferably one having a particle size of 10 nm to 20 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m. It is particularly preferable to use one of the above in order to enhance the transparency of the adhesive layer (a) and to achieve both good dispersibility of the inorganic filler and ease of coating.
  • SALD-3100 laser diffraction type particle size distribution measuring instrument manufactured by Shimadzu Corporation, and use a numerical value measured using isopropanol as a dispersion medium. Can be done.
  • the total amount of the polyolefin resin and the inorganic filler used is 1 part to 50 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer of one or more kinds. It is preferable to use parts by mass, and using 5 parts to 20 parts by mass is used in order to suppress the deterioration of the adhesiveness of the heat-sensitive adhesive layer (a) while reducing the dielectric constant contact and the specific dielectric constant of the adhesive sheet. More preferred.
  • the heat-sensitive adhesive sheet (A) used in the method of the present invention is, for example, coated on the surface of a release liner with a solution of the adhesive composition in which the adhesive composition is dissolved in an organic solvent or the like, and dried if necessary. It can be produced by forming the heat-sensitive adhesive layer (a).
  • organic solvent examples include ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone, and ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
  • ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone
  • ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
  • Examples of the method of applying the solution of the adhesive composition to the surface of the release liner include a method of applying using a comma coater, a lip coater, or the like.
  • the drying can be performed using, for example, a dryer set at a temperature of about 80 ° C. to 120 ° C.
  • the release liner examples include paper such as kraft paper, glassin paper, and high-quality paper, resin films such as polyethylene, biaxially stretched polypropylene, extruded polypropylene, and polyethylene terephthalate, and laminated paper in which the paper and the resin film are laminated. It is possible to use a paper that has been sealed with clay, polyvinyl alcohol, or the like, and one or both sides of which have been peeled from a silicone-based compound or the like. In order to enhance the transparency of the heat-sensitive adhesive sheet (A), it is preferable to use a release liner obtained by performing a release treatment on the resin film.
  • release treatment agent for the release liner examples include silicone-based release agents, aminoalkyd-based release agents, silicone-modified aminoalkyd-based release agents, long-chain alkyl-based release agents, and fluorine-based release agents.
  • the thickness of the release liner it is preferable to use one having a thickness of 38 ⁇ m to 150 ⁇ m, and more preferably one having a thickness of 50 ⁇ m to 100 ⁇ m.
  • the smoothness of the surface of the heat-sensitive adhesive layer (a) after drying is improved, the peeling liner is less likely to stretch in the drying process, and the curl after winding into a roll is prevented. Can be done.
  • the heat-sensitive adhesive sheet (A) is heated to 90 ° C. to 200 ° C. with the release liner laminated on one side, which will be described later, and the heat-sensitive adhesive of the heat-sensitive adhesive sheet (A) is first obtained.
  • the surface side of the layer (a) and the molded product (C) are pressed and bonded to each other, and after the release liner is peeled off and removed, only the thermoplastic bonding material (B) is heated to 90 ° C to 200 ° C.
  • the bonded product is manufactured through the step of pressurizing and bonding the thermoplastic bonding material (B) and the heat-sensitive adhesive layer (a), polyethylene, biaxially stretched polypropylene, extruded polypropylene, etc. It is more preferable to use a release liner based on a thermoplastic resin having a low softening temperature and easy heating and stretching.
  • the heat-sensitive adhesive sheet (A) may be sandwiched by another arbitrary release liner until it is used in the bonding process. It is preferable to use a peeling liner having different peeling forces on both sides in order to prevent the adhesive sheet from crying when the peeling liner is peeled off again after being sandwiched. Since the heat-sensitive adhesive layer (a) has poor pressure-sensitive adhesiveness at room temperature, floating is likely to occur when the heat-sensitive adhesive sheet (A) is rolled into a roll shape, and at least one surface is double-peeled with a peeling control agent or the like.
  • a silicone-based release agent or a release liner coated with a non-silicone-based release agent such as an aminoalkyd-based release agent, a silicone-modified aminoalkyd-based resin, or a long-chain alkyl-based resin.
  • the thickness of the heat-sensitive adhesive layer (a) it is preferable to use one having a thickness of 10 ⁇ m to 300 ⁇ m, more preferably one having a thickness of 25 ⁇ m to 250 ⁇ m, and a thickness of 50 ⁇ m to 200 ⁇ m. It is particularly preferable to use the one that is the same.
  • two or more heat-sensitive adhesive layers (a) may be laminated. When two or more heat-sensitive adhesive layers (a) are laminated, two or more heat-sensitive adhesive layers (a) having different compositions may be laminated as long as they satisfy the viscoelasticity in the predetermined range.
  • the adhesiveness is poor at room temperature. Therefore, the adhesive surfaces of the heat-sensitive adhesive layers (a) laminated on the release liner are heated to 90 ° C. or higher.
  • the method of heat-bonding while passing through the gap between the rotating rubber roller and metal roller, and the adhesive surfaces of the heat-sensitive adhesive layer (a) laminated on the release liner are temporarily bonded together at room temperature so that air bubbles do not enter. Then, it is preferable to use a method of laminating two or more layers of the heat-sensitive adhesive layer (a) by heating and curing for 24 hours or more in an atmosphere of 50 ° C. or higher.
  • the heat-sensitive adhesive sheet (A) may have a structure in which the heat-sensitive adhesive layer (a) is laminated on both surfaces of the base material.
  • the handleability of the heat-sensitive adhesive sheet (A) is improved, and the protrusion and chipping of the heat-sensitive adhesive layer (a) are reduced during cutting. It is preferable to obtain excellent dimensional stability.
  • any film or mesh material such as polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, polystyrene, etc. can be used, and the transparency and heat-stretchability can be improved.
  • the use of excellent polyethylene terephthalate, polypropylene, polyethylene, polystyrene is particularly preferred.
  • the base material preferably has a thickness of about 1/2 or less of the total thickness of the heat-sensitive adhesive sheet (A), and the thickness is 1 ⁇ m to 50 ⁇ m. It is preferable to use one having a thickness of 2 ⁇ m to 25 ⁇ m, and it is more preferable to use one having a thickness of 2 ⁇ m to 25 ⁇ m.
  • the heat-sensitive adhesive layer (a) When the heat-sensitive adhesive layer (a) is laminated on the base material, it is laminated by applying the composition of the heat-sensitive adhesive layer (a) to the surface of the base material, or the adhesiveness is poor at room temperature.
  • the heat-sensitive adhesive layer (a) laminated on the release liner is heat-bonded to the surface of the base material while passing through the gaps between the rotating rubber rollers and metal rollers heated to 90 ° C. or higher. It is preferable to stack a).
  • the heat-sensitive adhesive sheet (A) preferably has a thickness of 10 ⁇ m to 300 ⁇ m, more preferably 25 ⁇ m to 250 ⁇ m, and 50 ⁇ m to 200 ⁇ m. It is particularly preferred to use.
  • the heat-sensitive adhesive sheet (A) having a thickness in the above range has excellent heat-sensitive adhesiveness, and forms bubbles due to gas that can be generated from the thermoplastic bonding material (B) at the time of heat bonding and thermoplastic bonding.
  • the thickness does not include the release liner.
  • the heat-sensitive adhesive sheet (A) having the heat-sensitive adhesive layer (a) has excellent heat-sensitive adhesiveness, and the heat-sensitive adhesive sheet (A) is used as an adhesive layer to form a thermoplastic bonding material (B).
  • the thermoplastic bonding material (B) is formed by the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A). It is possible to suppress the formation of bubbles due to the gas that can be generated and the peeling due to the repulsion of the curved surface of the thermoplastic bonding material (B), and to obtain a bonded product without impairing the appearance.
  • the bonded product bonded with the heat-sensitive adhesive sheet (A) formed on the heat-sensitive adhesive layer (a) is thermoplastic even when left in a high-temperature and high-humidity environment, a cold environment, or a cold environment. It is possible to suppress the formation of bubbles due to the gas generated from at least one of the bonding material (B) or the molded product (C) and the peeling due to the strain generated due to the difference in thermal expansion.
  • the heat-sensitive adhesive sheet (A) is preferably transparent, and has a light transmittance of 80% or more and a haze of 5.0 or less at a wavelength of 380 nm to 780 nm with the release liner removed from both sides. It is preferable to use one having a light transmittance of 85% or more and a haze of 2.0 or less at a wavelength of 380 nm to 780 nm, and it is more preferable to use a light transmittance of 90% or more at a wavelength of 380 nm to 780 nm. It is particularly preferable to use one having a haze of 1.0 or less. By setting the range to the above range, the appearance of the bonded product is not impaired and the design can be enhanced.
  • the heat-sensitive adhesive sheet (A) preferably maintains the light transmittance and haze even after being left in a high temperature and high humidity environment.
  • the heat-sensitive adhesive sheet (A) has heat-sensitive adhesiveness, and the 180 ° peeling adhesive force immediately after application in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH is preferably 1 N / cm or less. It is more preferably 7 N / cm or less, and particularly preferably 0.1 N / cm to 0.5 N / cm.
  • the thermoplastic adhesive sheet (B) on which the thermal adhesive sheet (A) is laminated or the thermal adhesive sheet (A) laminated on the release liner can be used as a pressure-air forming machine, a vacuum forming machine, or a TOM forming machine.
  • the position When attached to a bonding device such as, etc., the position can be easily corrected, and dirt and dust do not adhere to the surface of the adhesive layer, and the appearance after bonding is not impaired. Further, when the thermoplastic bonding material is first molded so as to follow the shape of the molded product and then bonded to the surface of the molded product with the liquid adhesive or the adhesive sheet, the bonding position is deviated. However, since it is easy to peel off, it is easy to correct the position from the displaced position, and it is possible to prevent air bubbles from being caught in the interface between the heat-sensitive adhesive layer (a) and the molded product (C).
  • the 180 ° peeling adhesive force of the heat-sensitive adhesive sheet (A) after being heat-attached is 5 N / cm or more in each of a temperature of 23 ° C. and a relative humidity of 50% RH environment and a temperature of 90 ° C. environment. It is preferably 8 N / cm to 50 N / cm, more preferably 10 N / cm to 30 N / cm. Within the above range, when the thermal adhesive sheet (A) is used as an adhesive layer and the thermoplastic adhesive (B) is heated to 90 ° C. to 200 ° C. and bonded to the surface of the molded product (C).
  • the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A) Due to the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A), bubbles are formed by the gas that can be generated from the thermoplastic bonding material (B) and the curved surface repulsion of the thermoplastic bonding material (B) is caused. Peeling can be suppressed. Further, the bonded product bonded with the heat-sensitive adhesive sheet (A) configured in the heat-sensitive adhesive layer (a) is a thermoplastic bonding material (B) or molded even if it is left in a high temperature and high humidity environment. It is possible to suppress peeling due to the formation of bubbles due to the gas that can be generated from at least one of the object (C).
  • the 180 ° peeling adhesive force of the heat-sensitive adhesive sheet (A) after being heat-attached is preferably 1 N / cm or more and more preferably 2 N / cm to 30 N / cm in an environment of a temperature of ⁇ 20 ° C. It is preferable, and 3N / cm to 20N / cm is particularly preferable.
  • the 180 ° peeling adhesive force immediately after application in a temperature of 23 ° C. and a relative humidity of 50% RH is 120 by removing the peeling liner on one side of the heat-sensitive adhesive sheet (A) in which the peeling liner is laminated on both sides.
  • a 125 ⁇ m-thick polycarbonate sheet Teijin Co., Ltd., “Panlite PC-2151”
  • a thermal laminator heated to °C it is cut into 1 cm widths and thickened at 23 °C and in a 50% RH atmosphere.
  • the 180 ° peeling adhesive force after heat application is 140 ° C for 15 seconds with a heat press device (manufactured by Tester Sangyo Co., Ltd., "TP-750 air press") instead of pressurizing one round trip with the 2 kg roller.
  • a sample is prepared by heating and pressurizing at a pressure of 0.2 MPa, and in the same manner as described above, under an atmosphere of ⁇ 20 ° C., an atmosphere of 23 ° C. and a relative humidity of 50% RH, and an atmosphere of 90 ° C., respectively. It is obtained by measuring the peeling resistance when the polycarbonate sheet is pulled in the 180 ° direction at a speed of 50 mm / min. When measuring at temperatures of -20 ° C and 90 ° C, humidity is not controlled.
  • thermoplastic adhesive layer (B) was bonded to the surface of the molded product (C) using the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet described above as an adhesive layer. It is a method of manufacturing an article.
  • thermoplastic bonding material (B) examples include a transparent member made of plastic.
  • thermoplastic bonding material (B) examples include any resin base material, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose buty.
  • Acrylic resins and resin substrates such as these alloys can be used.
  • the resin base material polycarbonate, (meth) acrylic resin and their alloys are preferable in order to achieve both high transparency and surface hardness.
  • polycarbonate and (meth) acrylic resins and resin substrates such as these alloys tend to generate gas instantly when heated at about 85 ° C.
  • the bonding method of the present invention using the heat-sensitive adhesive sheet (A) is excellent because it is difficult to form bubbles due to the generation of the gas even when the resin base material is used, and the appearance is not impaired. It is possible to obtain a bonded product that retains transparency and surface hardness.
  • the thermoplastic binder (B) preferably has a thickness of 0.05 mm to 5 mm, more preferably 0.1 mm to 1 mm, and 0.125 mm to 1 mm. It is particularly preferable to use one having a thickness of 0.4 mm. By setting the thickness, durability for protecting the surface of the molded product (C) can be imparted.
  • thermoplastic bonding material (B) is optionally applied to the surface of the thermoplastic bonding material (B) by coating, transfer, co-extrusion, etc., for the purpose of preventing scratches on the surface and improving slipperiness.
  • a hard coat layer, a matte layer, or the like may be laminated.
  • thermoplastic bonding material (B) when used for an article used outdoors such as an automobile exterior, the thermoplastic bonding material (B) and the heat-sensitive adhesive sheet (A) on the back layer.
  • the molded product (C) may be provided with a layer that absorbs ultraviolet rays having a wavelength of 325 nm to 380 nm on the surface or inside of the thermoplastic bonding material (B).
  • a method for forming the ultraviolet absorbing layer a method of applying a coating agent or the like containing an arbitrary ultraviolet absorbing agent or the like to the surface of the thermoplastic bonding material (B), or the inside of the thermoplastic bonding material (B).
  • a method such as kneading an arbitrary ultraviolet absorber into the surface can be mentioned.
  • the ultraviolet transmittance at a wavelength of 325 nm to 380 nm is preferably 0% to 20%, and 0% to 10% for imparting outdoor light resistance. Is more preferable.
  • thermoplastic bonding material (B) it is preferable to use a material having a light transmittance of 80% to 100% and a haze of 0% to 5.0% at a wavelength of 380 nm to 780 nm, which corresponds to the visible light region. It is more preferable to use one having a light transmittance of 380 nm to 780 nm of 85% to 100% and a haze of 0% to 2.0% or less. Within the above range, the design of the bonded product can be enhanced.
  • thermoplastic bonding material (B) a decorative layer and a functional layer are laminated in advance on the surface side on which the heat-sensitive adhesive sheet (A) is laminated, and the heat-sensitive adhesive layer (a) and the thermoplastic bonding material (B) are laminated.
  • ) May be a heat-bonded sheet in which the decorative layer and the functional layer are laminated.
  • the thickness of the decorative layer or the functional layer is preferably 35% or less, more preferably 25% or less, and particularly preferably 10% or less of the thickness of the thermal adhesive sheet.
  • the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) is formed when the decorative layer and the functional layer are heat-bonded.
  • the method of laminating the decorative layer and the functional layer may be any processing method, and a colored paint, a metal-containing paint, or the like is applied to the thermoplastic bonding material (B) by a silk screen printing machine, a gravure printing machine, or the like.
  • a method of applying directly to the surface a method of transferring to the surface of the thermoplastic bonding material (B) using a transfer foil in which a decorative layer or a functional layer is laminated in advance, or a method of spraying a colored paint or a metal-containing paint.
  • thermoplastic bonding materials (B) may be bonded.
  • the same type of material may be bonded, or other types of materials mentioned in the above examples may be bonded.
  • molded product (C) Specific examples of the molded product (C) bonded by the method of the present invention include a molded product provided with a decorative layer for the purpose of imparting designability, light-shielding property, and the like.
  • the molded product (C) may be a molded product formed by an arbitrary molding method, for example, a molded product formed by an insert molding method, a press molding method, or the like, and decorated by printing, painting, plating, or the like. It may be there. Further, the molded product (C) may have any shape and thickness.
  • the material of the molded product (C) is an inorganic substance such as glass or ceramic; a metal such as stainless steel or aluminum; polycarbonate, polymethylmethacrylate, alloy of polycarbonate and acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate.
  • polycarbonate, acrylic resin, polycarbonate and acrylonitrile-butadiene -It is preferable to use a resin molded product such as an alloy of styrene copolymer.
  • a decorative layer or a functional layer is laminated in advance on the surface side on which the heat-sensitive adhesive sheet (A) is laminated, and the molded product (C) is added between the heat-sensitive adhesive layer (a) and the molded product (C).
  • It may be a heat-bonded sheet in which a decorative layer and a functional layer are laminated.
  • a decorative layer and a functional layer are laminated.
  • the thickness of each layer laminated on the surface side on which the thermal adhesive sheet (A) is laminated is preferably 35% or less, more preferably 25% or less, and 10% of the thickness of the thermal adhesive sheet. The following thickness is particularly preferable.
  • the decorative layer and the functional layer are the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A). It can be buried inside to eliminate the step and enhance the design of the bonded product.
  • the method of laminating the decorative layer and the functional layer may be any processing method, and the colored paint or the metal-containing paint is directly applied to the surface of the molded product (C) by a silk screen printing machine, a gravure printing machine or the like.
  • Examples thereof include a method of applying to the surface of the molded product (C), a method of performing a sputtering process A on the surface of the molded product (C), a plating process, a method of laminating a metal foil and then etching.
  • a plurality of the molded products (C) may be bonded to each other.
  • the same type may be bonded together, or other types of the molded products (C) mentioned in the above examples may be bonded together.
  • the method for producing an article of the present invention that is, a method for producing an article in which the thermoplastic bonding material (B) and the molded product (C) are bonded and bonded with the heat-sensitive adhesive sheet (A) is from ⁇ 50 ° C. to Tension loss tangent (tan ⁇ ) measured within the range of 200 ° C and at a frequency of 3 Hz has a peak temperature of at least one above 90 ° C and at least one below -20 ° C, and tensile storage at 100 ° C.
  • thermoplastic adhesive sheet (A) having a heat-sensitive adhesive layer (a) having an elasticity ( E'a100 ) of 5 ⁇ 10 5 Pa to 1 ⁇ 10 8 Pa is used as an adhesive layer, and a thermoplastic bonding material (B) is used. ) Is heated to 90 ° C. to 200 ° C. and bonded to the surface of the molded product (C).
  • the bonding method in the method for producing the article is not particularly limited, but among them, the first aspect in which the following steps [1] and [2] are performed in this order, the following steps [3] and [4] are performed.
  • a second aspect in which the steps [1] and the following steps [1] and [5] and [6] are performed in this order are preferable.
  • the first aspect of the method for manufacturing the article is a step of laminating the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) and the thermoplastic adhesive (B) to form a laminate.
  • the thermoplastic bonding material (B) or the heat-sensitive adhesive layer (a) is heated to 90 ° C. to 200 ° C., and the heat-sensitive adhesive layer of the laminate (
  • This is a method for manufacturing an article which comprises the step [2] of pressurizing and bonding the a) and the molded product (C) in this order.
  • the thermoplastic bonding material (B) and the molded product (C) two or more types may be bonded at the same time in each step.
  • the laminating process of the thermoplastic laminating material (B) and the molded product (C) by the molding machine described later is generally a batch production method and can be one of the rate-determining steps in the production process of the article. According to the method for manufacturing an article of the first aspect, the number of steps for using the molding machine can be reduced, so that the production efficiency is excellent.
  • the thermal adhesive sheet (A) may have a release liner using a thermoplastic resin material as a base material on one side or both sides.
  • the release liner A is peeled off.
  • the release liner B is peeled off to carry out the step [2].
  • the heat-sensitive adhesive sheet (A) since the heat-sensitive adhesive sheet (A) has poor adhesiveness at room temperature, it is preferable to temporarily bond the heat-sensitive adhesive layer (a) and the thermoplastic bonding material (B).
  • the heat-sensitive adhesive layer of the heat-sensitive adhesive sheet (A) is provided with a release liner laminated on the surface opposite to the thermoplastic bonding material (B) of the heat-sensitive adhesive sheet (A).
  • a method in which the (a) and the thermoplastic adhesive (B) are heated and brought into close contact with each other while passing through a gap between a rotating rubber roller or a metal roller heated at 90 ° C. or higher, and the thermal adhesive layer (a) of the thermal adhesive sheet (A).
  • thermoplastic adhesive (B) are temporarily bonded at room temperature so as not to contain air bubbles, and heat-cured in an atmosphere of 50 ° C. or higher for 24 hours or longer. ..
  • the heat-sensitive adhesive layer (a) and the thermoplastic bonding material (B) are mainly bonded when the step [2] is performed. Further, in the step [2], the molded product (C) is pressed against the surface of the heat-sensitive adhesive layer (a) with a molding machine at a pressure of about 0.1 MPa or more, or the thermoplastic bonding material (B).
  • thermoplastic bonding material (B) and the heat-sensitive adhesive sheet (A) are attached to the surface of the molded product (C) while being deformed in the three-dimensional direction. Is preferable.
  • the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) is heated to 90 ° C. to 200 ° C., and the heat-sensitive adhesive layer of the heat-sensitive adhesive sheet (A) is heated.
  • the thermoplastic bonding material (B) is heated to 90 ° C. to 200 ° C.
  • the step [4] of pressurizing and bonding the thermoplastic bonding material (B) and the heat-sensitive adhesive layer (a) is a method for manufacturing an article.
  • thermoplastic bonding material (B) and the molded product (C) two or more types may be bonded at the same time in each step.
  • thermoplastic adhesive (B) which can generate gas by heating, is heated, and after the gas is released from the thermoplastic adhesive (B), heat-sensitive adhesion is performed. Since it is bonded to the sheet (A), it is possible to reduce the swelling between the heat-sensitive adhesive layer (a) due to the gas generated from the thermoplastic bonding material (B).
  • a heat-sensitive adhesive sheet (A) on which a release liner based on a thermoplastic resin material is laminated is used, and the heat-sensitive adhesive sheet (A) is used together with the release liner.
  • the heat-sensitive adhesive layer (a) of the above is heated to 90 ° C. to 200 ° C., and the surface of the heat-sensitive adhesive sheet (A) opposite to the surface on which the release liner is laminated and the surface of the heat-sensitive adhesive sheet (A) and the surface opposite to the surface on which the release liner is laminated.
  • the thermoplastic bonding material (B) is heated to 90 ° C.
  • the method for producing an article includes the step [4] of pressurizing and adhering the material (B) and the heat-sensitive adhesive layer (a) after peeling and removing the release liner in this order.
  • the heat-sensitive adhesive sheet (A) on which the release liner based on the thermoplastic resin material was laminated the heat-sensitive adhesive layer (a) was heated together with the release liner in the step [3], and the release liner was laminated.
  • the tensile strength of the heat-sensitive adhesive sheet (A) is increased, the heat-sensitive adhesive sheet (A) is easily pressed against the molded product (C), and the heat-sensitive adhesive layer (A). This is because it is possible to prevent uneven adhesion at the interface between the a) and the molded product (C) and air bubbles from entering the interface.
  • the heat-sensitive adhesive sheet (A) in a state where a release liner using a thermoplastic resin material as a base material is laminated on one side is heated, and then the heat-sensitive adhesive layer (a) is heated by a molding machine.
  • the molded product (C) is pressed against the surface, or the surface side of the thermoplastic release liner of the heat-sensitive adhesive sheet (A) is pressed to move the heat-sensitive adhesive sheet (A) together with the release liner in a three-dimensional direction. It is preferable to attach it to the surface of the molded product (C) while deforming it. This is because the adhesion to the surface of the deformed molded product (C) is improved and the molded product (C) can be firmly attached.
  • the pressure when the molded product (C) is pressed against the surface of the heat-sensitive adhesive layer (a) in the heat-sensitive adhesive sheet (A) after heating is preferably about 0.1 MPa or more.
  • the thermal adhesive layer (a) is pressed against the thermoplastic bonding material (B) at a pressure of about 0.1 MPa or more, or the surface side of the thermoplastic bonding material (B). It is preferable that the thermoplastic adhesive (B) is three-dimensionally deformed and attached to the surface of the thermal adhesive layer (a) by pressurizing the thermoplastic adhesive layer (B) with compressed air of about 0.1 MPa or more.
  • the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) and the thermoplastic bonding material (B) are attached in the same manner as in the first aspect.
  • the thermoplastic bonding material (B) or the heat-sensitive adhesive layer (a) of the laminate is placed at 90 ° C. to 200 ° C. And pressurize a mold of the same type as the molded product (C) to form the laminate into the shape of the molded product (C), and after the step [5], molding.
  • the laminated product was placed on the surface of the molded product (C), and the heat-sensitive adhesive layer (a) was applied from at least one side of the thermoplastic bonding material (B) or the molded product (C) at 90 ° C. to
  • This is a method for producing an article which comprises a step [6] of heating to 200 ° C. and laminating the heat-sensitive adhesive layer (a) and the molded product (C) in this order.
  • the thermoplastic bonding material (B) and the molded product (C) two or more types may be bonded at the same time in each step.
  • the shape is stabilized by pre-molding the thermoplastic bonding material (B) on which the heat-sensitive adhesive sheet (A) is laminated, and the molded product (C) is heated. It is possible to reduce the distortion caused by the deformation of the thermoplastic bonding material (B) at the time of bonding to the surface of the material, and to reduce the floating and peeling after bonding. Further, since the heat-sensitive adhesive sheet of the present invention has low room temperature adhesiveness, the thermoplastic bonding material (B) previously molded into the shape of the molded product (C) is passed through the heat-sensitive adhesive sheet to the molded product (C). ) Can be easily fitted, and the molded thermoplastic bonding material (B) and the molded product (C) can be closely bonded.
  • Examples of the molding machine used in the method for manufacturing an article include any molding machine such as a pressure molding machine, a vacuum forming machine, a TOM molding machine, an NGF molding machine, and a hot press molding machine.
  • the thermoplastic laminating material (B) on which the heat-sensitive adhesive sheet (A) is laminated is heated at 90 ° C. to 200 ° C. through the steps of depressurizing the inside of the tank in which the molded product (C) is installed and the step [1].
  • the molded product (C) is raised and pressed against the heat-sensitive adhesive layer (a), and the thermoplastic bonding material (B) on which the heat-sensitive adhesive sheet (A) is laminated is pressed by air pressure or a press plate or the like.
  • the article is manufactured through a step of pressurizing, a step of removing the bonded product from the molding machine, and a step of trimming the thermoplastic bonding material (B) on which the heat-sensitive adhesive sheet (A) protruding from the molded product is laminated.
  • a heat-sensitive adhesive sheet (A) in which a release liner is laminated on one side a step of attaching the molded product (C) to the molding machine, and a molded product (C) are installed.
  • a step of depressurizing the inside of the tank a step of heating the heat-sensitive adhesive sheet (A) in which a release liner is laminated on one side at 90 ° C.
  • the step of attaching to the machine the step of depressurizing the inside of the tank in which the molded product (C) on which the heat-sensitive adhesive sheet (A) is laminated is installed, and the thermoplastic adhesive (B) at 90 ° C to 200 ° C.
  • the molded product (C) is raised to press the heat-sensitive adhesive layer (a) against the thermoplastic adhesive (B), and the thermoplastic adhesive (B) is pressed or pressed.
  • the article is manufactured through a step of pressurizing with a plate or the like, a step of removing the bonded product from the molding machine, and a step of trimming the thermoplastic adhesive bonding material (B) protruding from the molded product.
  • thermoplastic bonding material (B) and the molded product (C) on which the heat-sensitive adhesive sheet (A) is laminated are attached to the molding machine through the step [1].
  • Step a step of depressurizing the inside of a tank in which a mold of the same type as the molded product (C) having a mold releasable surface is installed, a step [1], and a thermoplastic bonding in which a heat-sensitive adhesive sheet (A) is laminated.
  • the mold is raised after heating and pressed against the heat-sensitive adhesive layer (a), and the thermoplastic bonding sheet (A) is laminated.
  • the molded product of the thermoplastic adhesive sheet (B) on which the heat-sensitive adhesive sheet (A) is laminated is removed from the molding machine, and the heat-sensitive adhesive sheet (A) is laminated.
  • the thermoplastic bonding material (B) in which the heat-sensitive adhesive sheet (A) is laminated on the surface of the molded product (C) is formed.
  • the article is manufactured through a step of press-pressing the thermoplastic bonding material (B) or the molded product (C) on which the heat-sensitive adhesive sheet (A) is laminated while heating at 90 ° C to 200 ° C.
  • the bonded product bonded by the bonding method has a structure in which the thermoplastic bonding material (B) and the molded product (C) are laminated via the heat-sensitive adhesive sheet (A). Further, if necessary, between the thermoplastic bonding material (B) and the heat-sensitive adhesive sheet (A), or between the heat-sensitive adhesive sheet (A) and the molded product (C), the said It may have a structure in which a decorative layer and a functional layer are laminated.
  • the bonded product by the bonding method of the present invention has the purpose of imparting design and functionality to the surface of the molded product, and is used for the exterior of home appliances and mobile terminals on which the decorative layer and the functional layer are laminated, and for automobiles. It is preferably used for resin molded products used for interior and exterior.
  • the molded product (C) is a part that is three-dimensionally molded by insert molding, press molding, or the like, and in the above-mentioned bonded product, for the purpose of preventing scratches on the surface of the molded product (C) and improving slipperiness.
  • the thermoplastic bonding material (B) having a hard coat layer or a mat layer on the surface is bonded by the method of the present invention.
  • the bonded product obtained by the manufacturing method including the bonding method of the present invention has the formation of bubbles and the thermoplasticity due to the gas that can be generated from the surface of the molded product (C) and the surface of the thermoplastic bonding material (B).
  • a bonded product with excellent appearance quality that suppresses the floating and peeling of the thermoplastic bonded material (B) caused by the curved surface repulsion of the bonded material (B) and achieves both excellent transparency. It has become.
  • a triblock copolymer composed of methyl polyacrylate-n-butyl polyacrylate-methyl methacrylate, which contains 64% by mass of n-butyl polyacrylate as a polymer block (S1) having a glass transition temperature. k-1) was obtained.
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-1) was determined by GPC measurement by the above method and found to be 82,000. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-1) was measured, the Tg of the polymer block of polymethyl methacrylate was 103 ° C., and that of n-butyl polyacrylic acid.
  • the Tg of the polymer block was ⁇ 51 ° C.
  • the glass transition temperature (Tg) of each polymer block of the block copolymer (k-1) is increased by using a differential scanning calorimeter (“DSC-7020” manufactured by Hitachi High-Tech Science Systems Co., Ltd.). In the curve obtained by measuring from ⁇ 100 ° C. to 150 ° C. under the condition of a temperature rate of 10 ° C./min, the external glass transition start temperature was defined as the glass transition temperature (Tg).
  • the glass transition temperatures (Tg) of the block copolymers (k-2) to (k-8) and each polymer block in Examples and Comparative Examples were also measured by the above-mentioned method.
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-2) was determined by GPC measurement of the above method and found to be 84,000. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-2) was measured, the Tg of the polymer block of polymethyl methacrylate was 103 ° C., and that of n-butyl polyacrylic acid. The Tg of the polymer block was ⁇ 52 ° C.
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-3) was determined by GPC measurement of the above method and found to be 79,000. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-3) was measured, the Tg of the polymer block of polymethyl methacrylate was 104 ° C., and that of n-butyl polyacrylic acid. The Tg of the polymer block was ⁇ 51 ° C.
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-4) was determined by GPC measurement of the above method and found to be 76,000. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-4) was measured, the Tg of the polymer block of polymethyl methacrylate was 104 ° C., and that of n-butyl polyacrylic acid. The Tg of the polymer block was ⁇ 52 ° C.
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-5) was determined by GPC measurement of the above method and found to be 83,000. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-5) was measured, the Tg of the polymer block of polymethyl methacrylate was 103 ° C., and that of n-butyl polyacrylic acid. The Tg of the polymer block was ⁇ 53 ° C.
  • reaction solution containing a polystyrene-polybutadiene-polystyrene triblock copolymer was obtained.
  • Palladium carbon (palladium-supported amount: 5% by mass) was added to this reaction solution as a hydrogenation catalyst in an amount of 10% by mass based on the block copolymer, and the reaction was carried out under the conditions of hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. ..
  • palladium carbon is removed by filtration, the filtrate is concentrated, and further vacuum dried to contain 30% by mass of polystyrene as a polymer block (S2) having a glass transition temperature of 90 ° C. or higher.
  • Pellets of polystyrene-hydride polybutadiene-polystyrene triblock copolymer (k-6) containing 70% by mass of hydride polybutadiene as a polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower are obtained. It was.
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-6) was determined by GPC measurement of the above method and found to be 200,000.
  • Tg glass transition temperature
  • ⁇ Synthesis of block copolymer (k-7)> In the same manner as the block copolymer (k-6), the amounts of styrene and butadiene used were adjusted, and 67% by mass of polystyrene was added as a hard block (polymer block (S2) having a glass transition temperature of 90 ° C. or higher).
  • the weight average molecular weight (Mw) of the obtained triblock copolymer (k-7) was determined by GPC measurement of the above method and found to be 100,000. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-7) was measured, the Tg of the polystyrene polymer block was 98 ° C., and the Tg of the hydrogenated polybutadiene polymer block was It was -23 ° C.
  • the weight average molecular weight (Mw) of the obtained (meth) acrylic random copolymer (k-8) was determined by GPC measurement of the above method and found to be 470,000. Moreover, when the glass transition temperature (Tg) of the (meth) acrylic random copolymer (k-8) was measured, no inflection point was observed.
  • the weight average molecular weight (Mw) of the obtained (meth) acrylic random copolymer (k-9) was determined by GPC measurement of the above method and found to be 220,000. Moreover, when the glass transition temperature (Tg) of the (meth) acrylic random copolymer (k-9) was measured, Tg was 72 ° C.
  • Example 1 ⁇ Preparation of thermal adhesive sheet (A-1)> 135 parts by mass of the triblock copolymer (k-1) was stirred and dissolved in 165 parts by mass of toluene to obtain a solution of the adhesive composition (a-1) having a solid content of 45% by mass.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 36 parts by mass
  • the content of the polymer block (S1) having a glass transition temperature of -20 ° C or lower is 36 parts by mass. It was 64% by mass.
  • the thickness after drying is on the peeled surface of a polyethylene terephthalate film (“TN100-75 ⁇ m” manufactured by Toyo Spinning Co., Ltd.) with a thickness of 75 ⁇ m, which is peeled with a non-silicone compound on one side.
  • the adhesive composition (a-1) is applied so as to have a thickness of 100 ⁇ m, dried at 70 ° C. for 3 minutes and at 120 ° C. for 4 minutes, and peeled with a silicone compound on one side as a peeling liner B on the light peeling side.
  • a heat-sensitive adhesive sheet (A-1) was prepared by laminating the peeled surface of a 50 ⁇ m-thick polyethylene terephthalate film (“50E-0010BD” manufactured by Fujimori Kogyo Co., Ltd.).
  • Example 2 ⁇ Making a thermal adhesive sheet (A-2)>
  • the adhesive composition (a) having a solid content of 45% by mass is obtained by stirring and dissolving 54 parts by mass of the triblock copolymer (k-2) and 81 parts by mass of the triblock copolymer (k-3) in 156 parts by mass of toluene.
  • the solution of -2) was obtained.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 36% by mass on average
  • the content of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower is 36% by mass on average.
  • the polymer block (S1) in the block copolymer mixture of the triblock copolymer (k-2) and the triblock copolymer (k-3) in the adhesive composition (a-2), ( The contents of S2) are the polymer blocks (S1) and (S2) in the block copolymer mixture described in the item "Heat-sensitive adhesive layer (a)" of the above "1. Heat-sensitive adhesive sheet (A)", respectively. ) was calculated based on the formula (1). The thickness after drying is 100 ⁇ m in the same manner as in Example 1 except that the solution of the adhesive composition (a-2) is used instead of the solution of the adhesive composition (a-1). In this way, a heat-sensitive adhesive sheet (A-2) was produced.
  • Example 3 ⁇ Making a thermal adhesive sheet (A-3)> 122 parts by mass of the triblock copolymer (k-3) and 13 parts by mass of pine crystal KE-311 (ultra-light rosin derivative manufactured by Arakawa Chemical Industry Co., Ltd.) as a tackifier were dissolved by stirring in 156 parts by mass of toluene. , A solution of the adhesive composition (a-3) having a solid content of 45% by mass was obtained.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 40% by mass
  • the content of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower is 40% by mass.
  • the thickness after drying is 100 ⁇ m in the same manner as in Example 1 except that the solution of the adhesive composition (a-3) is used instead of the solution of the adhesive composition (a-1). In this way, a heat-sensitive adhesive sheet (A-3) was produced.
  • Example 4 ⁇ Making a thermal adhesive sheet (A-4)> 54 parts by mass of the triblock copolymer (k-2) and 81 parts by mass of the triblock copolymer (k-4) are stirred and dissolved in 156 parts by mass of toluene to prepare an adhesive composition (a) having a solid content of 45% by mass.
  • the solution of -4) was obtained.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 42% by mass on average, and the content of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower is Was 58% by mass.
  • the polymer block (S1) in the block copolymer mixture of the triblock copolymer (k-2) and the triblock copolymer (k-4) in the adhesive composition (a-4), ( The contents of S2) are the polymer blocks (S1) and (S2) in the block copolymer mixture described in the item "Heat-sensitive adhesive layer (a)" of the above "1. Heat-sensitive adhesive sheet (A)", respectively. ) was calculated based on the formula (1). The thickness after drying is 100 ⁇ m in the same manner as in Example 1 except that the solution of the adhesive composition (a-4) is used instead of the solution of the adhesive composition (a-1). In this way, a heat-sensitive adhesive sheet (A-4) was produced.
  • Example 5 ⁇ Making a thermal adhesive sheet (A-5)> 135 parts by mass of the triblock copolymer (k-2) was stirred and dissolved in 156 parts by mass of toluene to obtain a solution of the adhesive composition (a-5) having a solid content of 45% by mass.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 30% by mass on average
  • the content of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower is 30% by mass on average.
  • the thickness after drying is 100 ⁇ m in the same manner as in Example 1 except that the solution of the adhesive composition (a-5) is used instead of the solution of the adhesive composition (a-1). In this way, a heat-sensitive adhesive sheet (A-5) was produced.
  • Example 6 ⁇ Making a thermal adhesive sheet (A-6)>
  • the thickness of the release liner B polyethylene terephthalate film "50E-0010BD" used in Example 1 after drying on the release-treated surface.
  • the solution of the adhesive composition (a-1) was applied so that the thickness was 100 ⁇ m, dried at 70 ° C. for 3 minutes and at 120 ° C. for 4 minutes, and the heat-sensitive adhesive sheet (A-1) prepared earlier was prepared.
  • Example 7 ⁇ Making a thermal adhesive sheet (A-7)>
  • the heat-sensitive adhesive sheet (A-1) was similarly applied to the heat-sensitive adhesive sheet (A-1) of Example 1 except that the adhesive composition (a-1) was applied so that the thickness after drying was 50 ⁇ m.
  • A-7) was prepared.
  • Example 8 ⁇ Making a thermal adhesive sheet (A-8)>
  • the adhesive composition (a) having a solid content of 30% by mass is obtained by stirring and dissolving 108 parts by mass of the triblock copolymer (k-6) and 27 parts by mass of the triblock copolymer (k-7) in 315 parts by mass of toluene.
  • a solution of -8) was obtained.
  • the content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 37.4% by mass on average, and that of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower.
  • the content was 62.6% by mass on average.
  • Example 9 ⁇ Making a thermal adhesive sheet (A-13)> 122 parts by mass of the triblock copolymer (k-1) and 13 parts by mass of YS Polystar TH130 (manufactured by Yasuhara Chemical Co., Ltd., terpenphenol resin) as a tackifier were stirred and dissolved in 156 parts by mass of toluene, and the solid content was 45 parts by mass. A solution of% adhesive composition (a-13) was obtained. The content of the polymer block (S2) having a glass transition temperature of 90 ° C. or higher in the triblock copolymer is 36% by mass, and the content of the polymer block (S1) having a glass transition temperature of ⁇ 20 ° C. or lower is 36% by mass. It was 64% by mass. In the same manner as in Example 1, a heat-sensitive adhesive sheet (A-13) was prepared so that the thickness after drying was 100 ⁇ m.
  • thermoplastic bonding material (B-1) A commercially available polycarbonate sheet having a thickness of 0.3 mm (manufactured by Teijin Limited, "Panlite PC-2151”) was cut into a size suitable for each evaluation and used.
  • thermoplastic bonding material (B-2) A commercially available polycarbonate sheet having a thickness of 0.125 mm (manufactured by Teijin Limited, "Panlite PC-2151”) was cut into a size suitable for each evaluation and used.
  • the release liner was sequentially removed from the adhesive sheets obtained in the above Examples and Comparative Examples, laminated to a thickness of 600 ⁇ m, and then left in a dryer at 120 ° C. for 30 seconds for heat-sensitive adhesion between the layers.
  • the test piece was a rectangular piece having a width of 5 mm and a length of the measuring portion of 20 mm, and the lengths of the handles at both ends cut into 20 mm each.
  • the peeling liners on both sides are peeled off, and using a tensile dynamic viscoelasticity measuring device (TA Instruments, RSA III), the temperature rise rate is 5 ° C./min, the measurement frequency is 3.0 Hz, and the measurement temperature range is-. measured in the range of 50 ⁇ 200 °C, -20 °C, 25 °C, 100 °C, storage modulus tensile at 0.99 ° C., respectively (E 'a-20, E ' a25, E 'a100, E' a150) and loss tangent (Tan ⁇ ) was measured. From the obtained graph of loss tangent (tan ⁇ ), the presence or absence of peak temperature and the loss tangent (tan ⁇ ) at that temperature and peak temperature were read.
  • TA Instruments, RSA III tensile dynamic viscoelasticity measuring device
  • the adhesive sheets obtained in the above Examples and Comparative Examples are cut into a size of 30 cm square, and the release liner B (PET film "50E-0010BD) of the adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 and 5) is cut.
  • the peeling liner on the light peeling side of the adhesive sheet used in Comparative Example 4 is removed, temporarily bonded to a thermoplastic bonding material (B-1) of the same size with a hand roller, and then heated to 120 ° C.
  • the adhesive sheet was heat-sensitively adhered to the thermoplastic bonding material (B-1) by passing it through a laminator (“SA-1010 small desktop test laminator” manufactured by Tester Sangyo Co., Ltd.) at a speed of 1 m / min and a pressure of 0.2 MPa. Next, the sample was cut into 10 cm squares, the peeling liner on the remaining one side was removed, and the sample was placed on the surface of a molded product (C-1) having a size of 12 cm square. The sample was set in a machine "TP-750 air press"), and only the surface side of the thermoplastic bonding material (B-1) was heated at a pressure of 0.2 MPa at 140 ° C. for 15 seconds, and the sample was molded (C-1).
  • SA-1010 small desktop test laminator manufactured by Tester Sangyo Co., Ltd.
  • Comparative Example 4 is a pressure-sensitive adhesive sheet
  • a bonded product was produced under the same conditions as described above.
  • a bonded product was prepared and used under the same conditions as in other examples and comparative examples. The appearance of the obtained bonded product was visually evaluated according to the following criteria.
  • the adhesive sheets obtained in Examples and Comparative Examples are cut into a size of 30 cm square, and the adhesive sheet release liner B (PET film "50E-0010BD)" of Examples 1 to 9 and Comparative Examples 1 to 3 and 5 is used.
  • the peeling liner on the light peeling side of the adhesive sheet used in Comparative Example 4 was removed, temporarily bonded to a thermoplastic bonding material (B-2) of the same size with a hand roller, and then heated to 120 ° C.
  • the adhesive sheet was heat-sensitively adhered to the thermoplastic bonding material (B-2) by passing it through a laminator at a speed of 1 m / min and a pressure of 0.2 MPa.
  • the sample was cut into a width of 1 cm and a length of 10 cm, the peeling liner on the remaining one side was removed under a temperature of 23 ° C. and a relative humidity of 50% RH, and the sample was cut into a size of 2 cm in width and 12 cm in length.
  • the average value of each peak of the intermittent peeling resistance was taken as the peeling adhesive force.
  • the peeling resistance of the obtained bonded product was measured in the same manner as in the evaluation of the peeling adhesive force immediately after the bonding in an atmosphere of 23 ° C. after heat bonding.
  • a bonded product was prepared in the same manner as described above, and the peeling resistance was measured in an environment of 90 ° C. and ⁇ 20 ° C. When peeling by the stick-slip phenomenon, the average value of each peak of the intermittent peeling resistance was taken as the peeling adhesive force.
  • thermoplastic bonding material (B-1) of the same size with a hand roller, and then heated to 120 ° C.
  • the heat-sensitive adhesive sheet was adhered to the thermoplastic adhesive (B-1) by passing it through a thermal laminator at a speed of 1 m / min and a pressure of 0.2 MPa.
  • the sample was cut into 10 cm squares, the peeling liner on the remaining one side was removed, and a polyurethane copper wire (UEW, manufactured by Sanko Densho Co., Ltd.) with a diameter of 0.2 mm cut into a length of 12 cm was placed on the surface of the adhesive layer.
  • UEW polyurethane copper wire
  • Five pieces are placed at equal intervals and heated from the thermoplastic bonding material (B-1) side with the heat press device at a pressure of 0.2 MPa at 140 ° C. for 15 seconds to form a thermoplastic bonding material (B-1).
  • thermoplastic bonding material (B-2) of the same size with a hand roller. Then, the adhesive sheet was passed through the thermal laminator heated to 120 ° C. at a speed of 1 m / min and a pressure of 0.2 MPa, and the adhesive sheet was heat-sensitively adhered to the thermoplastic bonding material (B-2). Next, it was cut into a size of 5 cm square, placed on a bright-annealed 1 mm thick SUS304 stainless steel plate in an environment of a temperature of 23 ° C.
  • thermoplastic bonding material (B-2) on which the adhesive sheet is laminated is peeled off. Evaluated the ease.
  • thermoplastic bonding material on which the heat-sensitive adhesive sheets are laminated is heated to 140 ° C. and bonded to the surface of the molded product.
  • the formation of bubbles and the peeling of the thermoplastic bonding material due to the possible gas are suppressed, and the bonding product has an excellent appearance. Further, even if these bonded products are left in a high temperature and high humidity environment, the formation and peeling of bubbles due to the gas that may be generated from at least one of the thermoplastic bonded material or the molded product is suppressed, and further, an environment in which cold heat is repeated.
  • the heat-sensitive adhesive sheet obtained in Comparative Example 2 has a tensile storage elastic modulus at 100 ° C. exceeding a specified range, and although no bubbles are formed in the bonding step, the heat-sensitive adhesive sheet is left in an environment where cold heat is repeated. When it is formed, bubbles are formed and peeled off, resulting in a bonded product having an inferior appearance.
  • the heat-sensitive adhesive sheet obtained in Comparative Example 5 has a tensile storage elastic modulus at 100 ° C. within a specified range, but has a peak temperature of tensile loss tangent (tan ⁇ ) in a temperature range of ⁇ 20 ° C. or lower. However, when it was left in an environment where cold heat was repeated, bubbles were formed and peeled off, resulting in a bonded product having an inferior appearance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne : une feuille adhésive qui, lorsqu'elle est utilisée pour stratifier un matériau de stratification thermoplastique chauffé ou similaire sur, par exemple, une surface d'un objet moulé tout en déformant en trois dimensions le matériau de stratification thermoplastique chauffé ou similaire, empêche non seulement la formation de bulles due à un gaz qui peut être généré à partir du matériau de stratification thermoplastique ou similaire, mais aussi le décollement du matériau de stratification thermoplastique ou similaire du fait d'une répulsion de surface incurvée et qui combine une excellente aptitude au refaçonnage juste après la stratification et l'adhérence ; et un procédé de production d'un article à l'aide de la feuille adhésive.　La présente invention concerne une feuille adhésive thermosensible comprenant une couche adhésive thermosensible (a) qui, lorsqu'elle est examinée pour une tangente de perte de traction (tanδ) dans la plage de -50 °C à 200 °C à une fréquence de 3 Hz, a au moins une température maximale à 90 °C ou plus et au moins une température maximale à -20 °C ou moins et qui a un module de conservation en traction de 100 °C (E'a100) de 5×105-1×108 Pa, la feuille adhésive thermosensible étant destinée à être utilisée dans la stratification d'un matériau de stratification thermoplastique (B) sur une surface d'un objet moulé (C) à l'aide de la couche adhésive thermosensible en tant que couche adhésive.
PCT/JP2020/032268 2019-09-10 2020-08-27 Feuille adhésive thermosensible et procédé de production d'un article obtenu par application d'une feuille adhésive thermosensible WO2021049301A1 (fr)

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CN202080059699.2A CN114286847A (zh) 2019-09-10 2020-08-27 热敏粘接片和贴合有热敏粘接片的物品的制造方法
JP2021545200A JP7111260B2 (ja) 2019-09-10 2020-08-27 感熱接着シート及び感熱接着シートを貼合した物品の製造方法

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6168076A (ja) * 1984-09-10 1986-04-08 日産自動車株式会社 ヘツドレストの製造方法
JPH09109266A (ja) * 1995-10-13 1997-04-28 Inoac Corp 表皮の貼着方法
JP2010065195A (ja) * 2008-09-12 2010-03-25 Kaneka Corp 熱可塑性エラストマー組成物および粘着剤
WO2015060224A1 (fr) * 2013-10-25 2015-04-30 株式会社クラレ Composition adhésive thermofusible
WO2016031550A1 (fr) * 2014-08-26 2016-03-03 株式会社クラレ Composition de polymère thermoplastique et article moulé
JP2017214597A (ja) * 2017-08-30 2017-12-07 株式会社クラレ 粘接着剤組成物
WO2019163812A1 (fr) * 2018-02-22 2019-08-29 日東シンコー株式会社 Feuille adhésive thermofusible et feuille décorative avec couche adhésive
JP2020041138A (ja) * 2018-09-10 2020-03-19 日東シンコー株式会社 ホットメルト接着シート

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI714815B (zh) * 2016-12-26 2021-01-01 日商迪愛生股份有限公司 物品、物品之製造方法及空隙之填充方法
JP7246858B2 (ja) * 2018-02-27 2023-03-28 日東電工株式会社 熱可塑性接着シートおよびその利用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6168076A (ja) * 1984-09-10 1986-04-08 日産自動車株式会社 ヘツドレストの製造方法
JPH09109266A (ja) * 1995-10-13 1997-04-28 Inoac Corp 表皮の貼着方法
JP2010065195A (ja) * 2008-09-12 2010-03-25 Kaneka Corp 熱可塑性エラストマー組成物および粘着剤
WO2015060224A1 (fr) * 2013-10-25 2015-04-30 株式会社クラレ Composition adhésive thermofusible
WO2016031550A1 (fr) * 2014-08-26 2016-03-03 株式会社クラレ Composition de polymère thermoplastique et article moulé
JP2017214597A (ja) * 2017-08-30 2017-12-07 株式会社クラレ 粘接着剤組成物
WO2019163812A1 (fr) * 2018-02-22 2019-08-29 日東シンコー株式会社 Feuille adhésive thermofusible et feuille décorative avec couche adhésive
JP2020041138A (ja) * 2018-09-10 2020-03-19 日東シンコー株式会社 ホットメルト接着シート

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