WO2017122797A1 - 表面改質熱可塑性樹脂の製造方法、接合構造体の製造方法、接合構造体、熱転写表面改質シート、熱転写表面改質シート付熱可塑性樹脂、および、表面改質熱可塑性樹脂 - Google Patents

表面改質熱可塑性樹脂の製造方法、接合構造体の製造方法、接合構造体、熱転写表面改質シート、熱転写表面改質シート付熱可塑性樹脂、および、表面改質熱可塑性樹脂 Download PDF

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WO2017122797A1
WO2017122797A1 PCT/JP2017/001066 JP2017001066W WO2017122797A1 WO 2017122797 A1 WO2017122797 A1 WO 2017122797A1 JP 2017001066 W JP2017001066 W JP 2017001066W WO 2017122797 A1 WO2017122797 A1 WO 2017122797A1
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WIPO (PCT)
Prior art keywords
thermoplastic resin
modified
easy
pps
thermal transfer
Prior art date
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PCT/JP2017/001066
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English (en)
French (fr)
Inventor
岡田 研一
啓輔 下北
亜樹子 田中
絵里子 船津
明日香 五味
島津 彰
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202210774568.3A priority Critical patent/CN115284695A/zh
Priority to EP17738549.9A priority patent/EP3404059B1/en
Priority to US16/070,239 priority patent/US20190030829A1/en
Priority to CN201780017239.1A priority patent/CN108834419A/zh
Publication of WO2017122797A1 publication Critical patent/WO2017122797A1/ja

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Definitions

  • the present invention relates to a method for producing a surface modified thermoplastic resin, a method for producing a bonded structure, a bonded structure, a thermal transfer surface modified sheet, a thermoplastic resin with a thermal transfer surface modified sheet, and a surface modified thermoplastic resin. .
  • metals such as iron and aluminum are generally used as constituent materials in transportation equipment such as railway vehicles, aircraft, ships, and automobiles.
  • metals such as iron and aluminum are generally used as constituent materials in transportation equipment such as railway vehicles, aircraft, ships, and automobiles.
  • rubber epoxy curable resin compositions have been widely used as such adhesives (for example, Patent Document 1).
  • FRP fiber reinforced plastic
  • FRTP fiber reinforced thermoplastic plastic
  • thermoplastic resin a thermoplastic resin as a matrix resin
  • thermoplastic resin is not easily compatible with the adhesive, and sufficient adhesive strength cannot be obtained even if a general-purpose adhesive or adhesive sheet is used.
  • a resin having high solvent resistance for example, PPS, In the case of PA, PP, etc.
  • thermoplastic resin In addition to the technique of applying the primer solution, various surface treatment methods such as sandblast treatment, corona treatment, and plasma treatment are known as means for imparting sufficient adhesive strength to the thermoplastic resin.
  • a surface treatment step and a drying step must be provided, and there is a problem that productivity is lowered.
  • thermoplastic resin it is necessary to use a mold release agent when molding the thermoplastic resin with a mold, but since the surface of the thermoplastic resin is contaminated by this mold release agent, sufficient adhesion to the thermoplastic resin is achieved. Strength cannot be imparted. For this reason, a cleaning process and a polishing process for removing the release agent are required. As a result, there is a problem of cost increase such as capital investment and running cost for performing these steps.
  • the present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a method for producing a surface-modified thermoplastic resin in which sufficient adhesive strength is imparted to the thermoplastic resin.
  • the present invention provides a method for producing a bonded structure capable of exhibiting sufficient adhesive strength, in which a surface-modified thermoplastic resin obtained by such a production method is laminated on an adherend via an adhesive layer. It is to provide.
  • this invention is providing the junction structure which can express sufficient adhesive strength.
  • this invention is providing the thermal transfer surface modification sheet which can be preferably employ
  • this invention is providing the thermoplastic resin with a thermal transfer surface modification sheet
  • this invention is providing the surface modification thermoplastic resin to which sufficient adhesive strength was provided to the thermoplastic resin.
  • the method for producing the surface-modified thermoplastic resin of the present invention comprises: A method for producing a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin having a melting point of T ° C, An easy adhesion layer is provided on at least a part of the surface of the thermoplastic resin, and heat welding is performed at a temperature of (T-50) ° C. or higher.
  • the heat welding is performed by a hot press.
  • thermoplastic resin is molded by the heating press.
  • the easy adhesion layer side of the thermal transfer surface modified sheet which is a laminate of a release sheet and an easy adhesion layer, is placed on at least a part of the surface of the thermoplastic resin to facilitate adhesion. Provide a layer.
  • the release sheet is removed after the heat welding.
  • the method for producing the surface-modified thermoplastic resin of the present invention comprises: A method for producing a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin, After making at least a part of the surface of the thermoplastic resin into a molten state, an easy-adhesion layer is provided on the molten surface of the thermoplastic resin.
  • the easy-adhesion layer includes a polymer component, and the polymer component includes a polar unit including a nonpolar unit and a polar group.
  • the polymer component is at least one selected from a methoxymethyl group-containing polymer, a hydroxyl group-containing polymer, a carboxyl group-containing polymer, and an amino group-containing polymer.
  • the easy-adhesion layer contains at least one selected from tertiary amine-containing compounds and strong acids.
  • the method for producing a bonded structure according to the present invention includes: A surface-modified thermoplastic resin (A) obtained by the production method of the present invention is a method for producing a bonded structure in which an adherend is laminated via an adhesive layer, An adhesive layer is provided on the surface of the surface-modified thermoplastic resin (A) on the easy-adhesion layer side and bonded to the adherend.
  • the component of the adhesive layer has a functional group that reacts with a polar group.
  • the adherend is a surface-modified thermoplastic resin (B) obtained by the production method of the present invention, and the adherend is the surface-modified thermoplastic resin (B).
  • An adhesive layer is laminated on the surface of the easy adhesion layer side.
  • thermoplastic resin constituting the surface-modified thermoplastic resin (A) is different from the thermoplastic resin constituting the surface-modified thermoplastic resin (B).
  • the bonded structure of the present invention is A bonded structure having, in this order, a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin, an adhesive layer, and a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin Because A tensile shear adhesive force between the two surface-modified thermoplastic resins at 25 ° C. and a tensile speed of 5 mm / min is defined as P (Pa), and the thermoplastic resin and the adhesive layer constituting the surface-modified thermoplastic resin, When the tensile shear adhesive force at 25 ° C. and a tensile speed of 5 mm / min between the two thermoplastic resins in the joined structure having the thermoplastic resins constituting the surface-modified thermoplastic resin in this order is P0 (Pa). In addition, P / P0> 2.
  • the bonded structure of the present invention is A bonded structure having, in this order, a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin, an adhesive layer, and a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin Because When the two surface-modified thermoplastic resins are pulled at 25 ° C. and a tensile speed of 5 mm / min to break the bonded structure, at least one of the adhesive layer and the two surface-modified thermoplastic resins Destruction occurs.
  • the thermal transfer surface modified sheet of the present invention is a laminate of a release sheet and an easy adhesion layer.
  • the thermal transfer surface-modified sheet of the present invention is used in the method for producing a surface-modified thermoplastic resin of the present invention.
  • the easy-adhesion layer includes a polymer component, and the polymer component includes a polar unit including a nonpolar unit and a polar group.
  • the polymer component is at least one selected from a methoxymethyl group-containing polymer, a hydroxyl group-containing polymer, a carboxyl group-containing polymer, and an amino group-containing polymer.
  • the easy-adhesion layer contains at least one selected from tertiary amine-containing compounds and strong acids.
  • thermoplastic resin with a thermal transfer surface modified sheet of the present invention is such that the thermal transfer surface modified sheet is the surface of the thermoplastic resin such that the easy adhesion layer side of the thermal transfer surface modified sheet of the present invention is the surface side of the thermoplastic resin. It has been placed on.
  • the surface-modified thermoplastic resin of the present invention is A surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin, A mixed layer in which the thermoplastic resin and the easy-adhesion layer are mixed is provided between the thermoplastic resin and the easy-adhesion layer, The thickness of the mixed layer is 1.5 nm or more.
  • a method for producing a surface-modified thermoplastic resin in which sufficient adhesive strength is imparted to the thermoplastic resin can be provided. Further, the present invention provides a method for producing a bonded structure capable of exhibiting sufficient adhesive strength, in which a surface-modified thermoplastic resin obtained by such a production method is laminated on an adherend via an adhesive layer. Can be provided. Moreover, this invention can provide the joining structure which can express sufficient adhesive strength. Furthermore, this invention can provide the thermal transfer surface modification sheet which can be preferably employ
  • thermoplastic resin It is a schematic sectional drawing which shows an example of a surface modification thermoplastic resin. It is a schematic sectional drawing which shows an example of a thermal transfer surface modification sheet. It is a schematic sectional drawing which shows the form which mounts this easily bonding layer side of the thermal transfer surface modification sheet
  • the first method for producing a surface-modified thermoplastic resin of the present invention is a method for producing a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin. That is, the first method for producing a surface-modified thermoplastic resin of the present invention may be a method for treating the surface of a thermoplastic resin (a method for treating a surface of a thermoplastic resin).
  • first method for producing a surface-modified thermoplastic resin of the present invention strong adhesive strength can be obtained, and preferably, a surface treatment step as conventionally performed can be reduced. Further, in one embodiment of the first method for producing a surface-modified thermoplastic resin of the present invention, by performing surface treatment simultaneously with the molding process, the use of a release agent becomes unnecessary, and the release agent removing step (Sandblasting, degreasing, etc.) can be reduced.
  • thermoplastic resin of the present invention when the melting point of the thermoplastic resin is T ° C., an easy-adhesion layer is provided on at least a part of the surface of the thermoplastic resin, and (T ⁇ 50) Heat welding is performed at a temperature equal to or higher than ° C.
  • an easy adhesion layer is provided on at least a part of the surface of the thermoplastic resin.
  • At least a part of the surface of the thermoplastic resin means at least a part of all the surfaces of the thermoplastic resin.
  • the thermoplastic resin is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface thereof, the whole of at least one surface thereof, or the like.
  • thermoplastic resin any appropriate thermoplastic resin can be adopted as long as the effects of the present invention can be exhibited.
  • thermoplastic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), and POM (polyacetal).
  • PEEK polyetheretherketone
  • PC polycarbonate
  • thermoplastic resin a fiber reinforced thermoplastic resin (FRTP) can be adopted.
  • FRTP fiber reinforced thermoplastic resin
  • CFRTP carbon fiber reinforced thermoplastic resin
  • GFRTP glass fiber reinforced thermoplastic resin
  • CFRTP carbon fiber reinforced thermoplastic resin
  • a carbon fiber reinforced thermoplastic resin include a PPS carbon fiber reinforced thermoplastic resin, a PA carbon fiber reinforced thermoplastic resin, and a PP carbon fiber reinforced thermoplastic resin.
  • any appropriate glass fiber reinforced thermoplastic resin may be employed as the glass fiber reinforced thermoplastic resin (GFRTP).
  • examples of such glass fiber reinforced thermoplastic resin include PPS glass fiber reinforced thermoplastic resin, PA glass fiber reinforced thermoplastic resin, and PP glass fiber reinforced thermoplastic resin.
  • thermoplastic resin any appropriate shape can be adopted as long as the effects of the present invention are not impaired.
  • a shape include a flat plate shape, a curved plate shape, a sheet shape, and a film shape.
  • any appropriate thickness can be adopted depending on the purpose and within a range not impairing the effects of the present invention.
  • a thickness is, for example, 0.001 mm to 10 mm.
  • any suitable method can be used as long as the effect of the present invention is not impaired.
  • a method may be employed. Examples of such a method include, for example, a method in which a solution containing an easy-adhesion layer material and a solvent is applied to at least a part of the surface of the thermoplastic resin, and an easy-adhesion layer is melt-extruded on at least a part of the surface of the thermoplastic resin. And a method of laminating an easy-adhesion layer in the form of a sheet on at least a part of the surface of the thermoplastic resin.
  • any appropriate method can be adopted as a method of applying the solution containing the material of the easy-adhesion layer and the solvent as long as the effects of the present invention are not impaired.
  • Examples of such a method include dipping a thermoplastic resin into a solution containing an easy-adhesion layer material and a solvent, and brushing a solution containing the material and the solvent in an easy-adhesion layer on at least a part of the surface of the thermoplastic resin.
  • Coating, coating with various coaters of a solution containing an easy-adhesion layer material and solvent on at least a part of the surface of the thermoplastic resin, a solution containing an easy-adhesion layer material and solvent on at least a part of the surface of the thermoplastic resin For example, spray coating.
  • Examples of the solution containing the material for the easy-adhesion layer and the solvent include a solution obtained by dissolving the material for the easy-adhesion layer in any appropriate solvent as long as the effects of the present invention are not impaired.
  • any appropriate solvent can be adopted as long as the effects of the present invention are not impaired.
  • solvents include alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic, and aromatic hydrocarbons; halogenated hydrocarbons; dimethylformamide and the like.
  • One type of solvent may be sufficient and 2 or more types may be sufficient as it.
  • the solid content concentration in the solution containing the material of the easy-adhesion layer and the solvent can be appropriately set according to the purpose. From the viewpoint of ease of handling and the like, the solid content concentration is preferably 0.01 wt% to 20 wt%, more preferably 0.05 wt% to 10 wt%, as a weight ratio. More preferably, it is 0.1 to 5% by weight.
  • the solution containing the easy-adhesive layer material and the solvent may contain any appropriate other component as long as the effects of the present invention are not impaired.
  • the easy-adhesion layer (may be a material for the easy-adhesion layer) has any appropriate component as long as the effects of the present invention are not impaired.
  • a component preferably comprises a polymer component, the polymer component having a polar unit comprising a nonpolar unit and a polar group.
  • the content ratio of the polymer component in the easy-adhesion layer is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and further preferably 90% by weight to 100% by weight. Particularly preferred is 92 to 100% by weight, and most preferred is 95 to 100% by weight.
  • non-polar unit in the polymer component any appropriate non-polar polymer unit can be adopted as long as the effects of the present invention are not impaired.
  • nonpolar units include a polyethylene unit, a polypropylene unit, and a polystyrene unit. Only one type of nonpolar unit may be used, or two or more types may be used.
  • any appropriate polymer unit having a polar group can be adopted as long as the effects of the present invention are not impaired.
  • polar groups include epoxy groups, carboxyl groups, nitrile groups, amide groups, ester groups, hydroxyl groups, acid anhydrides, silanol groups, and the like.
  • polar units having such polar groups include glycidyl methacrylate units, vinyl acetate units, acrylonitrile units, amide units, (meth) acrylic acid ester units, hydroxyethyl (meth) acrylate units, maleic anhydride units, and the like. Can be mentioned. Only one type of polar unit may be used, or two or more types may be used.
  • the polymer component that may be included in the easy adhesion layer (which may be a material for the easy adhesion layer) is at least one selected from a methoxymethyl group-containing polymer, a hydroxyl group-containing polymer, a carboxyl group-containing polymer, and an amino group-containing polymer. Also good.
  • Such a polymer component that may be included in the easy adhesion layer (which may be a material of the easy adhesion layer) is preferably an addition type curing agent, more preferably an addition type curing agent that reacts with an epoxy group. .
  • methoxymethyl group-containing polymer any appropriate polymer can be adopted as long as it contains a methoxymethyl group (—CH 2 —OCH 3 ) without impairing the effects of the present invention.
  • methoxymethyl group-containing polymer include methoxymethylated polyamide resin.
  • methoxymethyl group-containing polymer examples include “Fine Resin” (registered trademark) series (manufactured by Lead City Corporation).
  • the methoxymethyl group-containing polymer may be one type or two or more types.
  • the methoxymethyl group-containing polymer has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and even more preferably 5,000 to 1,000, in that the effects of the present invention can be further exhibited. 100000, particularly preferably 7000 to 70000, and most preferably 10,000 to 50000. A method for measuring the weight average molecular weight (Mw) will be described later.
  • any appropriate polymer can be adopted as long as it is a polymer containing a hydroxyl group (—OH) as long as the effects of the present invention are not impaired.
  • a hydroxyl group-containing polymer include a hydroxyl group-containing acrylic polymer.
  • hydroxyl group-containing polymer examples include “ARUFON (registered trademark) UH-2000 series” (manufactured by Toa Gosei Co., Ltd.).
  • the hydroxyl group-containing polymer may be one type or two or more types.
  • the hydroxyl group-containing polymer has a weight average molecular weight (Mw) of preferably from 500 to 1,000,000, more preferably from 700 to 500,000, and even more preferably from 1,000 to 100,000, from the viewpoint that the effects of the present invention can be further exhibited. Particularly preferably 1500 to 70000, most preferably 2000 to 50000. A method for measuring the weight average molecular weight (Mw) will be described later.
  • carboxyl group-containing polymer any appropriate polymer can be adopted as long as it contains a carboxyl group (—COOH) as long as the effects of the present invention are not impaired.
  • carboxyl group-containing polymers include carboxyl group-containing acrylic polymers.
  • carboxyl group-containing polymer examples include “ARUFON (registered trademark) UC-3000 series” (manufactured by Toa Gosei Co., Ltd.).
  • the carboxyl group-containing polymer may be one type or two or more types.
  • the carboxyl group-containing polymer has a weight average molecular weight (Mw) of preferably 500 to 1,000,000, more preferably 700 to 500,000, and still more preferably 1,000 to 100,000, in that the effects of the present invention can be further exhibited. And particularly preferably 1500 to 70000, most preferably 2000 to 50000.
  • Mw weight average molecular weight
  • a molecular weight in terms of polystyrene in GPC measurement was used.
  • amino group-containing polymer any appropriate polymer can be adopted as long as it contains an amino group (—NH 2 ) as long as the effects of the present invention are not impaired.
  • the amino group-containing polymer may be one type or two or more types.
  • the easy-adhesion layer (may be a material for the easy-adhesion layer) may contain at least one selected from tertiary amine-containing compounds and strong acids.
  • Such a tertiary amine-containing compound or strong acid that may be contained in the easy-adhesion layer is preferably a catalyst-type curing agent, more preferably a catalyst that reacts with an epoxy group. Mold curing agent.
  • tertiary amine-containing compound any appropriate compound can be adopted as long as it is a compound containing a tertiary amine as long as the effects of the present invention are not impaired.
  • tertiary amine-containing compounds include imidazole derivatives and polyethyleneimine.
  • tertiary amine-containing compound Commercially available products may be adopted as the tertiary amine-containing compound. Examples of such commercially available products include “Cureazole” series (imidazole epoxy resin curing agent, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as imidazole derivatives, and “Epomin” (registered trademark) series as polyethyleneimine. (Manufactured by Nippon Shokubai Co., Ltd.).
  • the tertiary amine-containing compound may be one kind or two or more kinds.
  • any appropriate strong acid can be adopted as long as the effects of the present invention are not impaired.
  • Examples of such strong acid include trifluoroborane, ionic liquid, and Nafion.
  • Examples of the ionic liquid include BF 3 —C 2 H 5 NH 2 , HMI-PF 6 and the like.
  • the strong acid may be one type or two or more types.
  • At least a part of the solvent is removed by drying.
  • any appropriate method can be adopted as long as the method can remove the solvent, such as oven heating, infrared heating, and high-frequency heating, as long as the effects of the present invention are not impaired.
  • the drying temperature any appropriate temperature can be appropriately set according to the boiling point of the solvent to be used.
  • any appropriate method can be adopted as long as the effects of the present invention are not impaired.
  • Examples of such a method include a method of melt-extruding the material of the easy-adhesion layer onto at least a part of the surface of the thermoplastic resin with a melt extruder or the like.
  • any appropriate method can be adopted as a method of laminating the easily adhesive layer in the form of a sheet as long as the effects of the present invention are not impaired.
  • a method for example, at least a part of the surface of the thermoplastic resin is coated with a thermal transfer surface-modified sheet (e.g., a release sheet and an easy-to-release sheet) described in detail in the section ⁇ Third surface treatment method of the present invention>.
  • a method of laminating the easy-adhesion layer side of the laminate of the adhesive layers is a thermal transfer surface-modified sheet (e.g., a release sheet and an easy-to-release sheet) described in detail in the section ⁇ Third surface treatment method of the present invention>.
  • thermoplastic resin of the present invention when the melting point of the thermoplastic resin is T ° C., an easy-adhesion layer is provided on at least a part of the surface of the thermoplastic resin, and (T ⁇ 50) Heat welding is performed at a temperature equal to or higher than ° C.
  • the heat welding temperature is preferably (T ⁇ 50) ° C. to (T + 150) ° C., more preferably (T ⁇ 25) ° C. to (T + 100) ° C., and further preferably (T ⁇ 10) ° C. (T + 75) ° C., particularly preferably (T) ° C. to (T + 50) ° C.
  • thermoplastic resin By performing the surface treatment of the thermoplastic resin by the method as described above with the heating welding temperature within the above range, the interface between the easy adhesion layer and the thermoplastic resin is melt-contacted and welded and mixed, which is sufficient for the thermoplastic resin.
  • Adhesive strength can be imparted, and preferably such impartation can be performed with high productivity and low cost.
  • Any appropriate method can be adopted as a method of heat welding as long as the effect of the present invention can be exhibited.
  • Examples of such a method include oven heating, infrared heating, high-frequency heating, and heating press, and the heating press is preferable because the effects of the present invention can be further exhibited.
  • any appropriate time can be adopted as the heat welding time as long as the effects of the present invention can be exhibited.
  • the time is preferably 1 second to 10 minutes from the viewpoint that the effects of the present invention can be further exhibited.
  • an easy-adhesion layer 10 is provided on the surface of the thermoplastic resin 100, and a surface-modified thermoplastic resin (with a thermoplastic resin and May be referred to as a laminated member of an easily adhesive layer).
  • the easy adhesion layer 10 is laminated on the surface of the thermoplastic resin 100, but preferably, the thermoplastic resin and the easy adhesion layer are interposed between the thermoplastic resin 100 and the easy adhesion layer 10.
  • a mixed layer (not shown) in which the layers are mixed is provided. The thickness of this mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more.
  • the thickness of the easy-adhesion layer any appropriate thickness can be adopted depending on the purpose and within a range not impairing the effects of the present invention.
  • the thickness is preferably 0.001 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 10 ⁇ m, and still more preferably 0.05 ⁇ m to 5 ⁇ m, from the viewpoint that the effects of the present invention can be further exhibited.
  • the thickness is 0.1 ⁇ m to 3 ⁇ m.
  • the manufacturing method of the 2nd surface modification thermoplastic resin of this invention is a manufacturing method of the surface modification thermoplastic resin by which the easily bonding layer was laminated
  • thermoplastic resin of the present invention After at least a part of the surface of the thermoplastic resin is in a molten state, an easy adhesion layer is provided on the molten surface of the thermoplastic resin.
  • an easy adhesion layer is provided on the molten surface of the thermoplastic resin.
  • thermoplastic resin of the present invention At least a part of the surface of the thermoplastic resin is in a molten state.
  • thermoplastic resin As the “at least part of the surface of the thermoplastic resin”, the description in the section ⁇ Method for producing the first surface-modified thermoplastic resin of the present invention> can be directly used.
  • thermoplastic resin the description in the section ⁇ Method for producing first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • the “molten state” is a state in which at least a part of the surface of the thermoplastic resin is melted, and can be preferably achieved by bringing the thermoplastic resin to a temperature equal to or higher than its melting point.
  • thermoplastic resin of the present invention After at least a part of the surface of the thermoplastic resin is in a molten state, an easy adhesion layer is provided on the molten surface of the thermoplastic resin.
  • an easy-adhesion layer By providing an easy-adhesion layer on the molten surface of the thermoplastic resin, the easy-adhesion layer can be welded and mixed by the heat of the surface of the thermoplastic resin, and sufficient adhesive strength can be imparted to the thermoplastic resin, preferably Such an application can be performed with high productivity and low cost.
  • the description in the section ⁇ Method for producing the first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • examples of the method for providing an easy-adhesion layer on the surface of the thermoplastic resin in a molten state include, for example, thermal transfer which is a laminate of a release sheet and an easy-adhesion layer.
  • thermal transfer which is a laminate of a release sheet and an easy-adhesion layer.
  • the third method for producing a surface-modified thermoplastic resin of the present invention is a method for producing a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin. That is, the third method for producing a surface-modified thermoplastic resin of the present invention may be a method for treating the surface of a thermoplastic resin (a method for treating a surface of a thermoplastic resin).
  • the easy adhesion of the thermal transfer surface-modified sheet which is a laminate of a release sheet and an easy-adhesion layer, on at least a part of the surface of the thermoplastic resin.
  • the layer side is placed and heat welding is performed.
  • the easy adhesion of the thermal transfer surface-modified sheet which is a laminate of a release sheet and an easy-adhesion layer, on at least a part of the surface of the thermoplastic resin. Place the layer side.
  • thermoplastic resin As the “at least part of the surface of the thermoplastic resin”, the description in the section ⁇ Method for producing the first surface-modified thermoplastic resin of the present invention> can be directly used.
  • thermoplastic resin the description in the section ⁇ Method for producing first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • the description in the section ⁇ Method for producing the first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • the thermal transfer surface modified sheet which is a laminate of the release sheet and the easy adhesion layer
  • a thermal transfer surface modified sheet 200 which is a laminate of the release sheet 20 and the easy adhesion layer 10, as shown in FIG.
  • thermoplastic resin of the present invention at least one surface of the thermoplastic resin is disposed on the side of the easy-adhesion layer of the thermal transfer surface-modification sheet, which is a laminate of a release sheet and an easy-adhesion layer.
  • the thermal transfer surface modified sheet 200 is placed on the heat transfer surface modified sheet 200 such that the easy-adhesion layer 10 side of the thermal transfer surface modified sheet 200 is the surface side of the thermoplastic resin 100.
  • the modified sheet 200 is placed on the surface of the thermoplastic resin 100.
  • the thermal transfer surface-modified sheet can be produced by any appropriate method as long as the effects of the present invention are not impaired.
  • a method of drying the release sheet as needed after dipping the release sheet into a solution containing the material of the easy-adhesion layer and a solvent, the material and solvent of the easy-adhesion layer on the surface of the release sheet A method of drying as needed after brush coating of a solution containing, a method of drying as necessary after application of a solution containing an easy-adhesive layer material and a solvent to the surface of the release sheet by various coaters, mold release Examples of the method include a method of drying, if necessary, after spray coating of a solution containing the material of the easy-adhesion layer and the solvent on the surface of the sheet.
  • the description in the section of ⁇ the 1st surface treatment method of this invention> can be employ
  • any appropriate release sheet can be adopted as long as the effects of the present invention are not impaired.
  • a release sheet for example, a fluororesin sheet film (Nitto Denko, Nitoflon), a polyester resin sheet, a polymethylpentene resin sheet (Mitsui Chemicals Tosero, Opulan (registered trademark)), a polystyrene resin sheet (Kurabo) Manufactured, Eudis (registered trademark)) and the like.
  • the thickness of the release sheet is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 20 ⁇ m to 250 ⁇ m, and particularly preferably 50 ⁇ m to 50 ⁇ m from the viewpoint that the effects of the present invention can be further exhibited. 200 ⁇ m.
  • thermoplastic resin of the present invention when an easy-adhesion layer is provided on at least a part of the surface of the thermoplastic resin, any appropriate device is used as long as the effects of the present invention are not impaired. Can be adopted.
  • an easy-adhesion layer may be provided on at least a part of the surface of a thermoplastic resin in a molding machine (for example, a press).
  • the easy-adhesion layer side of the thermal transfer surface-modified sheet is placed on at least a part of the surface of the thermoplastic resin, and heat welding is performed. .
  • heat welding may be performed simultaneously with the placement of the thermal transfer surface modified sheet or after the thermal transfer surface modified sheet is placed.
  • thermoplastic resin of the present invention for example, at least a part of the surface of the thermoplastic resin in a molding machine (for example, a press machine).
  • a molding machine for example, a press machine.
  • the easy-adhesion layer side of the thermal transfer surface modified sheet is placed on the surface, and a molding process (for example, heating press) with heating is performed.
  • a molding process for example, heating press
  • the heat welding is preferably performed at a temperature of (T-50) ° C. or higher, where the melting point of the thermoplastic resin is T ° C. Do.
  • the heat welding temperature is more preferably (T-50) ° C. to (T + 150) ° C., further preferably (T ⁇ 25) ° C. to (T + 100) ° C., and particularly preferably (T ⁇ 10) ° C. (T + 75) ° C., most preferably (T) ° C. to (T + 50) ° C.
  • the interface between the easy-adhesion layer of the thermal transfer surface modified sheet and the thermoplastic resin is melt-contacted and welded and mixed, and sufficient adhesive strength can be imparted by the thermoplastic resin.
  • such application can be performed with high productivity and low cost.
  • Any appropriate method can be adopted as a method of heat welding as long as the effect of the present invention can be exhibited.
  • Examples of such a method include oven heating, infrared heating, high-frequency heating, and heating press, and the heating press is preferable because the effects of the present invention can be further exhibited.
  • any appropriate time can be adopted as the heat welding time as long as the effects of the present invention can be exhibited.
  • the time is preferably 1 second to 10 minutes from the viewpoint that the effects of the present invention can be further exhibited.
  • the release sheet After placing the easy-adhesion layer side of the thermal transfer surface modified sheet, which is a laminate of the release sheet and the easy-adhesion layer, on at least a part of the surface of the thermoplastic resin, and preferably heat-welding, the release sheet is preferably Removed. By removing the release sheet in this way, the easy-adhesion layer is transferred to the surface of the thermoplastic resin, and a surface-modified thermoplastic resin (sometimes referred to as a laminated member of the thermoplastic resin and the easy-adhesion layer). can get.
  • a mixed layer in which the thermoplastic resin and the easy adhesion layer are mixed is provided between the thermoplastic resin and the easy adhesion layer. The thickness of this mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more.
  • thermoplastic resin joining method of the present invention since the thermoplastic resin has been surface-treated by the surface treatment method of the present invention, it is well-familiar with the adhesive layer and is well bonded to various adherends. It becomes possible to do.
  • any appropriate adhesive layer can be adopted as the adhesive layer as long as the effects of the present invention are not impaired.
  • Such an adhesive layer preferably has a functional group in which a component of the adhesive layer reacts with a polar group in that the effect of the present invention can be further expressed. When such an adhesive layer is employed, the effects of the present invention can be further exhibited.
  • any appropriate functional group can be adopted as long as the effects of the present invention are not impaired.
  • functional groups include epoxy groups, carboxyl groups, acid anhydride groups, amino groups, hydroxyl groups, silanol groups, and isocyanate groups.
  • an epoxy group is preferable because the effects of the present invention can be further expressed.
  • the thickness of the adhesive layer is preferably 1 ⁇ m to 5000 ⁇ m, more preferably 10 ⁇ m to 2000 ⁇ m, still more preferably 50 ⁇ m to 1000 ⁇ m, and particularly preferably 100 ⁇ m to 1000 ⁇ m, from the viewpoint that the effects of the present invention can be further exhibited. 500 ⁇ m.
  • the surface-modified thermoplastic resin of the present invention is a surface-modified thermoplastic resin in which an easy adhesion layer is laminated on a thermoplastic resin, and the thermoplastic resin and the easy adhesion layer are interposed between the thermoplastic resin and the easy adhesion layer.
  • a mixed layer mixed with an easy-adhesion layer is provided, and the thickness of the mixed layer is 1.5 nm or more.
  • thermoplastic resin the description in the section ⁇ Method for producing first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • the description in the section ⁇ Method for producing the first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • the mixed layer is a layer in which a thermoplastic resin and the easy-adhesion layer are mixed.
  • an easy-adhesion layer is formed by providing an easy-adhesion layer on at least a part of the surface of the thermoplastic resin and performing easy welding. The interface between the layer and the thermoplastic resin is in contact with the melt and is welded and mixed, whereby the welded mixed layer is obtained.
  • the thickness of the mixed layer can be appropriately determined according to the heat welding conditions and the kind of the thermoplastic resin or the easily adhesive layer.
  • the thickness of the mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more.
  • any appropriate thickness can be adopted as the thickness of the thermoplastic resin depending on the purpose and within a range not impairing the effects of the present invention.
  • a thickness is, for example, 0.001 mm to 10 mm.
  • any appropriate thickness can be adopted as the thickness of the easy-adhesion layer depending on the purpose and within a range not impairing the effects of the present invention.
  • the thickness is preferably 0.001 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 10 ⁇ m, and still more preferably 0.05 ⁇ m to 5 ⁇ m, from the viewpoint that the effects of the present invention can be further exhibited.
  • the thickness is 0.1 ⁇ m to 3 ⁇ m.
  • the surface-modified thermoplastic resin of the present invention is preferably obtained by the method for producing a surface-modified thermoplastic resin of the present invention.
  • the method for producing a joined structure of the present invention is a method for producing a joined structure in which the surface-modified thermoplastic resin (A) obtained by the production method of the present invention is laminated on an adherend via an adhesive layer. Then, an adhesive layer is provided on the surface of the surface-modified thermoplastic resin (A) on the easy-adhesion layer side and bonded to the adherend.
  • the component of the adhesive layer preferably has a functional group that reacts with a polar group.
  • a functional group that reacts with a polar group When such an adhesive layer is employed, the effects of the present invention can be further exhibited.
  • any appropriate functional group can be adopted as long as the effects of the present invention are not impaired.
  • functional groups include epoxy groups, carboxyl groups, acid anhydride groups, amino groups, hydroxyl groups, silanol groups, and isocyanate groups.
  • an epoxy group is preferable because the effects of the present invention can be further expressed.
  • the thickness of the adhesive layer is preferably 1 ⁇ m to 5000 ⁇ m, more preferably 10 ⁇ m to 2000 ⁇ m, still more preferably 50 ⁇ m to 1000 ⁇ m, and particularly preferably 100 ⁇ m to 1000 ⁇ m, from the viewpoint that the effects of the present invention can be further exhibited. 500 ⁇ m.
  • the adherend is a surface-modified thermoplastic resin (B) obtained by the production method of the present invention, and the surface modification is the adherend.
  • An adhesive layer is laminated on the surface of the thermoplastic resin (B) on the easy adhesive layer side.
  • the surface-modified thermoplastic resin (B) means a surface-modified thermoplastic resin different from the aforementioned surface-modified thermoplastic resin (A).
  • the thermoplastic resin constituting the surface-modified thermoplastic resin (A) is different from the thermoplastic resin constituting the surface-modified thermoplastic resin (B).
  • the bonded structure of the present invention includes a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin, an adhesive layer, and a surface-modified thermoplastic resin in which an easy-adhesion layer is laminated on a thermoplastic resin. , In this order.
  • the easy adhesion layer side of each of the two surface-modified thermoplastic resins is bonded to the adhesive layer. That is, as one embodiment, as shown in FIG. 4, the joint structure 1000 of the present invention is a laminate of a surface-modified thermoplastic resin 500, an adhesive layer 300, and a surface-modified thermoplastic resin 500. .
  • any appropriate adhesive layer can be adopted as the adhesive layer of the bonded structure of the present invention as long as the effects of the present invention are not impaired.
  • Such an adhesive layer preferably has a functional group that reacts with the polar group of the easy-adhesion layer in that the effect of the present invention can be further expressed.
  • any appropriate functional group can be adopted as long as the effects of the present invention are not impaired.
  • functional groups include epoxy groups, carboxyl groups, acid anhydride groups, amino groups, hydroxyl groups, silanol groups, and isocyanate groups.
  • an epoxy group is preferable because the effects of the present invention can be further expressed.
  • the thickness of the adhesive layer is preferably 1 ⁇ m to 5000 ⁇ m, more preferably 10 ⁇ m to 2000 ⁇ m, still more preferably 50 ⁇ m to 1000 ⁇ m, and particularly preferably 100 ⁇ m to 1000 ⁇ m, from the viewpoint that the effects of the present invention can be further exhibited. 500 ⁇ m.
  • the bonded structure of the present invention is preferably composed of two surface-modified thermoplastic resins having a tensile shear adhesive strength at 25 ° C. and a tensile speed of 5 mm / min as P (Pa). Tensile shear at 25 ° C. and a tensile speed of 5 mm / min between the two thermoplastic resins in a joined structure having in this order the thermoplastic resin to be bonded, the adhesive layer, and the thermoplastic resin constituting the surface-modified thermoplastic resin
  • the adhesive strength is P0 (Pa)
  • P / P0> 2 more preferably P / P0> 2.5, still more preferably P / P0> 3.0, and particularly preferably P. /P0>3.5, most preferably P / P0> 4.0.
  • the / P0 is in the above range, the bonded structure of the present invention can exhibit more sufficient adhesive strength.
  • the bonded structure of the present invention is preferably formed by pulling two surface-modified thermoplastic resins to each other at 25 ° C. and a tensile speed of 5 mm / min to break the bonded structure and the two surface-modified thermoplastic resins. Breakage occurs in at least one of the thermoplastic resins. By having such characteristics, the bonded structure of the present invention can exhibit more sufficient adhesive strength.
  • the thermal transfer surface modified sheet of the present invention is a laminate of a release sheet and an easy adhesion layer. Specifically, it is a thermal transfer surface-modified sheet 200 that is a laminate of the release sheet 20 and the easy adhesion layer 10 as shown in FIG.
  • the thermal transfer surface-modified sheet of the present invention preferably has its heat-adhesive layer side placed on at least a part of the surface of the thermoplastic resin, heat-welded, and then the release sheet is removed to remove the heat transfer layer.
  • the easy-adhesion layer is transferred to the surface of the plastic resin to obtain a surface-modified thermoplastic resin.
  • the use of the thermal transfer surface-modified sheet of the present invention makes it possible to easily produce a surface-modified thermoplastic resin, and imparts sufficient adhesive strength to the thermoplastic resin with high productivity and low cost. be able to.
  • the description in the section ⁇ Method for producing the first surface-modified thermoplastic resin of the present invention> can be used as it is.
  • thermoplastic resin with a thermal transfer surface modified sheet of the present invention is such that the thermal transfer surface modified sheet is the surface of the thermoplastic resin such that the easy adhesion layer side of the thermal transfer surface modified sheet of the present invention is the surface side of the thermoplastic resin. Is laminated. That is, as shown in FIG. 5, the thermoplastic resin 800 with a thermal transfer surface modification sheet of the present invention has an easy adhesion layer 10 side of the thermal transfer surface modification sheet 200, which is a laminate of the release sheet 20 and the easy adhesion layer 10. It is laminated on the surface of the thermoplastic resin 100.
  • thermoplastic resin with a thermal transfer surface modified sheet of the present invention can be used as it is in the method for producing a surface modified thermoplastic resin of the present invention. That is, for example, when the melting point of the thermoplastic resin in the thermoplastic resin with a thermal transfer surface modified sheet of the present invention is T ° C., heating is performed at a temperature of (T-50) ° C. or higher, and then preferably the mold release is performed. The sheet is removed. By removing the release sheet in this manner, an easy adhesion layer is provided on the surface of the thermoplastic resin, and a surface-modified thermoplastic resin is obtained. By performing the surface treatment of the thermoplastic resin by such a method, sufficient adhesive strength can be imparted to the thermoplastic resin, preferably with high productivity and low cost.
  • the first surface treatment method of the present invention is a method of treating the surface of a thermoplastic resin, and when the melting point of the thermoplastic resin is T ° C., the surface of the thermoplastic resin is treated.
  • An easy-adhesion layer is provided at least in part, and heat welding is performed at a temperature of (T-50) ° C. or higher.
  • the second surface treatment method of the present invention is a method of treating the surface of a thermoplastic resin, and after making at least a part of the surface of the thermoplastic resin into a molten state, the thermoplastic resin An easy adhesion layer is provided on the surface of the molten resin.
  • the method of providing the easy-adhesion layer on the surface of the thermoplastic resin in a molten state is the easy-adhesion layer side of the thermal transfer surface-modified sheet, which is a laminate of a release sheet and the easy-adhesion layer. Is placed on the molten surface of the thermoplastic resin.
  • the release sheet is removed after the above placement.
  • the easy-adhesion layer includes a polymer component, and the polymer component includes a polar unit including a nonpolar unit and a polar group.
  • thermoplastic resin joining method of the present invention is such that an adhesive layer is provided on the surface-treated surface of the surface-treated thermoplastic resin obtained by the surface treatment method of the present invention and joined to the adherend. .
  • the component of the adhesive layer has a functional group that reacts with a polar group.
  • the laminated member of the present invention is a laminated member of a thermoplastic resin and an easy adhesion layer obtained by the surface treatment method of the present invention.
  • the bonded structure of the present invention is a bonded structure having the laminated member of the present invention, the adhesive layer, and the laminated member of the present invention in this order, and each of the two laminated members is easily bonded.
  • the layer side is bonded to the adhesive layer.
  • the component of the adhesive layer has a functional group that reacts with a polar group.
  • the tensile shear adhesive force at 25 ° C. and a tensile speed of 5 mm / min between the two laminated members is P (Pa), and the thermoplastic resin, the adhesive layer, and the laminated material constituting the laminated member are used.
  • P (Pa) the tensile shear adhesive force at 25 ° C. and a tensile speed of 5 mm / min between the two thermoplastic resins in the joined structure having the thermoplastic resins constituting the members in this order.
  • the thermal transfer surface-modified sheet of the present invention is a laminate of a release sheet and an easy adhesion layer.
  • the easy-adhesion layer side is placed on the molten surface of a thermoplastic resin in which at least a part of the surface is in a molten state, and the release sheet is removed to remove the easy-to-adhere layer.
  • the adhesive layer is transferred to the surface of the thermoplastic resin.
  • the easy-adhesion layer includes a polymer component, and the polymer component includes a polar unit including a nonpolar unit and a polar group.
  • thermoplastic resin with a thermal transfer surface modification sheet of the present invention is such that the thermal transfer surface modification sheet of the thermal transfer surface modification sheet of the present invention is such that the easy adhesion layer side of the thermal transfer surface modification sheet is the surface side of the thermoplastic resin. It is laminated on the surface of the thermoplastic resin.
  • thermoplastic resin ⁇ Measurement of melting point T (°C) of thermoplastic resin ⁇
  • the melting point T (° C.) of the thermoplastic resins used in Examples and Comparative Examples was measured by DSC (differential scanning calorimeter) while increasing the temperature from ⁇ 90 ° C. to 350 ° C. at 2 ° C./min.
  • the melting point of polyphenylene sulfide (PPS) was 284 ° C.
  • the melting point of polypropylene (PP) was 167 ° C.
  • the melting point of 6-nylon (PA6) was 221 ° C.
  • the melting point of 6,6-nylon (PA66) was 260 ° C.
  • an epoxy adhesive manufactured by Nagase ChemteX, Denatite XNR3503
  • an adhesive tape Nitoflon, No. 973UL
  • the bonding area was 25 mm ⁇ 10 mm.
  • the curing condition of the adhesive was 100 ° C. ⁇ 30 minutes.
  • an acrylic adhesive (Y611black, manufactured by Cemedine Co., Ltd.) was used, and the adhesive area was 25 mm ⁇ 10 mm.
  • the curing condition of the adhesive was room temperature ⁇ 1 day or more.
  • an acrylic adhesive (C320K, manufactured by Denka Co., Ltd.) was used, and the adhesion area was 25 mm ⁇ 10 mm.
  • the curing condition of the adhesive was room temperature ⁇ 1 day or more.
  • ⁇ Shear adhesive strength The tensile shear adhesive strength between the two laminated members in the bonded structure was measured with a tensile tester (manufactured by Minebea, model number: TG-100 kN). The measurement was performed at 25 ° C. and a tensile speed of 5 mm / min. The obtained measured value was converted per unit area to obtain the shear adhesive strength. In addition, when an adherend fracture
  • Example A-1 Thermal transfer surface modified sheet (1)
  • Resin (1) Suditomo Chemical Co., Ltd., Bond First 7B (ethylene-glycidyl methacrylate-vinyl acetate copolymer)
  • a release sheet Nitoflon No. 900UL (thickness 0.18 mm)
  • a thermal transfer surface modified sheet (1) which is a release sheet provided with an easy adhesion layer, was prepared.
  • Example A-2 Thermal transfer surface modified sheet (2) An easy-adhesion layer was prepared in the same manner as in Example A-1, except that the resin (1) was changed to the resin (2) (Sumitomo Chemical Co., Ltd., Bond First CG5001 (ethylene-glycidyl methacrylate copolymer)). A thermal transfer surface modified sheet (2), which is a release sheet, was prepared.
  • Example A-3 Thermal transfer surface modified sheet (3) Except that resin (1) was changed to resin (3) (Fine-Blend SAG-005 (styrene-acrylonitrile-glycidyl methacrylate copolymer) manufactured by SUNNY FC), the same procedure as in Example A-1 was performed. A thermal transfer surface-modified sheet (3), which is a release sheet provided with an easy-adhesion layer, was produced.
  • resin (3) Fine-Blend SAG-005 (styrene-acrylonitrile-glycidyl methacrylate copolymer) manufactured by SUNNY FC
  • Example A-4 Thermal transfer surface modified sheet (4) Resin (1) was changed to Resin (4) (Fine Resin, Fine Resin FR-101 (methoxymethylated polyamide resin) / p-toluenesulfonic acid (PTS) (weight ratio 99/1 mixture))
  • Resin (4) Fine Resin, Fine Resin FR-101 (methoxymethylated polyamide resin) / p-toluenesulfonic acid (PTS) (weight ratio 99/1 mixture)
  • a thermal transfer surface modified sheet (4) which is a release sheet provided with an easy-adhesion layer, was produced in the same manner as in Example A-1, except that hot toluene (60 ° C.) was changed to methanol (normal temperature).
  • Example A-5 Thermal transfer surface modified sheet (5) Resin (1) was changed to Resin (5) (Fine Resin FR-101 (methoxymethylated polyamide resin) manufactured by Lead City Co., Ltd.) and hot toluene (60 ° C.) was changed to methanol (normal temperature).
  • Resin (5) Fine Resin FR-101 (methoxymethylated polyamide resin) manufactured by Lead City Co., Ltd.
  • hot toluene 60 ° C.
  • methanol normal temperature
  • Example A-6 Thermal transfer surface modified sheet (6) Resin (1) was changed to Resin (6) (Fine Resin, Fine Resin FR-105 (methoxymethylated polyamide resin)), and hot toluene (60 ° C.) was changed to methanol (normal temperature). In the same manner as in Example A-1, a thermal transfer surface modified sheet (6), which is a release sheet provided with an easy-adhesion layer, was produced.
  • Thermal transfer surface modified sheet (7) Resin (1) is Resin (7) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toa Gosei Co., Ltd., ARUFON (registered trademark) UH-2041 (hydroxyl group-containing acrylic polymer) (Weight ratio 50/50 mixture)), except that hot toluene (60 ° C.) was changed to methanol (room temperature) in the same manner as in Example A-1, with a release sheet having an easy-adhesion layer.
  • a thermal transfer surface modified sheet (7) was prepared.
  • Thermal transfer surface modified sheet (8) Resin (1) is resin (8) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toa Gosei Co., Ltd., ARUFON (registered trademark) UH-2170 (hydroxyl group-containing acrylic polymer) (Weight ratio 50/50 mixture)), except that hot toluene (60 ° C.) was changed to methanol (room temperature) in the same manner as in Example A-1, with a release sheet having an easy-adhesion layer. A thermal transfer surface modified sheet (8) was produced.
  • resin (8) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toa Gosei Co., Ltd., ARUFON (registered trademark) UH-2170 (hydroxyl group-containing acrylic polymer) (Weight ratio 50/50 mixture)
  • hot toluene 60 ° C.
  • methanol room temperature
  • Example A-9 Thermal transfer surface modified sheet (9) Resin (1) is replaced with Resin (9) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toa Gosei Co., Ltd., ARUFON (registered trademark) UC-3000 (carboxyl group-containing acrylic polymer) ) (50/50 mixture by weight)), and release sheet provided with an easy-adhesive layer in the same manner as in Example A-1, except that hot toluene (60 ° C.) was changed to methanol (room temperature).
  • a thermal transfer surface modified sheet (9) was prepared.
  • Thermal transfer surface modified sheet (10) Resin (1) is Resin (10) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toa Gosei Co., Ltd., ARUFON (registered trademark) UC-3150 (carboxyl group-containing acrylic polymer) ) (50/50 mixture by weight)), and release sheet provided with an easy-adhesive layer in the same manner as in Example A-1, except that hot toluene (60 ° C.) was changed to methanol (room temperature).
  • a thermal transfer surface modified sheet (10) was prepared.
  • Thermal transfer surface modified sheet (11) Resin (1) is resin (11) (Toa Gosei Co., Ltd., ARUFON (registered trademark) UH-2041 (hydroxyl group-containing acrylic polymer) / Toa Gosei Co., Ltd., ARUFON (registered trademark) UH-2170 (Hydroxyl group-containing acrylic) System polymer) (weight ratio 50/50 mixture)), and in the same manner as in Example A-1, except that hot toluene (60 ° C.) was changed to methanol (room temperature), a release layer equipped with an easy-adhesion layer.
  • Thermal transfer surface modified sheet (12) Resin (1) is resin (12) (Toa Gosei Co., Ltd., ARUFON (registered trademark) UC-3000 (carboxyl group-containing acrylic polymer) / Toa Gosei Co., Ltd. (ARUFON (registered trademark) UC-3150 (carboxyl group)) (Including acrylic polymer) (weight ratio 50/50 mixture)), and an easy-adhesion layer is provided in the same manner as in Example A-1, except that hot toluene (60 ° C.) is changed to methanol (normal temperature).
  • Example A-13 Thermal transfer surface modified sheet (13) Resin (1) is replaced with Resin (13) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Nippon Shokubai, Epomin (registered trademark) SP-200 (polyethyleneimine) (weight ratio) 50/50 mixture)) and heat transfer surface which is a release sheet having an easy-adhesion layer in the same manner as in Example A-1, except that hot toluene (60 ° C.) is changed to methanol (room temperature). A modified sheet (13) was produced.
  • Resin (13) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Nippon Shokubai, Epomin (registered trademark) SP-200 (polyethyleneimine) (weight ratio) 50/50 mixture)
  • heat transfer surface which is a release sheet having an easy-adhesion layer in the same manner as in Example A-1, except that hot toluene (60 ° C.) is
  • Example A-14 Thermal transfer surface modified sheet (14) Resin (1) is replaced with Resin (14) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curesol 2P4MHZ-PW (Imidazole-based epoxy resin curing agent) (weight) Thermal transfer that is a release sheet having an easy-adhesive layer in the same manner as in Example A-1, except that the mixture was changed to a 50/50 mixture)) and hot toluene (60 ° C.) was changed to methanol (room temperature). A surface modified sheet (14) was produced.
  • Resin (14) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curesol 2P4MHZ-PW (Imidazole-based epoxy resin curing agent) (weight) Thermal transfer that is a release sheet having an easy-adhesive
  • Example A-15 Thermal transfer surface modified sheet (15) Resin (1) is replaced with Resin (15) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Tokyo Chemical Industry Co., Ltd., trifluoroborane (BF 3 ) (weight ratio 50/50 mixture) )), Except that hot toluene (60 ° C.) is changed to methanol (room temperature), in the same manner as in Example A-1, a thermal transfer surface-modified sheet that is a release sheet having an easy-adhesion layer ( 15) was produced.
  • Resin (1) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Tokyo Chemical Industry Co., Ltd., trifluoroborane (BF 3 ) (weight ratio 50/50 mixture)
  • hot toluene 60 ° C.
  • methanol room temperature
  • Example A-16 Thermal transfer surface modified sheet (16) Resin (1) is replaced with Resin (16) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toyo Gosei Co., Ltd., HMI-PF 6 (ionic liquid) (weight ratio 50/50)
  • Resin (16) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Toyo Gosei Co., Ltd., HMI-PF 6 (ionic liquid) (weight ratio 50/50)
  • the thermal transfer surface-modified sheet which is a release sheet having an easy-adhesion layer, as in Example A-1, except that the mixture was changed to a mixture)) and hot toluene (60 ° C.) was changed to methanol (room temperature). (16) was produced.
  • Example A-17 Thermal transfer surface modified sheet (17) Resin (1) was changed to Resin (17) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Wako Pure Chemical Industries, Nafion (50/50 mixture by weight))
  • Resin (17) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Wako Pure Chemical Industries, Nafion (50/50 mixture by weight)
  • a thermal transfer surface modified sheet (17) which is a release sheet provided with an easy-adhesion layer, was prepared in the same manner as in Example A-1, except that hot toluene (60 ° C.) was changed to methanol (normal temperature). .
  • Thermal transfer surface modified sheet (18) Resin (1) is Resin (18) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curesol C11Z-CN (Imidazole-based epoxy resin curing agent) (weight) Thermal transfer that is a release sheet having an easy-adhesion layer in the same manner as in Example A-1, except that the mixture was changed to 40/60 mixture)) and hot toluene (60 ° C.) was changed to methanol (room temperature). A surface modified sheet (18) was produced.
  • Resin (1) is Resin (18) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curesol C11Z-CN (Imidazole-based epoxy resin curing agent) (weight) Thermal transfer that is a release sheet having an easy-adhesion layer in the same manner as in Example A-1
  • Thermal transfer surface modified sheet (19) Resin (1) is Resin (19) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curesol C11Z-CN (Imidazole-based epoxy resin curing agent) (weight) Thermal transfer that is a release sheet having an easy-adhesive layer in the same manner as in Example A-1, except that the mixture was changed to a 50/50 mixture)) and hot toluene (60 ° C.) was changed to methanol (room temperature). A surface modified sheet (19) was produced.
  • Resin (1) is Resin (19) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curesol C11Z-CN (Imidazole-based epoxy resin curing agent) (weight) Thermal transfer that is a release sheet having an easy-adhesive layer in the same manner as
  • Example A-20 Thermal transfer surface modified sheet (20) Resin (1) is replaced with Resin (20) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight) Thermal transfer that is a release sheet provided with an easy-adhesive layer in the same manner as in Example A-1, except that the mixture was changed to 60/40 ratio)) and hot toluene (60 ° C.) was changed to methanol (room temperature). A surface modified sheet (20) was produced.
  • Resin (20) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight) Thermal transfer that is a release sheet provided with an easy-adhesive layer in the same manner as in Example A-1
  • Example A-21 Thermal transfer surface modified sheet (21) Resin (1) was replaced with Resin (21) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight)
  • the thermal transfer is a release sheet having an easy-adhesive layer in the same manner as in Example A-1, except that the mixture was changed to 70/30 ratio)) and hot toluene (60 ° C.) was changed to methanol (room temperature).
  • a surface modified sheet (21) was produced.
  • Example A-22 Thermal transfer surface modified sheet (22) Resin (1) is replaced with Resin (22) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight) Ratio 80/20 mixture)), and thermal transfer which is a release sheet having an easy-adhesion layer in the same manner as in Example A-1, except that hot toluene (60 ° C.) is changed to methanol (room temperature). A surface modified sheet (22) was produced.
  • Resin (22) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight) Ratio 80/20 mixture
  • thermal transfer which is a release sheet having an easy-adhesion layer in the same manner as in Example A
  • Example A-23 Thermal transfer surface modified sheet (23) Resin (1) is replaced with Resin (23) (Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight) Ratio 90/10 mixture)), and thermal transfer which is a release sheet provided with an easy-adhesive layer in the same manner as in Example A-1, except that hot toluene (60 ° C.) is changed to methanol (room temperature) A surface modified sheet (23) was produced.
  • Resin (23) Lead City, Fine Resin FR-105 (methoxymethylated polyamide resin) / Shikoku Kasei Kogyo Co., Ltd., Curazole C11Z-CN (imidazole epoxy resin curing agent) (weight) Ratio 90/10 mixture
  • thermal transfer which is a release sheet provided with an easy-adhesive layer in the same
  • Example B-1 Laminated member (G-PPS-1) On the glass fiber reinforced polyphenylene sulfide (manufactured by Nippon Test Panel Co., Ltd., G-PPS, dimensions: width 25 mm ⁇ length 100 mm ⁇ thickness 2 mm), the thermal transfer surface modified sheet (1) is on the inside of the easy adhesion layer And heat-pressing (270 ° C. ⁇ 10 minutes), thermally bonding the easy-adhesion layer to the glass fiber reinforced PPS surface, removing the release sheet, performing surface treatment, and laminating member (G-PPS-1) Manufactured.
  • G-PPS-1 Laminated member
  • Example B-2 Laminated member (G-PPS-2) A laminated member (G-PPS-2) was produced in the same manner as in Example B-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (2). .
  • Example B-3 Laminated member (G-PPS-3) A laminated member (G-PPS-3) was produced in the same manner as in Example B-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (3). .
  • Example B-4 Laminated member (G-PPS-4) A laminated member (G-PPS-4) was produced in the same manner as in Example B-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (4). .
  • Example C-1 Laminated member (C-PPS-1) On the carbon fiber reinforced polyphenylene sulfide (manufactured by Nippon Test Panel Co., Ltd., C-PPS, dimensions: width 25 mm x length 100 mm x thickness 2 mm), the thermal transfer surface modified sheet (1) is on the inner side of the easy adhesion layer And heat-pressing (270 ° C. ⁇ 10 minutes), thermally bonding the easy-adhesion layer to the carbon fiber reinforced PPS surface, removing the release sheet, performing surface treatment, and laminating member (C-PPS-1) Manufactured.
  • C-PPS-1 Laminated member
  • Example C-1 ′ Laminated member (C-PPS-1 ′) A laminated member (C-PPS-1 ′) was produced by performing a surface treatment in the same manner as in Example C-1, except that the heating press was changed to 250 ° C. ⁇ 10 minutes.
  • Example C-1 ′′ Laminated member (C-PPS-1 ′′) A laminated member (C-PPS-1 ′′) was produced by performing a surface treatment in the same manner as in Example C-1, except that the heating press was changed to 300 ° C. ⁇ 10 minutes.
  • Example C-2 Laminated member (C-PPS-2) A laminated member (C-PPS-2) was produced in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (2). .
  • Example C-3 Laminated member (C-PPS-3) A laminated member (C-PPS-3) was produced in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (3). .
  • Example C-4 Laminated member (C-PPS-4) A laminated member (C-PPS-4) was produced in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (4). .
  • Comparative Example B-4 Laminated member (G-PPS-8) Surface treatment was performed in the same manner as in Comparative Example B-1, except that the resin (1) was changed to the resin (4) and hot toluene (60 ° C.) was changed to methanol (room temperature). PPS-8) was produced.
  • Comparative Example C-4 Laminated member (C-PPS-8) A surface treatment was performed in the same manner as in Comparative Example C-1, except that the resin (1) was changed to the resin (4) and hot toluene (60 ° C.) was changed to methanol (room temperature). PPS-8) was produced.
  • Example B-5 Laminated member (G-PPS-9)
  • the laminated member (G-PPS-5) produced in Comparative Example B-1 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, surface-treated, and laminated member (G-PPS-9) is produced. did.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example B-6 Laminated member (G-PPS-10) The laminated member (G-PPS-6) produced in Comparative Example B-2 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, and subjected to surface treatment to produce a laminated member (G-PPS-10). did. During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example B-7 Laminated member (G-PPS-11)
  • the laminated member (G-PPS-7) produced in Comparative Example B-3 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, and subjected to surface treatment to produce a laminated member (G-PPS-11). did.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • Example B-8 Laminated member (G-PPS-12)
  • the laminated member (G-PPS-8) produced in Comparative Example B-4 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, surface treated, and laminated member (G-PPS-12) is produced. did.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • Example C-5 Laminated member (C-PPS-9)
  • the laminated member (C-PPS-5) produced in Comparative Example C-1 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, surface-treated, and laminated member (C-PPS-9) is produced. did.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-5 ′ Laminated member (C-PPS-9 ′) A laminated member (C-PPS-9 ′) was produced by performing a surface treatment in the same manner as in Example C-5 except that the heating press was changed to 250 ° C. ⁇ 10 minutes.
  • Example C-5 ′′ Laminated member (C-PPS-9 ′′) A laminated member (C-PPS-9 ′′) was produced by performing a surface treatment in the same manner as in Example C-5 except that the heating press was changed to 300 ° C. ⁇ 10 minutes.
  • Example C-6 Laminated member (C-PPS-10) The laminated member (C-PPS-6) produced in Comparative Example C-2 was heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, surface-treated, and laminated member (C-PPS-10) was produced. did. During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-7 Laminated member (C-PPS-11)
  • the laminated member (C-PPS-7) produced in Comparative Example C-3 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, surface-treated, and laminated member (C-PPS-11) is produced. did.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • Example C-8 Laminated member (C-PPS-12)
  • the laminated member (C-PPS-8) produced in Comparative Example C-4 is heated and pressed (270 ° C. ⁇ 10 minutes), subjected to heat treatment, surface-treated, and laminated member (C-PPS-12) is produced. did.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • Example C-9 Laminated member (C-PPS-13) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (5) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-13) was produced.
  • Example C-10 Laminated member (C-PPS-14) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (6) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-14) was produced.
  • Example C-11 Laminated member (C-PPS-15) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (7) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-15) was produced.
  • Example C-12 Laminated member (C-PPS-16) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (8) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-16) was produced.
  • Example C-13 Laminated member (C-PPS-17) The surface treatment was performed in the same manner as in Example C-1, except that the heat transfer surface modified sheet (1) was changed to the heat transfer surface modified sheet (9) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-17) was produced.
  • Example C-14 Laminated member (C-PPS-18) A surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (10) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-18) was produced.
  • Example C-15 Laminated member (C-PPS-19) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (11) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-19) was produced.
  • Example C-16 Laminated member (C-PPS-20) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (12) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-20) was produced.
  • Example C-17 Laminated member (C-PPS-21) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (13) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-21) was produced.
  • Example C-18 Laminated member (C-PPS-22) A surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (14) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-22) was produced.
  • Example C-19 Laminated member (C-PPS-23) A surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (15) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-23) was produced.
  • Example C-20 Laminated member (C-PPS-24) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (16) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-24) was produced.
  • Example C-21 Laminated member (C-PPS-25) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (17) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-25) was produced.
  • Example C-22 Laminated member (C-PPS-26) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (18) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-26) was produced.
  • Example C-23 Laminated member (C-PPS-27) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (19) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-27) was produced.
  • Example C-24 Laminated member (C-PPS-28) The surface treatment was performed in the same manner as in Example C-1, except that the heat transfer surface modified sheet (1) was changed to the heat transfer surface modified sheet (20) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-28) was produced.
  • Example C-25 Laminated member (C-PPS-29) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (21) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-29) was produced.
  • Example C-26 Laminated member (C-PPS-30) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (22) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-30) was produced.
  • Example C-27 Laminated member (C-PPS-31) The surface treatment was performed in the same manner as in Example C-1, except that the thermal transfer surface modified sheet (1) was changed to the thermal transfer surface modified sheet (23) and the heating press was changed to 290 ° C. ⁇ 1 minute. A laminated member (C-PPS-31) was produced.
  • Example C-28 Laminated member (C-PPS-32) Except for changing the resin (1) to the resin (5), in the same manner as in Comparative Example C-1, the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute), and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-32). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-29 Laminated member (C-PPS-33) Except for changing the resin (1) to the resin (6), the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to manufacture a laminated member (C-PPS-33). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-30 Laminated member (C-PPS-34) Except for changing the resin (1) to the resin (7), the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-34). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-31 Laminated member (C-PPS-35) Except for changing the resin (1) to the resin (8), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to manufacture a laminated member (C-PPS-35). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-32 Laminated member (C-PPS-36) Except for changing the resin (1) to the resin (9), the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-36). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-33 Laminated member (C-PPS-37) Except for changing the resin (1) to the resin (10), the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-37). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-34 Laminated member (C-PPS-38) Except for changing the resin (1) to the resin (11), the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to manufacture a laminated member (C-PPS-38). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-35 Laminated member (C-PPS-39) Except for changing the resin (1) to the resin (12), the laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-39). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-36 Laminated member (C-PPS-40) Except for changing the resin (1) to the resin (13), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-40). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-37 Laminated member (C-PPS-41) Except for changing the resin (1) to the resin (14), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to manufacture a laminated member (C-PPS-41). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-38 Laminated member (C-PPS-42) Except that the resin (1) was changed to the resin (15), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-42). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-39 Laminated member (C-PPS-43) Except for changing the resin (1) to the resin (16), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-43). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-40 Laminated member (C-PPS-44) Except for changing the resin (1) to the resin (17), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to manufacture a laminated member (C-PPS-44). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-41 Laminated member (C-PPS-45) Except for changing the resin (1) to the resin (19), the laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute) in the same manner as in Comparative Example C-1, and the heat treatment was performed. And surface treatment was performed to produce a laminated member (C-PPS-45). During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-42 Laminated member (C-PPS-46) Surface treatment was performed in the same manner as in Comparative Example C-1, except that Resin (1) was changed to Resin (24) (ARUFON (registered trademark) UH-2041 (hydroxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.)
  • Resin (24) ARUFON (registered trademark) UH-2041 (hydroxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.
  • the laminated member produced by the above process was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, and subjected to surface treatment to produce a laminated member (C-PPS-46).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-43 Laminated member (C-PPS-47) Surface treatment was performed in the same manner as in Comparative Example C-1, except that Resin (1) was changed to Resin (25) (ARUFON (registered trademark) UH-2170 (hydroxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.)
  • Resin (25) ARUFON (registered trademark) UH-2170 (hydroxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.
  • the laminated member produced by performing the above was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, and surface-treated to produce a laminated member (C-PPS-47).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-44 Laminated member (C-PPS-48) Surface treatment was performed in the same manner as in Comparative Example C-1, except that the resin (1) was changed to resin (26) (ARUFON (registered trademark) UH-2190 (hydroxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.)
  • the laminated member produced by the above process was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, and subjected to surface treatment to produce a laminated member (C-PPS-48).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • the adherend fiber reinforced resin
  • Example C-45 Laminated member (C-PPS-49)
  • the resin (1) was changed to the resin (27) (ARUFON (registered trademark) UC-3000 (carboxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.)
  • the laminated member produced by the treatment was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, surface-treated, and a laminated member (C-PPS-49) was produced.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • the adherend fiber reinforced resin
  • Example C-46 Laminated member (C-PPS-50)
  • Resin (1) was changed to Resin (28) (ARUFON (registered trademark) UC-3080 (carboxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.)
  • the laminated member produced by the treatment was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, surface-treated, and a laminated member (C-PPS-50) was produced.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • adherend fiber reinforced resin
  • Example C-47 Laminated member (C-PPS-51)
  • Resin (1) was changed to Resin (29) (ARUFON (registered trademark) UC-3150 (carboxyl group-containing acrylic polymer) manufactured by Toa Gosei Co., Ltd.)
  • the laminated member produced by the treatment was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, surface-treated, and a laminated member (C-PPS-51) was produced.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • adherend fiber reinforced resin
  • Example C-48 Laminated member (C-PPS-52)
  • the resin (1) was changed to the material (30) for easy adhesion layer (manufactured by Nippon Shokubai Co., Ltd., Epomin (registered trademark) SP-200 (polyethyleneimine))
  • the laminated member produced by the treatment was heated and pressed (290 ° C. ⁇ 1 minute), subjected to heat treatment, surface-treated, and a laminated member (C-PPS-52) was produced.
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • the adherend fiber reinforced resin
  • Example C-49 Laminated member (C-PPS-53) Except for changing the resin (1) to the material (31) for easy adhesion layer (Shikoku Kasei Kogyo Co., Ltd., Curazole 2P4MHZ-PW (imidazole epoxy resin curing agent)), the same as in Comparative Example C-1, The laminated member produced by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute), subjected to the heat treatment, subjected to the surface treatment, and a laminated member (C-PPS-53) was produced. During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-50 Laminated member (C-PPS-54) A laminated member produced by performing a surface treatment in the same manner as in Comparative Example C-1, except that the resin (1) is changed to the material (32) (Nafion, manufactured by Wako Pure Chemical Industries, Ltd.) for the easy adhesion layer.
  • the resin (1) is changed to the material (32) (Nafion, manufactured by Wako Pure Chemical Industries, Ltd.) for the easy adhesion layer.
  • a heat press 290 ° C. ⁇ 1 minute
  • heat treatment was performed
  • surface treatment was performed to produce a laminated member (C-PPS-54).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm
  • Example C-51 Laminated member (C-PPS-55) Except for changing the resin (1) to the easy-adhesion layer material (32) (Chiazole C11Z-CN (imidazole epoxy resin curing agent) manufactured by Shikoku Kasei Kogyo Co., Ltd.), the same as in Comparative Example C-1, The laminated member manufactured by performing the surface treatment was heated and pressed (290 ° C. ⁇ 1 minute), subjected to the heat treatment, surface-treated, and the laminated member (C-PPS-55) was produced. During the heating press, a release sheet (manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm) was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • the easy-adhesion layer material (32) Choazole C11Z-CN (imidazole epoxy resin curing agent) manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Example 1 Joined structure (1) Two of the laminated members (G-PPS-1) obtained in Example B-1 were joined by (joining method 1) to produce a joined structure (1). The results are shown in Table 2.
  • Example 2 Bonded structure (2) Two of the laminated members (G-PPS-2) obtained in Example B-2 were joined by (Joining Method 1) to produce a joined structure (2). The results are shown in Table 2.
  • Example 3 Bonded structure (3) Two of the laminated members (G-PPS-3) obtained in Example B-3 were joined by (Joining Method 1) to produce a joined structure (3). The results are shown in Table 2.
  • Example 4 Joined structure (4) Two of the laminated members (G-PPS-4) obtained in Example B-4 were joined by (Joining Method 1) to produce a joined structure (4). The results are shown in Table 2.
  • Example 5 Bonded structure (5) Two of the laminated members (C-PPS-1) obtained in Example C-1 were joined by (Joining Method 1) to produce a joined structure (5). The results are shown in Table 2.
  • Example 6 Bonded structure (6) Two of the laminated members (C-PPS-1 ′) obtained in Example C-1 ′ were joined by (Joining Method 1) to produce a joined structure (6). The results are shown in Table 2.
  • Example 7 Joined structure (7)
  • Two of the laminated members (C-PPS-1 ′′) obtained in Example C-1 ′′ were joined by (Joining Method 1) to produce a joined structure (7).
  • the results are shown in Table 2.
  • Example 8 Bonded structure (8) Two of the laminated members (C-PPS-2) obtained in Example C-2 were joined by (Joining Method 1) to produce a joined structure (8). The results are shown in Table 2.
  • Example 9 Joined structure (9) Two of the laminated members (C-PPS-3) obtained in Example C-3 were joined by (Joining Method 1) to produce a joined structure (9). The results are shown in Table 2.
  • Example 10 Joined structure (10) Two of the laminated members (C-PPS-4) obtained in Example C-4 were joined by (Joining Method 1) to produce a joined structure (10). The results are shown in Table 2.
  • Example 11 Joined structure (11) Two of the laminated members (C-PPS-2) obtained in Example C-2 were joined by (Joining Method 2) to produce a joined structure (11). The results are shown in Table 2.
  • Example 12 bonded structure (12) Two of the laminated members (G-PPS-9) obtained in Example B-5 were joined by (Joining method 1) to produce a joined structure (12). The results are shown in Table 2.
  • Example 13 bonded structure (13) Two of the laminated members (G-PPS-10) obtained in Example B-6 were joined by (Joining Method 1) to produce a joined structure (13). The results are shown in Table 2.
  • Example 14 Bonded structure (14) Two of the laminated members (G-PPS-11) obtained in Example B-7 were joined by (Joining Method 1) to produce a joined structure (14). The results are shown in Table 2.
  • Example 15 bonded structure (15) Two of the laminated members (G-PPS-12) obtained in Example B-8 were joined by (Joining method 1) to produce a joined structure (15). The results are shown in Table 2.
  • Example 16 bonded structure (16) Two of the laminated members (C-PPS-9) obtained in Example C-5 were joined by (Joining method 1) to produce a joined structure (16). The results are shown in Table 2.
  • Example 17 bonded structure (17) Two of the laminated members (C-PPS-9 ′) obtained in Example C-5 ′ were joined by (Joining Method 1) to produce a joined structure (17). The results are shown in Table 2.
  • Example 18 bonded structure (18) Two of the laminated members (C-PPS-9 ′′) obtained in Example C-5 ′′ were joined by (Joining Method 1) to produce a joined structure (18). The results are shown in Table 2.
  • Example 19 Bonding structure (19) Two of the laminated members (C-PPS-10) obtained in Example C-6 were joined by (Joining Method 1) to produce a joined structure (19). The results are shown in Table 2.
  • Example 20 bonded structure (20) Two of the laminated members (C-PPS-11) obtained in Example C-7 were joined by (Joining Method 1) to produce a joined structure (20). The results are shown in Table 2.
  • Example 21 bonded structure (21) Two of the laminated members (C-PPS-12) obtained in Example C-8 were joined by (Joining Method 1) to produce a joined structure (21). The results are shown in Table 2.
  • Example 22 bonded structure (22) Two of the laminated members (C-PPS-10) obtained in Example C-6 were joined by (joining method 2) to produce a joined structure (22). The results are shown in Table 2.
  • Comparative Example 1 Joined structure (C1) Glass fiber reinforced polyphenylene sulfide (manufactured by Nippon Test Panel Co., Ltd., G-PPS, dimensions: width 25 mm ⁇ length 100 mm ⁇ thickness 2 mm) are joined by (joining method 1), and the joined structure (C1) is joined. Manufactured. The results are shown in Table 3.
  • Example 23 bonded structure (23) Two of the laminated members (C-PPS-13) obtained in Example C-9 were joined by (Joining method 2) to produce a joined structure (23). The results are shown in Table 4.
  • Example 24 bonded structure (24) Two of the laminated members (C-PPS-14) obtained in Example C-10 were joined by (Joining method 2) to produce a joined structure (24). The results are shown in Table 4.
  • Example 25 bonded structure (25) Two of the laminated members (C-PPS-15) obtained in Example C-11 were joined by (Joining method 2) to produce a joined structure (25). The results are shown in Table 4.
  • Example 26 bonded structure (26) Two of the laminated members (C-PPS-16) obtained in Example C-12 were joined by (Joining method 2) to produce a joined structure (26). The results are shown in Table 4.
  • Example 27 bonded structure (27) Two of the laminated members (C-PPS-17) obtained in Example C-13 were joined by (Joining Method 2) to produce a joined structure (27). The results are shown in Table 4.
  • Example 28 bonded structure (28) Two of the laminated members (C-PPS-18) obtained in Example C-14 were joined by (Joining method 2) to produce a joined structure (28). The results are shown in Table 4.
  • Example 29 bonded structure (29) Two of the laminated members (C-PPS-19) obtained in Example C-15 were joined by (Joining method 2) to produce a joined structure (29). The results are shown in Table 4.
  • Example 30 bonded structure (30) Two of the laminated members (C-PPS-20) obtained in Example C-16 were joined by (Joining method 2) to produce a joined structure (30). The results are shown in Table 4.
  • Example 31 Bonded structure (31) Two of the laminated members (C-PPS-21) obtained in Example C-17 were joined by (Joining method 2) to produce a joined structure (31). The results are shown in Table 4.
  • Example 32 bonded structure (32) Two of the laminated members (C-PPS-22) obtained in Example C-18 were joined by (joining method 2) to produce a joined structure (32). The results are shown in Table 4.
  • Example 33 bonded structure (33) Two of the laminated members (C-PPS-23) obtained in Example C-19 were joined by (joining method 2) to produce a joined structure (33). The results are shown in Table 4.
  • Example 34 bonded structure (34) Two of the laminated members (C-PPS-24) obtained in Example C-20 were joined by (Joining method 2) to produce a joined structure (34). The results are shown in Table 4.
  • Example 35 bonded structure (35) Two of the laminated members (C-PPS-25) obtained in Example C-21 were joined by (Joining method 2) to produce a joined structure (35). The results are shown in Table 4.
  • Example 36 bonded structure (36) Two of the laminated members (C-PPS-26) obtained in Example C-22 were joined by (Joining method 2) to produce a joined structure (36). The results are shown in Table 4.
  • Example 37 bonded structure (37) Two of the laminated members (C-PPS-27) obtained in Example C-23 were joined by (Joining Method 2) to produce a joined structure (37). The results are shown in Table 4.
  • Example 38 bonded structure (38) Two of the laminated members (C-PPS-28) obtained in Example C-24 were joined by (joining method 2) to produce a joined structure (38). The results are shown in Table 4.
  • Example 39 bonded structure (39) Two of the laminated members (C-PPS-29) obtained in Example C-25 were joined by (Joining Method 2) to produce a joined structure (39). The results are shown in Table 4.
  • Example 40 bonded structure (40) Two of the laminated members (C-PPS-30) obtained in Example C-26 were joined by (joining method 2) to produce a joined structure (40). The results are shown in Table 4.
  • Example 41 bonded structure (41) Two of the laminated members (C-PPS-31) obtained in Example C-27 were joined by (joining method 2) to produce a joined structure (41). The results are shown in Table 4.
  • Example 42 bonded structure (42) Two of the laminate members (C-PPS-18) obtained in Example C-14 were joined by (Joining method 1) to produce a joined structure (42). The results are shown in Table 4.
  • Example 43 bonded structure (43) Two of the laminated members (C-PPS-18) obtained in Example C-14 were joined by (Joining Method 4) to produce a joined structure (43). The results are shown in Table 4.
  • Example 44 bonded structure (44) Two of the laminated members (C-PPS-18) obtained in Example C-14 were joined by (Joining method 5) to produce a joined structure (44). The results are shown in Table 4.
  • Example 45 bonded structure (45) Two of the laminated members (C-PPS-18) obtained in Example C-14 were joined by (Joining Method 6) to produce a joined structure (45). The results are shown in Table 4.
  • Example 46 bonded structure (46) Two of the laminated members (C-PPS-27) obtained in Example C-23 were joined by (Joining Method 1) to produce a joined structure (46). The results are shown in Table 4.
  • Example 47 bonded structure (47) Two of the laminated members (C-PPS-27) obtained in Example C-23 were joined by (Joining Method 4) to produce a joined structure (47). The results are shown in Table 4.
  • Example 48 bonded structure (48) Two of the laminated members (C-PPS-27) obtained in Example C-23 were joined by (Joining Method 5) to produce a joined structure (48). The results are shown in Table 4.
  • Example 49 bonded structure (49) Two of the laminated members (C-PPS-27) obtained in Example C-14 were joined by (Joining Method 6) to produce a joined structure (49). The results are shown in Table 4.
  • Example 50 bonded structure (50) Two of the laminated members (C-PPS-32) obtained in Example C-28 were joined by (Joining method 2) to produce a joined structure (50). The results are shown in Table 5.
  • Example 51 bonded structure (51) Two of the laminated members (C-PPS-33) obtained in Example C-29 were joined by (Joining method 2) to produce a joined structure (51). The results are shown in Table 5.
  • Example 52 bonded structure (52) Two of the laminated members (C-PPS-34) obtained in Example C-30 were joined by (joining method 2) to produce a joined structure (52). The results are shown in Table 5.
  • Example 53 bonded structure (53) Two of the laminated members (C-PPS-35) obtained in Example C-31 were joined by (joining method 2) to produce a joined structure (53). The results are shown in Table 5.
  • Example 54 bonded structure (54) Two of the laminated members (C-PPS-36) obtained in Example C-32 were joined by (Joining Method 2) to produce a joined structure (54). The results are shown in Table 5.
  • Example 55 bonded structure (55) Two of the laminated members (C-PPS-37) obtained in Example C-33 were joined by (joining method 2) to produce a joined structure (55). The results are shown in Table 5.
  • Example 56 bonded structure (56) Two of the laminated members (C-PPS-38) obtained in Example C-34 were joined by (Joining method 2) to produce a joined structure (56). The results are shown in Table 5.
  • Example 57 bonded structure (57) Two of the laminated members (C-PPS-39) obtained in Example C-35 were joined by (joining method 2) to produce a joined structure (57). The results are shown in Table 5.
  • Example 58 bonded structure (58) Two of the laminated members (C-PPS-40) obtained in Example C-36 were joined by (Joining method 2) to produce a joined structure (58). The results are shown in Table 5.
  • Example 59 bonded structure (59) Two of the laminated members (C-PPS-41) obtained in Example C-37 were joined by (joining method 2) to produce a joined structure (59). The results are shown in Table 5.
  • Example 60 bonded structure (60) Two of the laminated members (C-PPS-42) obtained in Example C-38 were joined by (joining method 2) to produce a joined structure (60). The results are shown in Table 5.
  • Example 61 bonded structure (61) Two of the laminated members (C-PPS-43) obtained in Example C-39 were joined by (joining method 2) to produce a joined structure (61). The results are shown in Table 5.
  • Example 62 bonded structure (62) Two of the laminated members (C-PPS-44) obtained in Example C-40 were joined by (joining method 2) to produce a joined structure (62). The results are shown in Table 5.
  • Example 63 bonded structure (63) Two of the laminated members (C-PPS-45) obtained in Example C-41 were joined by (joining method 2) to produce a joined structure (63). The results are shown in Table 5.
  • Example 64 bonded structure (64) Two of the laminated members (C-PPS-46) obtained in Example C-42 were joined by (joining method 2) to produce a joined structure (64). The results are shown in Table 5.
  • Example 65 bonded structure (65) Two of the laminated members (C-PPS-47) obtained in Example C-43 were joined by (Joining method 2) to produce a joined structure (65). The results are shown in Table 5.
  • Example 66 Bonded structure (66) Two of the laminated members (C-PPS-48) obtained in Example C-44 were joined by (Joining method 2) to produce a joined structure (66). The results are shown in Table 5.
  • Example 67 bonded structure (67) Two of the laminated members (C-PPS-49) obtained in Example C-45 were joined by (joining method 2) to produce a joined structure (67). The results are shown in Table 5.
  • Example 68 bonded structure (68) Two of the laminated members (C-PPS-50) obtained in Example C-46 were joined by (Joining method 2) to produce a joined structure (68). The results are shown in Table 5.
  • Example 69 bonded structure (69) Two of the laminated members (C-PPS-51) obtained in Example C-47 were joined by (joining method 2) to produce a joined structure (69). The results are shown in Table 5.
  • Example 70 bonded structure (70) Two of the laminated members (C-PPS-52) obtained in Example C-48 were joined by (joining method 2) to produce a joined structure (70). The results are shown in Table 5.
  • Example 71 bonded structure (71) Two of the laminated members (C-PPS-53) obtained in Example C-49 were joined by (joining method 2) to produce a joined structure (71). The results are shown in Table 5.
  • Example 72 bonded structure (72) Two of the laminated members (C-PPS-54) obtained in Example C-50 were joined by (joining method 2) to produce a joined structure (72). The results are shown in Table 5.
  • Example 73 bonded structure (73) Two of the laminated members (C-PPS-55) obtained in Example C-51 were joined by (Joining Method 2) to produce a joined structure (73). The results are shown in Table 5.
  • Comparative Example C-5 Laminated member (C-PPS-56) A surface treatment was performed in the same manner as in Comparative Example C-1, except that the resin (1) was changed to the resin (6) and hot toluene (60 ° C.) was changed to methanol (room temperature). PPS-56) was produced.
  • Comparative Example C-6 Laminated member (C-PPS-57) A surface treatment was performed in the same manner as in Comparative Example C-1, except that the resin (1) was changed to the resin (19) and hot toluene (60 ° C.) was changed to methanol (room temperature). PPS-57) was produced.
  • Example A-24 Thermal transfer surface modified sheet (24) Resin (33) (manufactured by NOF Corporation, Modiper A5400 (ethylene / ethyl acrylate-graft-styrene / acrylonitrile copolymer) was dissolved in hot toluene (60 ° C.), cooled to room temperature, and 5% by weight solution Was made.
  • a release sheet Nitoflon No. 900UL (thickness 0.18 mm) was dipped in the 5 wt% solution, air-dried, and further dried at 100 ° C for 1 minute in a constant temperature dryer.
  • a thermal transfer surface modified sheet (24) which is a release sheet provided with an easy adhesion layer, was prepared.
  • Example A-25 Thermal transfer surface modified sheet (25) Except that Resin (33) was changed to Resin (34) (manufactured by NOF Corporation, Modiper A6600 (ethylene / vinyl acetate-graft-modified methyl methacrylate copolymer), the same procedure as in Example A-24 was conducted.
  • Example D-1 Laminated member (PP-1 / transfer) On a PP plate (dimensions: width 25 mm ⁇ length 100 mm ⁇ thickness 2 mm), the thermal transfer surface modified sheet (24) is placed so that the easy-adhesion layer side is inside, and heated and pressed (120 ° C. ⁇ 10 minutes), An easy-adhesion layer was thermally welded to the PP plate surface, the release sheet was removed, and surface treatment was performed to produce a laminated member (PP-1 / transfer).
  • Example D-2 Laminated member (PP-2 / transfer) A laminated member (PP-2 / transfer) was produced by performing a surface treatment in the same manner as in Example D-1, except that the thermal transfer surface modified sheet (24) was changed to the thermal transfer surface modified sheet (25). .
  • Comparative Example D-2 Laminated member (PP-2 / coating) A laminated member (PP-2 / coated) was produced by performing a surface treatment in the same manner as in Comparative Example D-1, except that the resin (33) was changed to the resin (34).
  • Example D-3 Laminated member (PP-1 / coating heating)
  • the laminated member (PP-1 / coating) produced in Comparative Example D-1 was heated and pressed (120 ° C. ⁇ 10 minutes), subjected to heat treatment, surface treatment, and laminated member (PP-1 / coating heating).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • Example D-4 Laminated member (PP-2 / coating heating)
  • the laminated member (PP-2 / coating) produced in Comparative Example D-2 was heated and pressed (120 ° C. ⁇ 10 minutes), subjected to heat treatment, surface treatment, and laminated member (PP-2 / coating / heating).
  • a release sheet manufactured by Nitto Denko Corporation, Nitoflon No. 900UL, thickness 0.18 mm was sandwiched between the press plate and the adherend (fiber reinforced resin).
  • Example 74 bonded structure (74) Two of the laminated members (PP-1 / transfer) obtained in Example D-1 were joined by (Joining Method 3) to produce a joined structure (74). The results are shown in Table 7.
  • Example 75 bonded structure (75) Two of the laminated members (PP-2 / transfer) obtained in Example D-2 were joined by (Joining Method 3) to produce a joined structure (75). The results are shown in Table 7.
  • Example 76 bonded structure (76) Two of the laminated members (PP-1 / coating and heating) obtained in Example D-3 were joined by (Joining Method 3) to produce a joined structure (76). The results are shown in Table 7.
  • Example 77 bonded structure (77) Two of the laminated members (PP-2 / coating and heating) obtained in Example D-4 were joined by (Joining Method 3) to produce a joined structure (77). The results are shown in Table 7.
  • Example D-5 Laminated member (G-PP-1) On the glass fiber reinforced polypropylene (N-Test Panel Co., Ltd., G-PP, dimensions: width 25 mm x length 100 mm x thickness 2 mm), the thermal transfer surface modified sheet (6) faces the easy-adhesion layer side. And heat press (170 ° C. ⁇ 1 minute) to heat-weld the easy-adhesion layer to the glass fiber reinforced PP surface, remove the release sheet, perform surface treatment, and laminate member (G-PP-1). Manufactured.
  • Example D-6 Laminated member (G-PP-2) A laminated member (G-PP-2) was produced in the same manner as in Example D-5 except that the thermal transfer surface modified sheet (6) was changed to the thermal transfer surface modified sheet (19). .
  • Example D-7 Laminated member (G-PP-3) A laminated member (G-PP-3) was produced in the same manner as in Example D-5 except that the thermal transfer surface modified sheet (6) was changed to the thermal transfer surface modified sheet (10). .
  • Example 78 bonded structure (78) Two of the laminated members (G-PP-1) obtained in Example D-5 were joined by (Joining Method 7) to produce a joined structure (78). The results are shown in Table 8.
  • Example 79 bonded structure (79) Two of the laminated members (G-PP-2) obtained in Example D-6 were joined by (Joining Method 7) to produce a joined structure (79). The results are shown in Table 8.
  • Example 80 bonded structure (80) Two of the laminate members (G-PP-2) obtained in Example D-6 were joined by (Joining method 6) to produce a joined structure (80). The results are shown in Table 8.
  • Example 81 bonded structure (81) Two of the laminated members (G-PP-3) obtained in Example D-7 were joined by (Joining Method 6) to produce a joined structure (81). The results are shown in Table 8.
  • Example E-1 Laminated member (C-PA6-1) Heat transfer surface modified sheet (6) on the inside of the easy adhesion layer side on carbon fiber reinforced nylon 6 (Sanwa Trading Co., Ltd., C-PA6, dimensions: width 25 mm x length 100 mm x thickness 2 mm) And heat press (225 ° C x 1 minute) to heat-weld the easy-adhesion layer to the surface of carbon fiber reinforced nylon 6, remove the release sheet, perform surface treatment, and laminate member (C-PA6-1) Manufactured.
  • C-PA6-1 Heat transfer surface modified sheet (6) on the inside of the easy adhesion layer side on carbon fiber reinforced nylon 6 (Sanwa Trading Co., Ltd., C-PA6, dimensions: width 25 mm x length 100 mm x thickness 2 mm) And heat press (225 ° C x 1 minute) to heat-weld the easy-adhesion layer to the surface of carbon fiber reinforced nylon 6, remove the release sheet, perform surface treatment, and laminate member (C-PA6-1)
  • Example E-2 Laminated member (C-PA66-1) On the carbon fiber reinforced nylon 66 (C-PA66, manufactured by Sanwa Trading Co., Ltd., dimensions: width 25 mm x length 100 mm x thickness 2 mm), the thermal transfer surface modified sheet (6) is placed so that the easy adhesion layer side is on the inside. And heat press (265 ° C x 1 minute), heat-weld an easy-adhesion layer to the surface of carbon fiber reinforced nylon 66, remove the release sheet, perform surface treatment, and laminate member (C-PA66-1) Manufactured.
  • Example E-3 Laminated member (C-PA6-2) A laminated member (C-PA6-2) was produced in the same manner as in Example E-1, except that the thermal transfer surface modified sheet (6) was changed to the thermal transfer surface modified sheet (19). .
  • Example E-4 Laminated member (C-PA66-2) A laminated member (C-PA66-2) was produced in the same manner as in Example E-2 except that the thermal transfer surface modified sheet (6) was changed to the thermal transfer surface modified sheet (19). .
  • Example 82 bonded structure (82) Two of the laminated members (C-PA6-1) obtained in Example E-1 were joined by (joining method 2) to produce a joined structure (82). The results are shown in Table 9.
  • Example 83 bonded structure (83) Two of the laminated members (C-PA66-1) obtained in Example E-2 were joined by (Joining method 2) to produce a joined structure (83). The results are shown in Table 9.
  • Example 84 bonded structure (84) Two of the laminated members (C-PA6-2) obtained in Example E-3 were joined by (Joining Method 2) to produce a joined structure (84). The results are shown in Table 9.
  • Example 85 bonded structure (85) Two of the laminated members (C-PA66-2) obtained in Example E-4 were joined by (Joining method 2) to produce a joined structure (85). The results are shown in Table 9.
  • a structure optimization calculation was performed by a molecular mechanics method using a force field, and a unit cell was gradually compressed under a three-dimensional boundary condition to obtain a model having a density of 0.5 g / cm 3 .
  • LAMMPS molecular dynamics simulator
  • molecular dynamics calculation of NPT ensemble under conditions of 25 ° C. and 1 atm to 100 atm was performed for 10 ns or more, and finally ethylene-glycidyl methacrylate copolymer
  • An energetically stable interface model was obtained in which the coalescence and polyphenylene sulfide were evenly contacted at 25 ° C. and 1 atm.
  • the thickness of the mixed layer of ethylene-glycidyl methacrylate copolymer and polyphenylene sulfide was 2.0 nm.
  • the thickness of the mixed layer of ethylene-glycidyl methacrylate copolymer and polyphenylene sulfide was 0.8 nm.
  • the thickness of the mixed layer of ethylene-glycidyl methacrylate copolymer and polyphenylene sulfide was 0.9 nm.
  • the method for producing a surface-modified thermoplastic resin of the present invention a method for producing a bonded structure, a bonded structure, a thermal transfer surface-modified sheet, a thermoplastic resin with a thermal transfer surface-modified sheet, and a surface-modified thermoplastic resin are:
  • it can be suitably used in the field of transportation equipment such as railway vehicles, aircraft, ships and automobiles.
  • Adhesive layer 20 Release sheet 100 Thermoplastic resin 200 Thermal transfer surface modified sheet 300 Adhesive layer 500 Surface modified thermoplastic resin 800 Thermoplastic resin with thermal transfer surface modified sheet 1000 Bonded structure

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Abstract

熱可塑性樹脂に十分な接着強度が付与された表面改質熱可塑性樹脂の製造方法を提供する。そのような製造方法で得られる表面改質熱可塑性樹脂を、接着剤層を介して被着体に積層させた、十分な接着強度を発現できる接合構造体の製造方法を提供する。十分な接着強度を発現できる接合構造体を提供する。表面改質熱可塑性樹脂の製造方法に好ましく採用し得る熱転写表面改質シートを提供する。そのような熱転写表面改質シートを有する熱転写表面改質シート付熱可塑性樹脂を提供する。熱可塑性樹脂に十分な接着強度が付与された表面改質熱可塑性樹脂を提供する。 本発明の表面改質熱可塑性樹脂の製造方法は、融点がT℃の熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法であって、熱可塑性樹脂の表面の少なくとも一部に易接着層を設け、(T-50)℃以上の温度で加熱溶着を行う。

Description

表面改質熱可塑性樹脂の製造方法、接合構造体の製造方法、接合構造体、熱転写表面改質シート、熱転写表面改質シート付熱可塑性樹脂、および、表面改質熱可塑性樹脂
 本発明は、表面改質熱可塑性樹脂の製造方法、接合構造体の製造方法、接合構造体、熱転写表面改質シート、熱転写表面改質シート付熱可塑性樹脂、および、表面改質熱可塑性樹脂に関する。
 鉄道車両、航空機、船舶、自動車などの輸送機器においては、従来、その構成材料として、鉄やアルミニウムなどの金属が一般に用いられている。鉄やアルミニウムなどの金属を構成材料として輸送機器を製造する場合、鉄やアルミニウムなどの金属を他の被着体に十分に接着させる必要がある。このような接着剤としては、従来、ゴムエポキシ系の硬化性樹脂組成物が汎用されている(例えば、特許文献1など)。
 近年、燃費向上等のため、このような輸送機器の軽量化が求められている。輸送機器の軽量化のためには、その構成材料の軽量化が重要な鍵となる。
 鉄やアルミニウムなどの金属に代わり得る軽量材料として、繊維強化プラスチック(FRP)が挙げられる。特に、輸送機器の構成材料としては、成形のし易さ等の要求から、熱可塑性樹脂をマトリックス樹脂として用いた繊維強化熱可塑性プラスチック(FRTP)が好ましい軽量材料として挙げられる。
 しかしながら、熱可塑性樹脂は接着剤となじみにくく、汎用の接着剤や接着シートを用いても十分な接着強度が得られない。このような接着強度を得るための常套手段として、熱可塑性樹脂の表面に適切なプライマー溶液を塗布する技術(例えば、特許文献2など)があるが、耐溶剤性の高い樹脂(例えば、PPS、PA、PPなど)の場合、十分な接着強度を発現できないという問題がある。
 また、プライマー溶液を塗布する技術の他にも、熱可塑性樹脂に十分な接着強度を付与するための手段として、サンドブラスト処理、コロナ処理、プラズマ処理などの各種表面処理方法が知られている。しかし、このような表面処理方法においては、表面処理工程および乾燥工程を設けなければならず、生産性が低下するという問題がある。
 さらに、熱可塑性樹脂を金型で成形加工する際には離型剤を用いることが必要であるが、この離型剤により熱可塑性樹脂の表面が汚染されるため、熱可塑性樹脂に十分な接着強度を付与することができない。このため、離型剤を除去するための洗浄処理工程や研磨処理工程が必要となる。その結果、これらの工程を行うための設備投資やランニング費用など、コスト上昇という問題がある。
特許第3229467号公報 特開2000-226536号公報
 本発明は、上記従来の課題を解決するためになされたものであり、その目的とするところは、熱可塑性樹脂に十分な接着強度が付与された表面改質熱可塑性樹脂の製造方法を提供することにある。また、本発明は、そのような製造方法で得られる表面改質熱可塑性樹脂を、接着剤層を介して被着体に積層させた、十分な接着強度を発現できる接合構造体の製造方法を提供することにある。また、本発明は、十分な接着強度を発現できる接合構造体を提供することにある。さらに、本発明は、表面改質熱可塑性樹脂の製造方法に好ましく採用し得る熱転写表面改質シートを提供することにある。さらに、本発明は、そのような熱転写表面改質シートを有する熱転写表面改質シート付熱可塑性樹脂を提供することにある。さらに、本発明は、熱可塑性樹脂に十分な接着強度が付与された表面改質熱可塑性樹脂を提供することにある。
 本発明の表面改質熱可塑性樹脂の製造方法は、
 融点がT℃の熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法であって、
 熱可塑性樹脂の表面の少なくとも一部に易接着層を設け、(T-50)℃以上の温度で加熱溶着を行う。
 一つの実施形態としては、上記加熱溶着が加熱プレスによって行われる。
 一つの実施形態としては、上記加熱プレスによって前記熱可塑性樹脂の成型加工がなされる。
 一つの実施形態としては、離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を、上記熱可塑性樹脂の表面の少なくとも一部に載置することにより易接着層を設ける。
 一つの実施形態としては、上記加熱溶着の後、離型シートが除去される。
 本発明の表面改質熱可塑性樹脂の製造方法は、
 熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法であって、
 熱可塑性樹脂の表面の少なくとも一部を溶融状態とした後、該熱可塑性樹脂の溶融状態の表面に易接着層を設ける。
 一つの実施形態としては、上記易接着層がポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットを有する。
 一つの実施形態としては、上記ポリマー成分が、メトキシメチル基含有ポリマー、水酸基含有ポリマー、カルボキシル基含有ポリマー、アミノ基含有ポリマーから選ばれる少なくとも1種である。
 一つの実施形態としては、上記易接着層が、3級アミン含有化合物、強酸から選ばれる少なくとも1種を含む。
 本発明の接合構造体の製造方法は、
 本発明の製造方法で得られる表面改質熱可塑性樹脂(A)を、接着剤層を介して被着体に積層させた接合構造体の製造方法であって、
 表面改質熱可塑性樹脂(A)の易接着層側の面に接着剤層を設けて被着体に接合させる。
 一つの実施形態としては、上記接着剤層の成分が極性基と反応する官能基を有する。
 一つの実施形態としては、上記被着体が、本発明の製造方法で得られる表面改質熱可塑性樹脂(B)であり、該被着体である該表面改質熱可塑性樹脂(B)における易接着層側の面に接着剤層を積層させる。
 一つの実施形態としては、上記表面改質熱可塑性樹脂(A)を構成する熱可塑性樹脂が、上記表面改質熱可塑性樹脂(B)を構成する熱可塑性樹脂と異なる。
 本発明の接合構造体は、
 熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、接着剤層と、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、をこの順に有する接合構造体であって、
 該2つの表面改質熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP(Pa)とし、該表面改質熱可塑性樹脂を構成する熱可塑性樹脂と接着剤層と該表面改質熱可塑性樹脂を構成する熱可塑性樹脂とをこの順に有する接合構造体における該2つの熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP0(Pa)としたときに、P/P0>2である。
 本発明の接合構造体は、
 熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、接着剤層と、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、をこの順に有する接合構造体であって、
 該2つの表面改質熱可塑性樹脂同士を25℃、引張速度5mm/minにおいて引張り、接合構造体を破壊した際に、該接着剤層および該2つの表面改質熱可塑性樹脂の少なくとも1つで破壊が生じる。
 本発明の熱転写表面改質シートは、離型シートと易接着層の積層体である。
 一つの実施形態としては、本発明の熱転写表面改質シートは、本発明の表面改質熱可塑性樹脂の製造方法で用いられる。
 一つの実施形態としては、上記易接着層がポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットを有する。
 一つの実施形態としては、上記ポリマー成分が、メトキシメチル基含有ポリマー、水酸基含有ポリマー、カルボキシル基含有ポリマー、アミノ基含有ポリマーから選ばれる少なくとも1種である。
 一つの実施形態としては、上記易接着層が、3級アミン含有化合物、強酸から選ばれる少なくとも1種を含む。
 本発明の熱転写表面改質シート付熱可塑性樹脂は、本発明の熱転写表面改質シートの易接着層側が熱可塑性樹脂の表面側になるように該熱転写表面改質シートが該熱可塑性樹脂の表面に載置されたものである。
 本発明の表面改質熱可塑性樹脂は、
 熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂であって、
 熱可塑性樹脂と易接着層との間に、該熱可塑性樹脂と該易接着層とが混合した混合層を備え、
 該混合層の厚さが1.5nm以上である。
 本発明によれば、熱可塑性樹脂に十分な接着強度が付与された表面改質熱可塑性樹脂の製造方法を提供することができる。また、本発明は、そのような製造方法で得られる表面改質熱可塑性樹脂を、接着剤層を介して被着体に積層させた、十分な接着強度を発現できる接合構造体の製造方法を提供することができる。また、本発明は、十分な接着強度を発現できる接合構造体を提供することができる。さらに、本発明は、表面改質熱可塑性樹脂の製造方法に好ましく採用し得る熱転写表面改質シートを提供することができる。さらに、本発明は、そのような熱転写表面改質シートを有する熱転写表面改質シート付熱可塑性樹脂を提供することができる。さらに、本発明は、熱可塑性樹脂に十分な接着強度が付与された表面改質熱可塑性樹脂を提供することができる。
表面改質熱可塑性樹脂の一例を示す概略断面図である。 熱転写表面改質シートの一例を示す概略断面図である。 離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を該熱可塑性樹脂の表面の少なくとも一部に載置する形態を示す概略断面図である。 接合構造体の一つの実施形態を示す概略断面図である。 熱転写表面改質シート付熱可塑性樹脂一つの実施形態を示す概略断面図である。 実施例、比較例で作製する接合構造体の一つの実施形態を示す概略断面図である。
≪本発明の第一の表面改質熱可塑性樹脂の製造方法≫
 本発明の第一の表面改質熱可塑性樹脂の製造方法は、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法である。すなわち、本発明の第一の表面改質熱可塑性樹脂の製造方法は、熱可塑性樹脂の表面を処理する方法(熱可塑性樹脂の表面処理方法)でもあり得る。
 本発明の第一の表面改質熱可塑性樹脂の製造方法においては、強い接着強度が得られるとともに、好ましくは、従来行われていたような表面処理工程を削減できる。また、本発明の第一の表面改質熱可塑性樹脂の製造方法の一つの実施形態においては、成形加工と同時に表面処理を行うことにより、離型剤の使用が不要となり、離型剤除去工程(サンドブラスト処理、脱脂処理など)を削減できる。
 本発明の第一の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の融点をT℃としたとき、該熱可塑性樹脂の表面の少なくとも一部に易接着層を設け、(T-50)℃以上の温度で加熱溶着を行う。このような方法で熱可塑性樹脂の表面処理を行うことにより、熱可塑性樹脂に十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。
 本発明の第一の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の表面の少なくとも一部に易接着層を設ける。
 「熱可塑性樹脂の表面の少なくとも一部」とは、熱可塑性樹脂が有する全ての表面の中の少なくとも一部を意味する。例えば、熱可塑性樹脂が板状やシート状やフィルム状の場合は、その少なくとも一方の表面の一部や、その少なくとも一方の表面の全部などを意味する。
 熱可塑性樹脂としては、本発明の効果を発現し得る範囲で、任意の適切な熱可塑性樹脂を採用し得る。このような熱可塑性樹脂としては、例えば、PP(ポリプロピレン)、PA(ポリアミド)、PPE(ポリフェニレンエーテル)、PPS(ポリフェニレンサルファイド)、PET(ポリエチレンテレフタレート)、PBT(ポリブチレンテレフタレート)、POM(ポリアセタール)、PEEK(ポリエーテルエーテルケトン)、PC(ポリカーボネート)などが挙げられる。これらの樹脂の中でも、本発明の効果を有利に発現し得る熱可塑性樹脂としては、PPS(ポリフェニレンサルファイド)、PA(ポリアミド)、PP(ポリプロピレン)が挙げられる。
 熱可塑性樹脂としては、繊維強化熱可塑性樹脂(FRTP)を採用し得る。
 繊維強化熱可塑性樹脂(FRTP)としては、例えば、炭素繊維強化熱可塑性樹脂(CFRTP)、ガラス繊維強化熱可塑性樹脂(GFRTP)などが挙げられる。
 炭素繊維強化熱可塑性樹脂(CFRTP)としては、任意の適切な炭素繊維強化熱可塑性樹脂(CFRTP)を採用し得る。このような炭素繊維強化熱可塑性樹脂(CFRTP)としては、例えば、PPS系炭素繊維強化熱可塑性樹脂、PA系炭素繊維強化熱可塑性樹脂、PP系炭素繊維強化熱可塑性樹脂などが挙げられる。
 ガラス繊維強化熱可塑性樹脂(GFRTP)としては、任意の適切なガラス繊維強化熱可塑性樹脂(GFRTP)を採用し得る。このようなガラス繊維強化熱可塑性樹脂(GFRTP)としては、例えば、PPS系ガラス繊維強化熱可塑性樹脂、PA系ガラス繊維強化熱可塑性樹脂、PP系ガラス繊維強化熱可塑性樹脂などが挙げられる。
 熱可塑性樹脂の形状としては、本発明の効果を損なわない範囲で、任意の適切な形状を採用し得る。このような形状としては、例えば、平面を有する板状、曲面を有する板状、シート状、フィルム状などが挙げられる。
 熱可塑性樹脂の厚みは、目的に応じて、また、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。このような厚みとしては、例えば、0.001mm~10mmである。
 本発明の第一の表面改質熱可塑性樹脂の製造方法において、熱可塑性樹脂の表面の少なくとも一部に易接着層を設ける方法としては、本発明の効果を損なわない範囲で、任意の適切な方法を採用し得る。このような方法としては、例えば、熱可塑性樹脂の表面の少なくとも一部に易接着層の材料と溶剤を含む溶液を塗布する方法、熱可塑性樹脂の表面の少なくとも一部に易接着層を溶融押出する方法、熱可塑性樹脂の表面の少なくとも一部にシート形態の易接着層を積層する方法などが挙げられる。
 易接着層の材料と溶剤を含む溶液の塗布の方法としては、本発明の効果を損なわない範囲で、任意の適切な方法を採用し得る。このような方法としては、例えば、易接着層の材料と溶剤を含む溶液への熱可塑性樹脂のディッピング、熱可塑性樹脂の表面の少なくとも一部への易接着層の材料と溶剤を含む溶液の刷毛塗り、熱可塑性樹脂の表面の少なくとも一部への易接着層の材料と溶剤を含む溶液の各種コーターによる塗布、熱可塑性樹脂の表面の少なくとも一部への易接着層の材料と溶剤を含む溶液のスプレー塗布などが挙げられる。
 易接着層の材料と溶剤を含む溶液としては、易接着層の材料を、本発明の効果を損なわない範囲で、任意の適切な溶剤に溶解した溶液が挙げられる。
 このような溶剤としては、本発明の効果を損なわない範囲で、任意の適切な溶剤を採用し得る。このような溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコールなどのアルコール類;メチルエチルケトンなどのケトン類;エステル;脂肪族、脂環族、並びに芳香族炭化水素;ハロゲン化炭化水素;ジメチルホルムアミドなどのアミド類;ジメチルスルホキシドなどのスルホキシド類;ジメチルエーテル、テトラヒドロフランなどのエーテル類;などが挙げられる。溶剤は、1種のみであってもよいし、2種以上であってもよい。
 易接着層の材料と溶剤を含む溶液における固形分濃度は、目的に応じて適宜設定し得る。取り扱い性の簡便さ等の観点から、このような固形分濃度は、重量割合として、好ましくは0.01重量%~20重量%であり、より好ましくは0.05重量%~10重量%であり、さらに好ましくは0.1重量%~5重量%である。
 易接着層の材料と溶剤を含む溶液には、本発明の効果を損なわない範囲で、任意の適切なその他の成分が含まれていても良い。
 易接着層(易接着層の材料であってもよい)は、本発明の効果を損なわない範囲で、任意の適切な構成成分を有する。このような構成成分は、好ましくは、ポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットを有する。易接着層中の上記ポリマー成分の含有割合は、好ましくは50重量%~100重量%であり、より好ましくは70重量%~100重量%であり、さらに好ましくは90重量%~100重量%であり、特に好ましくは92重量%~100重量%であり、最も好ましくは95重量%~100重量%である。
 ポリマー成分における非極性ユニットとしては、本発明の効果を損なわない範囲で、任意の適切な、非極性のポリマーユニットを採用し得る。このような非極性ユニットとしては、例えば、ポリエチレンユニット、ポリプロピレンユニット、ポリスチレンユニットなどが挙げられる。非極性ユニットは、1種のみであってもよいし、2種以上であってもよい。
 ポリマー成分における極性基を備える極性ユニットとしては、本発明の効果を損なわない範囲で、任意の適切な、極性基を備えるポリマーユニットを採用し得る。このような極性基としては、例えば、エポキシ基、カルボキシル基、ニトリル基、アミド基、エステル基、水酸基、酸無水物、シラノール基などが挙げられる。このような極性基を有する極性ユニットとしては、例えば、グリシジルメタクリレートユニット、酢酸ビニルユニット、アクリロニトリルユニット、アミドユニット、(メタ)アクリル酸エステルユニット、ヒドロキシエチル(メタ)アクリレートユニット、無水マレイン酸ユニットなどが挙げられる。極性ユニットは、1種のみであってもよいし、2種以上であってもよい。
 易接着層(易接着層の材料であってもよい)が含み得るポリマー成分は、メトキシメチル基含有ポリマー、水酸基含有ポリマー、カルボキシル基含有ポリマー、アミノ基含有ポリマーから選ばれる少なくとも1種であってもよい。
 易接着層(易接着層の材料であってもよい)が含み得るこのようなポリマー成分は、好ましくは、付加型硬化剤であり、より好ましくは、エポキシ基と反応する付加型硬化剤である。
 メトキシメチル基含有ポリマーとしては、メトキシメチル基(-CH-OCH)を含有するポリマーであれば、本発明の効果を損なわない範囲で、任意の適切なポリマーを採用し得る。このようなメトキシメチル基含有ポリマーとしては、例えば、メトキシメチル化ポリアミド樹脂などが挙げられる。
 メトキシメチル基含有ポリマーとしては、市販品を採用してもよい。このような市販品としては、例えば、「Fine Resin」(登録商標)シリーズ(株式会社鉛市製)などが挙げられる。
 メトキシメチル基含有ポリマーは、1種であってもよいし、2種以上であってもよい。
 メトキシメチル基含有ポリマーは、本発明の効果をより発現させ得る点で、その重量平均分子量(Mw)が、好ましくは1000~1000000であり、より好ましくは3000~500000であり、さらに好ましくは5000~100000であり、特に好ましくは7000~70000であり、最も好ましくは10000~50000である。重量平均分子量(Mw)の測定方法については後述する。
 水酸基含有ポリマーとしては、水酸基(-OH)を含有するポリマーであれば、本発明の効果を損なわない範囲で、任意の適切なポリマーを採用し得る。このような水酸基含有ポリマーとしては、例えば、水酸基含有アクリル系ポリマーなどが挙げられる。
 水酸基含有ポリマーとしては、市販品を採用してもよい。このような市販品としては、例えば、「ARUFON(登録商標) UH-2000シリーズ」(東亜合成株式会社製)などが挙げられる。
 水酸基含有ポリマーは、1種であってもよいし、2種以上であってもよい。
 水酸基含有ポリマーは、本発明の効果をより発現させ得る点で、その重量平均分子量(Mw)が、好ましくは500~1000000であり、より好ましくは700~500000であり、さらに好ましくは1000~100000であり、特に好ましくは1500~70000であり、最も好ましくは2000~50000である。重量平均分子量(Mw)の測定方法については後述する。
 カルボキシル基含有ポリマーとしては、カルボキシル基(-COOH)を含有するポリマーであれば、本発明の効果を損なわない範囲で、任意の適切なポリマーを採用し得る。このようなカルボキシル基含有ポリマーとしては、例えば、カルボキシル基含有アクリル系ポリマーなどが挙げられる。
 カルボキシル基含有ポリマーとしては、市販品を採用してもよい。このような市販品としては、例えば、「ARUFON(登録商標) UC-3000シリーズ」(東亜合成株式会社製)などが挙げられる。
 カルボキシル基含有ポリマーは、1種であってもよいし、2種以上であってもよい。
 カルボキシル基含有ポリマーは、本発明の効果をより発現させ得る点で、その重量平均分子量(Mw)が、好ましくは500~1000000であり、より好ましくは700~500000であり、さらに好ましくは1000~100000であり、特に好ましくは1500~70000であり、最も好ましくは2000~50000である。重量平均分子量(Mw)はGPC測定におけるポリスチレン換算分子量を用いた。
 アミノ基含有ポリマーとしては、アミノ基(-NH)を含有するポリマーであれば、本発明の効果を損なわない範囲で、任意の適切なポリマーを採用し得る。
 アミノ基含有ポリマーとしては、市販品を採用してもよい。
 アミノ基含有ポリマーは、1種であってもよいし、2種以上であってもよい。
 易接着層(易接着層の材料であってもよい)は、3級アミン含有化合物、強酸から選ばれる少なくとも1種を含んでいてもよい。
 易接着層(易接着層の材料であってもよい)が含み得るこのような3級アミン含有化合物や強酸は、好ましくは、触媒型硬化剤であり、より好ましくは、エポキシ基と反応する触媒型硬化剤である。
 3級アミン含有化合物としては、3級アミンを含有する化合物であれば、本発明の効果を損なわない範囲で、任意の適切な化合物を採用し得る。このような3級アミン含有化合物としては、例えば、イミダゾール誘導体、ポリエチレンイミンなどが挙げられる。
 3級アミン含有化合物としては、市販品を採用してもよい。このような市販品としては、例えば、イミダゾール誘導体として、「キュアゾール」シリーズ(イミダゾール系エポキシ樹脂硬化剤、四国化成工業株式会社製)などが挙げられ、ポリエチレンイミンとして、「エポミン」(登録商標)シリーズ(株式会社日本触媒製)などが挙げられる。
 3級アミン含有化合物は、1種であってもよいし、2種以上であってもよい。
 強酸としては、本発明の効果を損なわない範囲で、任意の適切な強酸を採用し得る。このような強酸としては、例えば、トリフルオロボラン、イオン液体、ナフィオンなどが挙げられる。
 イオン液体としては、例えば、BF-CNH、HMI-PFなどが挙げられる。
 強酸としては、市販品を採用してもよい。
 強酸は、1種であってもよいし、2種以上であってもよい。
 熱可塑性樹脂の表面の少なくとも一部に易接着層の材料と溶剤を含む溶液を塗布した場合は、その後、溶剤の少なくとも一部を乾燥によって除去する。このような乾燥においては、溶剤の少なくとも一部が除去されればよいが、溶剤の50重量%以上が除去されることが好ましく、溶剤の80重量%以上が除去されることがより好ましく、溶剤の90重量%以上が除去されることがさらに好ましく、溶剤の95重量%以上が除去されることが特に好ましく、全ての溶剤が除去されることが最も好ましい。
 乾燥の方法としては、オーブン加熱、赤外線加熱、高周波加熱など、溶剤を除去させることができる方法であれば、本発明の効果を損なわない範囲で、任意の適切な方法を採用し得る。また、乾燥温度としては、用いる溶剤の沸点に応じて、任意の適切な温度を適宜設定し得る。
 易接着層を溶融押出する方法としては、本発明の効果を損なわない範囲で、任意の適切な方法を採用し得る。このような方法としては、例えば、易接着層の材料を、溶融押出機等によって、熱可塑性樹脂の表面の少なくとも一部に溶融押出する方法などが挙げられる。
 シート形態の易接着層を積層する方法としては、本発明の効果を損なわない範囲で、任意の適切な方法を採用し得る。このような方法としては、例えば、熱可塑性樹脂の表面の少なくとも一部に、<本発明の第三の表面処理方法>の項で詳述するような熱転写表面改質シート(離型シートと易接着層の積層体)の易接着層側を積層する方法などが挙げられる。
 本発明の第一の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の融点をT℃としたとき、該熱可塑性樹脂の表面の少なくとも一部に易接着層を設け、(T-50)℃以上の温度で加熱溶着を行う。この加熱溶着の温度は、好ましくは(T-50)℃~(T+150)℃であり、より好ましくは(T-25)℃~(T+100)℃であり、さらに好ましくは(T-10)℃~(T+75)℃であり、特に好ましくは(T)℃~(T+50)℃である。加熱溶着温度を上記範囲内として、上記のような方法で熱可塑性樹脂の表面処理を行うことにより、易接着層と熱可塑性樹脂の界面が溶融接触して溶着混合し、熱可塑性樹脂に十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。
 加熱溶着の方法としては、本発明の効果を発現し得る範囲で、任意の適切な方法を採用し得る。このような方法としては、例えば、オーブン加熱、赤外線加熱、高周波加熱、加熱プレスなどが挙げられ、本発明の効果をより発現させ得る点で、好ましくは加熱プレスである。
 加熱溶着の時間は、本発明の効果を発現し得る範囲で、任意の適切な時間を採用し得る。本発明の効果をより発現させ得る点で、好ましくは1秒~10分である。
 本発明の第一の表面改質熱可塑性樹脂の製造方法により、図1に示すように、熱可塑性樹脂100の表面に易接着層10が設けられ、表面改質熱可塑性樹脂(熱可塑性樹脂と易接着層の積層部材と称することもある)が得られる。なお、図1においては、熱可塑性樹脂100の表面に易接着層10が積層されているが、好ましくは、熱可塑性樹脂100と易接着層10との間に、該熱可塑性樹脂と該易接着層とが混合した混合層(図示せず)を備える。この混合層の厚さは、好ましくは1.5nm以上であり、より好ましくは2.0nm以上である。
 易接着層の厚みは、目的に応じて、また、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。このような厚みとしては、本発明の効果をより発現させ得る点で、好ましくは0.001μm~100μmであり、より好ましくは0.01μm~10μmであり、さらに好ましくは0.05μm~5μmであり、特に好ましくは0.1μm~3μmである。
<本発明の第二の表面改質熱可塑性樹脂の製造方法>
 本発明の第二の表面改質熱可塑性樹脂の製造方法は、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法である。すなわち、本発明の第二の表面改質熱可塑性樹脂の製造方法は、熱可塑性樹脂の表面を処理する方法(熱可塑性樹脂の表面処理方法)でもあり得る。
 本発明の第二の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の表面の少なくとも一部を溶融状態とした後、該熱可塑性樹脂の溶融状態の表面に易接着層を設ける。このような方法で熱可塑性樹脂の表面処理を行うことにより、熱可塑性樹脂に十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。
 本発明の第二の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の表面の少なくとも一部を溶融状態とする。
 「熱可塑性樹脂の表面の少なくとも一部」としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 熱可塑性樹脂としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 「溶融状態」とは、熱可塑性樹脂の表面の少なくとも一部が溶融した状態であり、好ましくは、熱可塑性樹脂をその融点以上の温度にすることによって成し得る。
 本発明の第二の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の表面の少なくとも一部を溶融状態とした後、該熱可塑性樹脂の溶融状態の表面に易接着層を設ける。熱可塑性樹脂の溶融状態の表面に易接着層を設けることにより、熱可塑性樹脂の表面の熱によって易接着層が溶着混合し、熱可塑性樹脂に十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。
 易接着層としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 本発明の第二の表面改質熱可塑性樹脂の製造方法において、熱可塑性樹脂の溶融状態の表面に易接着層を設ける方法としては、例えば、離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を熱可塑性樹脂の溶融状態の表面に載置する方法が挙げられる。このような方法により、熱可塑性樹脂により十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。離型シートと易接着層の積層体である熱転写表面改質シートやその載置の仕方については<本発明の第三の表面改質熱可塑性樹脂の製造方法>の項において詳述する。
<本発明の第三の表面改質熱可塑性樹脂の製造方法>
 本発明の第三の表面改質熱可塑性樹脂の製造方法は、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法である。すなわち、本発明の第三の表面改質熱可塑性樹脂の製造方法は、熱可塑性樹脂の表面を処理する方法(熱可塑性樹脂の表面処理方法)でもあり得る。
 本発明の第三の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の表面の少なくとも一部に、離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を載置し、加熱溶着を行う。このような方法で熱可塑性樹脂の表面処理を行うことにより、熱可塑性樹脂に十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。
 本発明の第三の表面改質熱可塑性樹脂の製造方法においては、熱可塑性樹脂の表面の少なくとも一部に、離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を載置する。
 「熱可塑性樹脂の表面の少なくとも一部」としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 熱可塑性樹脂としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 易接着層としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 離型シートと易接着層の積層体である熱転写表面改質シートは、図2に示すように、離型シート20と易接着層10の積層体である熱転写表面改質シート200である。
 本発明の第三の表面改質熱可塑性樹脂の製造方法において、離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を該熱可塑性樹脂の表面の少なくとも一部に載置する形態は、図3に示すように、熱転写表面改質シート200を、該熱転写表面改質シート200の易接着層10側が熱可塑性樹脂100の表面側になるように該熱転写表面改質シート200を該熱可塑性樹脂100の表面に載置させた形態である。
 熱転写表面改質シートは、本発明の効果を損なわない範囲で、任意の適切な方法によって製造し得る。このような方法としては、例えば、易接着層の材料と溶剤を含む溶液への離型シートのディッピングの後に必要に応じて乾燥する方法、離型シートの表面への易接着層の材料と溶剤を含む溶液の刷毛塗りの後に必要に応じて乾燥する方法、離型シートの表面への易接着層の材料と溶剤を含む溶液の各種コーターによる塗布の後に必要に応じて乾燥する方法、離型シートの表面への易接着層の材料と溶剤を含む溶液のスプレー塗布の後に必要に応じて乾燥する方法などが挙げられる。なお、「易接着層の材料と溶剤を含む溶液」については、<本発明の第一の表面処理方法>の項における説明をそのまま採用し得る。
 離型シートとしては、本発明の効果を損なわない範囲で、任意の適切な離型シートを採用し得る。このような離型シートとしては、例えば、フッ素樹脂シートフィルム(日東電工製、ニトフロン)、ポリエステル樹脂シート、ポリメチルペンテン樹脂シート(三井化学東セロ製、オピュラン(登録商標))、ポリスチレン樹脂シート(クラボウ製、オイディス(登録商標))などが挙げられる。離型シートの厚みは、本発明の効果をより発現させ得る点で、好ましくは1μm~1000μmであり、より好ましくは10μm~500μmであり、さらに好ましくは20μm~250μmであり、特に好ましくは50μm~200μmである。
 本発明の第三の表面改質熱可塑性樹脂の製造方法において、熱可塑性樹脂の表面の少なくとも一部に易接着層を設ける際は、本発明の効果を損なわない範囲で、任意の適切な装置を採用し得る。例えば、成形加工機(例えば、プレス機など)内において熱可塑性樹脂の表面の少なくとも一部に易接着層を設けることが挙げられる。
 本発明の第三の表面改質熱可塑性樹脂の製造方法においては、該熱可塑性樹脂の表面の少なくとも一部に、上記熱転写表面改質シートの易接着層側を載置し、加熱溶着を行う。このような加熱溶着は、熱転写表面改質シートの載置と同時に行ってもよいし、熱転写表面改質シートを載置した後に行ってもよい。
 本発明の第三の表面改質熱可塑性樹脂の製造方法における加熱溶着の代表的な態様としては、例えば、成形加工機(例えば、プレス機など)内で、熱可塑性樹脂の表面の少なくとも一部に熱転写表面改質シートの易接着層側を載置し、加熱を伴う成形加工(例えば、加熱プレス)を行う態様である。このような態様によれば、熱可塑性樹脂の表面処理とともに、熱可塑性樹脂の成型加工も同時に行うことができるため、高い生産性と低コストを提供できる。
 本発明の第三の表面改質熱可塑性樹脂の製造方法においては、加熱溶着は、熱可塑性樹脂の融点をT℃としたとき、好ましくは、(T-50)℃以上の温度で加熱溶着を行う。この加熱溶着の温度は、より好ましくは(T-50)℃~(T+150)℃であり、さらに好ましくは(T-25)℃~(T+100)℃であり、特に好ましくは(T-10)℃~(T+75)℃であり、最も好ましくは(T)℃~(T+50)℃である。加熱溶着温度を上記範囲内とすることにより、熱転写表面改質シートが有する易接着層と熱可塑性樹脂の界面が溶融接触して溶着混合し、熱可塑性樹脂により十分な接着強度を付与することができ、好ましくは、このような付与を高い生産性と低コストで行うことができる。
 加熱溶着の方法としては、本発明の効果を発現し得る範囲で、任意の適切な方法を採用し得る。このような方法としては、例えば、オーブン加熱、赤外線加熱、高周波加熱、加熱プレスなどが挙げられ、本発明の効果をより発現させ得る点で、好ましくは加熱プレスである。
 加熱溶着の時間は、本発明の効果を発現し得る範囲で、任意の適切な時間を採用し得る。本発明の効果をより発現させ得る点で、好ましくは1秒~10分である。
 離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を熱可塑性樹脂の表面の少なくとも一部に載置し、加熱溶着した後、好ましくは、離型シートが除去される。このように離型シートが除去されることにより、熱可塑性樹脂の表面に易接着層が転写され、表面改質熱可塑性樹脂(熱可塑性樹脂と易接着層の積層部材と称することもある)が得られる。なお、前述したように、好ましくは、熱可塑性樹脂と易接着層との間に、該熱可塑性樹脂と該易接着層とが混合した混合層を備える。この混合層の厚さは、好ましくは1.5nm以上であり、より好ましくは2.0nm以上である。
≪熱可塑性樹脂の接合方法≫
 本発明の熱可塑性樹脂の接合方法は、本発明の表面処理方法で得られる表面処理された熱可塑性樹脂の表面処理面に接着剤層を設けて被着体に接合させる。本発明の熱可塑性樹脂の接合方法においては、該熱可塑性樹脂が本発明の表面処理方法で表面処理されたものであるため、接着剤層とのなじみがよく、各種被着体と良好に接合することが可能となる。
 接着剤層は、本発明の効果を損なわない範囲で、任意の適切な接着剤層を採用し得る。本発明の効果をより発現させ得る点で、このような接着剤層は、好ましくは、該接着剤層の成分が極性基と反応する官能基を有する。このような接着剤層を採用すると、本発明の効果がより一層発現し得る。
 極性基と反応する官能基としては、本発明の効果を損なわない範囲で、任意の適切な官能基を採用し得る。このような官能基としては、例えば、エポキシ基、カルボキシル基、酸無水物基、アミノ基、水酸基、シラノール基、イソシアネート基などが挙げられる。このような官能基の中でも、本発明の効果をより発現させ得る点で、好ましくは、エポキシ基である。
 接着剤層の厚みは、本発明の効果をより発現させ得る点で、好ましくは1μm~5000μmであり、より好ましくは10μm~2000μmであり、さらに好ましくは50μm~1000μmであり、特に好ましくは100μm~500μmである。
≪表面改質熱可塑性樹脂≫
 本発明の表面改質熱可塑性樹脂は、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂であって、熱可塑性樹脂と易接着層との間に、該熱可塑性樹脂と該易接着層とが混合した混合層を備え、該混合層の厚さが1.5nm以上である。
 熱可塑性樹脂としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 易接着層としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
 混合層は、熱可塑性樹脂と該易接着層とが混合した層であり、代表的には、熱可塑性樹脂の表面の少なくとも一部に易接着層を設けて加熱溶着を行うことによって、易接着層と熱可塑性樹脂の界面が溶融接触して溶着混合し、それによって得られる溶着混合部分の層である。
 混合層の厚みは、加熱溶着の条件や、熱可塑性樹脂や易接着層の種類に応じて、適宜決定し得る。混合層の厚みは、好ましくは1.5nm以上であり、より好ましくは2.0nm以上である。
 本発明の表面改質熱可塑性樹脂において、熱可塑性樹脂の厚みは、目的に応じて、また、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。このような厚みとしては、例えば、0.001mm~10mmである。
 本発明の表面改質熱可塑性樹脂において、易接着層の厚みは、目的に応じて、また、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。このような厚みとしては、本発明の効果をより発現させ得る点で、好ましくは0.001μm~100μmであり、より好ましくは0.01μm~10μmであり、さらに好ましくは0.05μm~5μmであり、特に好ましくは0.1μm~3μmである。
 本発明の表面改質熱可塑性樹脂は、好ましくは、本発明の表面改質熱可塑性樹脂の製造方法によって得られる。
≪接合構造体の製造方法≫
 本発明の接合構造体の製造方法は、本発明の製造方法で得られる表面改質熱可塑性樹脂(A)を、接着剤層を介して被着体に積層させた接合構造体の製造方法であって、表面改質熱可塑性樹脂(A)の易接着層側の面に接着剤層を設けて被着体に接合させる。
 接着剤層の成分は、好ましくは、極性基と反応する官能基を有する。このような接着剤層を採用すると、本発明の効果がより一層発現し得る。
 極性基と反応する官能基としては、本発明の効果を損なわない範囲で、任意の適切な官能基を採用し得る。このような官能基としては、例えば、エポキシ基、カルボキシル基、酸無水物基、アミノ基、水酸基、シラノール基、イソシアネート基などが挙げられる。このような官能基の中でも、本発明の効果をより発現させ得る点で、好ましくは、エポキシ基である。
 接着剤層の厚みは、本発明の効果をより発現させ得る点で、好ましくは1μm~5000μmであり、より好ましくは10μm~2000μmであり、さらに好ましくは50μm~1000μmであり、特に好ましくは100μm~500μmである。
 本発明の接合構造体の製造方法においては、好ましくは、被着体が、本発明の製造方法で得られる表面改質熱可塑性樹脂(B)であり、該被着体である該表面改質熱可塑性樹脂(B)における易接着層側の面に接着剤層を積層させる。ここで、表面改質熱可塑性樹脂(B)は、前述の表面改質熱可塑性樹脂(A)とは別の表面改質熱可塑性樹脂を意味する。この場合、好ましくは、表面改質熱可塑性樹脂(A)を構成する熱可塑性樹脂が表面改質熱可塑性樹脂(B)を構成する熱可塑性樹脂と異なる。このような形態を採用すると、本発明の効果がより一層発現し得る。
≪接合構造体≫
 本発明の接合構造体は、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、接着剤層と、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、をこの順に有する接合構造体である。2つの表面改質熱可塑性樹脂それぞれの易接着層側が接着剤層に接合している。すなわち、一つの実施形態として、図4に示すように、本発明の接合構造体1000は、表面改質熱可塑性樹脂500と接着剤層300と表面改質熱可塑性樹脂500との積層体である。
 本発明の接合構造体が有する接着剤層は、本発明の効果を損なわない範囲で、任意の適切な接着剤層を採用し得る。本発明の効果をより発現させ得る点で、このような接着剤層は、好ましくは、易接着層が有する極性基と反応する官能基を有する。
 極性基と反応する官能基としては、本発明の効果を損なわない範囲で、任意の適切な官能基を採用し得る。このような官能基としては、例えば、エポキシ基、カルボキシル基、酸無水物基、アミノ基、水酸基、シラノール基、イソシアネート基などが挙げられる。このような官能基の中でも、本発明の効果をより発現させ得る点で、好ましくは、エポキシ基である。
 接着剤層の厚みは、本発明の効果をより発現させ得る点で、好ましくは1μm~5000μmであり、より好ましくは10μm~2000μmであり、さらに好ましくは50μm~1000μmであり、特に好ましくは100μm~500μmである。
 本発明の接合構造体は、好ましくは、2つの表面改質熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP(Pa)とし、該表面改質熱可塑性樹脂を構成する熱可塑性樹脂と接着剤層と該表面改質熱可塑性樹脂を構成する熱可塑性樹脂とをこの順に有する接合構造体における該2つの熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP0(Pa)としたときに、P/P0>2であり、より好ましくはP/P0>2.5であり、さらに好ましくはP/P0>3.0であり、特に好ましくはP/P0>3.5であり、最も好ましくはP/P0>4.0である。上記P/P0が上記範囲にあることにより、本発明の接合構造体は、より十分な接着強度を発現できる。
 本発明の接合構造体は、好ましくは、2つの表面改質熱可塑性樹脂同士を25℃、引張速度5mm/minにおいて引張り、接合構造体を破壊した際に、接着剤層および2つの表面改質熱可塑性樹脂の少なくとも1つで破壊が生じる。このような特徴を有することにより、本発明の接合構造体は、より十分な接着強度を発現できる。
≪熱転写表面改質シート≫
 本発明の熱転写表面改質シートは、離型シートと易接着層の積層体である。具体的には、前述した図2に示すような、離型シート20と易接着層10の積層体である熱転写表面改質シート200である。
 本発明の熱転写表面改質シートは、好ましくは、その易接着層側を熱可塑性樹脂の表面の少なくとも一部に載置し、加熱溶着した後に、前記離型シートを除去することにより、該熱可塑性樹脂の表面に該易接着層が転写され、表面改質熱可塑性樹脂が得られる。このように、本発明の熱転写表面改質シートを用いると、表面改質熱可塑性樹脂を容易に製造することが可能となり、熱可塑性樹脂に十分な接着強度を高い生産性と低コストで付与することができる。
 易接着層としては、<本発明の第一の表面改質熱可塑性樹脂の製造方法>の項における説明をそのまま援用し得る。
≪熱転写表面改質シート付熱可塑性樹脂≫
 本発明の熱転写表面改質シート付熱可塑性樹脂は、本発明の熱転写表面改質シートの易接着層側が熱可塑性樹脂の表面側になるように該熱転写表面改質シートが該熱可塑性樹脂の表面に積層されたものである。すなわち、図5に示すように、本発明の熱転写表面改質シート付熱可塑性樹脂800は、離型シート20と易接着層10の積層体である熱転写表面改質シート200の易接着層10側が熱可塑性樹脂100の表面に積層されたものである。
 本発明の熱転写表面改質シート付熱可塑性樹脂は、そのまま、本発明の表面改質熱可塑性樹脂の製造方法に用いることができる。すなわち、例えば、本発明の熱転写表面改質シート付熱可塑性樹脂における熱可塑性樹脂の融点をT℃としたとき、(T-50)℃以上の温度で加熱を行い、その後、好ましくは、離型シートが除去される。このように離型シートが除去されることにより、熱可塑性樹脂の表面に易接着層が設けられ、表面改質熱可塑性樹脂が得られる。このような方法で熱可塑性樹脂の表面処理を行うことにより、該熱可塑性樹脂に十分な接着強度を好ましくは高い生産性と低コストで付与することができる。
≪その他≫
 本発明の他の好ましい実施形態としては以下のようなものが挙げられる。
 一つの実施形態として、本発明の第一の表面処理方法は、熱可塑性樹脂の表面を処理する方法であって、該熱可塑性樹脂の融点をT℃としたとき、該熱可塑性樹脂の表面の少なくとも一部に易接着層を設け、(T-50)℃以上の温度で加熱溶着を行う。
 一つの実施形態として、本発明の第二の表面処理方法は、熱可塑性樹脂の表面を処理する方法であって、該熱可塑性樹脂の表面の少なくとも一部を溶融状態とした後、該熱可塑性樹脂の溶融状態の表面に易接着層を設ける。
 一つの実施形態としては、上記熱可塑性樹脂の溶融状態の表面に上記易接着層を設ける方法が、離型シートと該易接着層の積層体である熱転写表面改質シートの該易接着層側を該熱可塑性樹脂の溶融状態の表面に載置する方法である。
 一つの実施形態としては、上記載置の後、離型シートが除去される。
 一つの実施形態としては、上記易接着層がポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットを有する。
 一つの実施形態として、本発明の熱可塑性樹脂の接合方法は、本発明の表面処理方法で得られる表面処理された熱可塑性樹脂の表面処理面に接着剤層を設けて被着体に接合させる。
 一つの実施形態としては、上記接着剤層の成分が極性基と反応する官能基を有する。
 一つの実施形態として、本発明の積層部材は、本発明の表面処理方法で得られる、熱可塑性樹脂と易接着層の積層部材である。
 一つの実施形態として、本発明の接合構造体は、本発明の積層部材と接着剤層と本発明の積層部材とをこの順に有する接合構造体であって、該2つの積層部材それぞれの易接着層側が該接着剤層に接合している。
 一つの実施形態としては、上記接着剤層の成分が極性基と反応する官能基を有する。
 一つの実施形態としては、上記2つの積層部材同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP(Pa)とし、該積層部材を構成する熱可塑性樹脂と接着剤層と該積層部材を構成する熱可塑性樹脂とをこの順に有する接合構造体における該2つの熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP0(Pa)としたときに、P/P0>2である。
 一つの実施形態として、本発明の熱転写表面改質シートは、離型シートと易接着層の積層体である。
 一つの実施形態としては、上記易接着層側を表面の少なくとも一部が溶融状態にある熱可塑性樹脂の該溶融状態にある表面に載置させ、上記離型シートを除去することにより、該易接着層が該熱可塑性樹脂の表面に転写される。
 一つの実施形態としては、上記易接着層がポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットを有する。
 一つの実施形態として、本発明の熱転写表面改質シート付熱可塑性樹脂は、本発明の熱転写表面改質シートの易接着層側が熱可塑性樹脂の表面側になるように該熱転写表面改質シートが該熱可塑性樹脂の表面に積層されたものである。
≪熱可塑性樹脂の融点T(℃)の測定≫
 DSC(示差走査熱量計)によって、-90℃から350℃までを2℃/分で昇温させながら、実施例・比較例で用いた熱可塑性樹脂の融点T(℃)を測定した。
 ポリフェニレンサルファイド(PPS)の融点は284℃であった。
 ポリプロピレン(PP)の融点は167℃であった。
 6-ナイロン(PA6)の融点は221℃であった。
 6,6-ナイロン(PA66)の融点は260℃であった。
≪重量平均分子量(Mw)の測定≫
 易接着層に含まれ得るポリマー成分の重量平均分子量(Mw)を測定する必要がある場合は、GPCにより測定し、ポリスチレン換算分子量とした。
≪積層部材の接合方法≫
(接合方法1)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着剤としては、エポキシ系接着剤(3M製、SW2214)を用い、接着剤層の厚みを0.2mmに調整するために、粘着テープ(日東電工製、ニトフロン、No.973UL)をスペーサーとして用いた。接着面積は25mm×10mmとした。接着剤の硬化条件は140℃×20分とした。
(接合方法2)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着シートとしては、特開2012-197427号公報記載のゴム変性エポキシ接着シートを用いて接着した。接着面積は25mm×10mmとした。接着剤の硬化条件は150℃×20分とした。
(接合方法3)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着剤としては、エポキシ系接着剤(ナガセケムテックス製、デナタイトXNR3503)を用い、接着剤層の厚みを0.2mmに調整するために、粘着テープ(日東電工製、ニトフロン、No.973UL)をスペーサーとして用いた。接着面積は25mm×10mmとした。接着剤の硬化条件は100℃×30分とした。
(接合方法4)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着剤としては、アクリル系接着剤(セメダイン株式会社製、Y611black)を用い、接着面積は25mm×10mmとした。接着剤の硬化条件は室温×1日以上とした。
(接合方法5)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着剤としては、アクリル系接着剤(デンカ株式会社製、C320K)を用い、接着面積は25mm×10mmとした。接着剤の硬化条件は室温×1日以上とした。
(接合方法6)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着剤としては、ウレタン系接着剤(Henkel社製、U-10FL)を用い、接着面積は25mm×10mmとした。接着剤の硬化条件は室温×1日以上とした。
(接合方法7)
 実施例、比較例で得られた積層部材の2つを、それぞれの易接着剤層側同士が接合するように、接着剤を用いて図6の形態で接合し、接合構造体とした。接着剤としては、エポキシ系接着剤(3M製、SW2214)を用い、接着面積は25mm×10mmとした。接着剤の硬化条件は120℃×40分以上とした。
≪せん断接着力≫
 接合構造体における2つの積層部材同士の引っ張りせん断接着力を、引張試験機(ミネベア製、型番:TG-100kN)にて測定した。測定は、25℃にて引張速度5mm/minで実施した。得られた測定値を単位面積あたりに換算し、せん断接着力とした。なお、測定によって被着体破壊が生じる場合は、せん断接着力が測定値として得られる限界を超えて大きいことを意味する。
〔実施例A-1〕:熱転写表面改質シート(1)
 樹脂(1)(住友化学(株)製、ボンドファースト7B(エチレン-グリシジルメタクリレート-酢酸ビニル共重合体))を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 離型シート(日東電工(株)製、ニトフロンNo.900UL(厚み0.18mm))をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、易接着層を備えた離型シートである熱転写表面改質シート(1)を作製した。
〔実施例A-2〕:熱転写表面改質シート(2)
 樹脂(1)を樹脂(2)(住友化学(株)製、ボンドファーストCG5001(エチレン-グリシジルメタクリレート共重合体))に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(2)を作製した。
〔実施例A-3〕:熱転写表面改質シート(3)
 樹脂(1)を樹脂(3)(SUNNY FC(株)製、Fine-Blend SAG-005(スチレン-アクリロニトリル-グリシジルメタクリレート共重合体))に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(3)を作製した。
〔実施例A-4〕:熱転写表面改質シート(4)
 樹脂(1)を樹脂(4)(株式会社鉛市製、Fine Resin FR-101(メトキシメチル化ポリアミド樹脂)/p-トルエンスルホン酸(PTS)(重量比99/1混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(4)を作製した。
〔実施例A-5〕:熱転写表面改質シート(5)
 樹脂(1)を樹脂(5)(株式会社鉛市製、Fine Resin FR-101(メトキシメチル化ポリアミド樹脂))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(5)を作製した。
〔実施例A-6〕:熱転写表面改質シート(6)
 樹脂(1)を樹脂(6)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(6)を作製した。
〔実施例A-7〕:熱転写表面改質シート(7)
 樹脂(1)を樹脂(7)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/東亜合成株式会社製、ARUFON(登録商標) UH-2041(水酸基含有アクリル系ポリマー)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(7)を作製した。
〔実施例A-8〕:熱転写表面改質シート(8)
 樹脂(1)を樹脂(8)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/東亜合成株式会社製、ARUFON(登録商標) UH-2170(水酸基含有アクリル系ポリマー)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(8)を作製した。
〔実施例A-9〕:熱転写表面改質シート(9)
 樹脂(1)を樹脂(9)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/東亜合成株式会社製、ARUFON(登録商標) UC-3000(カルボキシル基含有アクリル系ポリマー)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(9)を作製した。
〔実施例A-10〕:熱転写表面改質シート(10)
 樹脂(1)を樹脂(10)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/東亜合成株式会社製、ARUFON(登録商標) UC-3150(カルボキシル基含有アクリル系ポリマー)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(10)を作製した。
〔実施例A-11〕:熱転写表面改質シート(11)
 樹脂(1)を樹脂(11)(東亜合成株式会社製、ARUFON(登録商標) UH-2041(水酸基含有アクリル系ポリマー)/東亜合成株式会社製、ARUFON(登録商標) UH-2170(水酸基含有アクリル系ポリマー)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(11)を作製した。
〔実施例A-12〕:熱転写表面改質シート(12)
 樹脂(1)を樹脂(12)(東亜合成株式会社製、ARUFON(登録商標) UC-3000(カルボキシル基含有アクリル系ポリマー)/東亜合成株式会社製、ARUFON(登録商標) UC-3150(カルボキシル基含有アクリル系ポリマー)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(12)を作製した。
〔実施例A-13〕:熱転写表面改質シート(13)
 樹脂(1)を樹脂(13)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/株式会社日本触媒製、エポミン(登録商標) SP-200(ポリエチレンイミン)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(13)を作製した。
〔実施例A-14〕:熱転写表面改質シート(14)
 樹脂(1)を樹脂(14)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール 2P4MHZ-PW(イミダゾール系エポキシ樹脂硬化剤)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(14)を作製した。
〔実施例A-15〕:熱転写表面改質シート(15)
 樹脂(1)を樹脂(15)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/東京化成工業株式会社製、トリフルオロボラン(BF)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(15)を作製した。
〔実施例A-16〕:熱転写表面改質シート(16)
 樹脂(1)を樹脂(16)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/東洋合成工業株式会社製、HMI-PF(イオン液体)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(16)を作製した。
〔実施例A-17〕:熱転写表面改質シート(17)
 樹脂(1)を樹脂(17)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/和光純薬工業株式会社製、ナフィオン(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(17)を作製した。
〔実施例A-18〕:熱転写表面改質シート(18)
 樹脂(1)を樹脂(18)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤)(重量比40/60混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(18)を作製した。
〔実施例A-19〕:熱転写表面改質シート(19)
 樹脂(1)を樹脂(19)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤)(重量比50/50混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(19)を作製した。
〔実施例A-20〕:熱転写表面改質シート(20)
 樹脂(1)を樹脂(20)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤)(重量比60/40混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(20)を作製した。
〔実施例A-21〕:熱転写表面改質シート(21)
 樹脂(1)を樹脂(21)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤)(重量比70/30混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(21)を作製した。
〔実施例A-22〕:熱転写表面改質シート(22)
 樹脂(1)を樹脂(22)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤)(重量比80/20混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(22)を作製した。
〔実施例A-23〕:熱転写表面改質シート(23)
 樹脂(1)を樹脂(23)(株式会社鉛市製、Fine Resin FR-105(メトキシメチル化ポリアミド樹脂)/四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤)(重量比90/10混合物))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、実施例A-1と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(23)を作製した。
Figure JPOXMLDOC01-appb-T000001
〔実施例B-1〕:積層部材(G-PPS-1)
 ガラス繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、G-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の上に、熱転写表面改質シート(1)を易接着層側が内側になるように載せ、加熱プレス(270℃×10分)し、ガラス繊維強化PPS表面に易接着層を熱溶着させ、離型シートを除去し、表面処理を行い、積層部材(G-PPS-1)を製造した。
〔実施例B-2〕:積層部材(G-PPS-2)
 熱転写表面改質シート(1)を熱転写表面改質シート(2)に変更した以外は、実施例B-1と同様にして、表面処理を行い、積層部材(G-PPS-2)を製造した。
〔実施例B-3〕:積層部材(G-PPS-3)
 熱転写表面改質シート(1)を熱転写表面改質シート(3)に変更した以外は、実施例B-1と同様にして、表面処理を行い、積層部材(G-PPS-3)を製造した。
〔実施例B-4〕:積層部材(G-PPS-4)
 熱転写表面改質シート(1)を熱転写表面改質シート(4)に変更した以外は、実施例B-1と同様にして、表面処理を行い、積層部材(G-PPS-4)を製造した。
〔実施例C-1〕:積層部材(C-PPS-1)
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の上に、熱転写表面改質シート(1)を易接着層側が内側になるように載せ、加熱プレス(270℃×10分)し、炭素繊維強化PPS表面に易接着層を熱溶着させ、離型シートを除去し、表面処理を行い、積層部材(C-PPS-1)を製造した。
〔実施例C-1´〕:積層部材(C-PPS-1´)
 加熱プレスを250℃×10分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-1´)を製造した。
〔実施例C-1´´〕:積層部材(C-PPS-1´´)
 加熱プレスを300℃×10分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-1´´)を製造した。
〔実施例C-2〕:積層部材(C-PPS-2)
 熱転写表面改質シート(1)を熱転写表面改質シート(2)に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-2)を製造した。
〔実施例C-3〕:積層部材(C-PPS-3)
 熱転写表面改質シート(1)を熱転写表面改質シート(3)に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-3)を製造した。
〔実施例C-4〕:積層部材(C-PPS-4)
 熱転写表面改質シート(1)を熱転写表面改質シート(4)に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-4)を製造した。
〔比較例B-1〕:積層部材(G-PPS-5)
 樹脂(1)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 ガラス繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、G-PPS、寸法:幅25mm×長さ100mm×厚み2mm)をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、表面処理を行い、積層部材(G-PPS-5)を製造した。
〔比較例B-2〕:積層部材(G-PPS-6)
 樹脂(1)を樹脂(2)に変更した以外は、比較例B-1と同様にして、表面処理を行い、積層部材(G-PPS-6)を製造した。
〔比較例B-3〕:積層部材(G-PPS-7)
 樹脂(1)を樹脂(3)に変更した以外は、比較例B-1と同様にして、表面処理を行い、積層部材(G-PPS-7)を製造した。
〔比較例B-4〕:積層部材(G-PPS-8)
 樹脂(1)を樹脂(4)に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例B-1と同様にして、表面処理を行い、積層部材(G-PPS-8)を製造した。
〔比較例C-1〕:積層部材(C-PPS-5)
 樹脂(1)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、表面処理を行い、積層部材(C-PPS-5)を製造した。
〔比較例C-2〕:積層部材(C-PPS-6)
 樹脂(1)を樹脂(2)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-6)を製造した。
〔比較例C-3〕:積層部材(C-PPS-7)
 樹脂(1)を樹脂(3)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-7)を製造した。
〔比較例C-4〕:積層部材(C-PPS-8)
 樹脂(1)を樹脂(4)に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-8)を製造した。
〔実施例B-5〕:積層部材(G-PPS-9)
 比較例B-1で製造した積層部材(G-PPS-5)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(G-PPS-9)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例B-6〕:積層部材(G-PPS-10)
 比較例B-2で製造した積層部材(G-PPS-6)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(G-PPS-10)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例B-7〕:積層部材(G-PPS-11)
 比較例B-3で製造した積層部材(G-PPS-7)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(G-PPS-11)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例B-8〕:積層部材(G-PPS-12)
 比較例B-4で製造した積層部材(G-PPS-8)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(G-PPS-12)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-5〕:積層部材(C-PPS-9)
 比較例C-1で製造した積層部材(C-PPS-5)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-9)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-5´〕:積層部材(C-PPS-9´)
 加熱プレスを250℃×10分に変更した以外は、実施例C-5と同様にして、表面処理を行い、積層部材(C-PPS-9´)を製造した。
〔実施例C-5´´〕:積層部材(C-PPS-9´´)
 加熱プレスを300℃×10分に変更した以外は、実施例C-5と同様にして、表面処理を行い、積層部材(C-PPS-9´´)を製造した。
〔実施例C-6〕:積層部材(C-PPS-10)
 比較例C-2で製造した積層部材(C-PPS-6)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-10)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-7〕:積層部材(C-PPS-11)
 比較例C-3で製造した積層部材(C-PPS-7)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-11)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-8〕:積層部材(C-PPS-12)
 比較例C-4で製造した積層部材(C-PPS-8)を加熱プレス(270℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-12)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-9〕:積層部材(C-PPS-13)
 熱転写表面改質シート(1)を熱転写表面改質シート(5)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-13)を製造した。
〔実施例C-10〕:積層部材(C-PPS-14)
 熱転写表面改質シート(1)を熱転写表面改質シート(6)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-14)を製造した。
〔実施例C-11〕:積層部材(C-PPS-15)
 熱転写表面改質シート(1)を熱転写表面改質シート(7)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-15)を製造した。
〔実施例C-12〕:積層部材(C-PPS-16)
 熱転写表面改質シート(1)を熱転写表面改質シート(8)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-16)を製造した。
〔実施例C-13〕:積層部材(C-PPS-17)
 熱転写表面改質シート(1)を熱転写表面改質シート(9)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-17)を製造した。
〔実施例C-14〕:積層部材(C-PPS-18)
 熱転写表面改質シート(1)を熱転写表面改質シート(10)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-18)を製造した。
〔実施例C-15〕:積層部材(C-PPS-19)
 熱転写表面改質シート(1)を熱転写表面改質シート(11)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-19)を製造した。
〔実施例C-16〕:積層部材(C-PPS-20)
 熱転写表面改質シート(1)を熱転写表面改質シート(12)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-20)を製造した。
〔実施例C-17〕:積層部材(C-PPS-21)
 熱転写表面改質シート(1)を熱転写表面改質シート(13)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-21)を製造した。
〔実施例C-18〕:積層部材(C-PPS-22)
 熱転写表面改質シート(1)を熱転写表面改質シート(14)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-22)を製造した。
〔実施例C-19〕:積層部材(C-PPS-23)
 熱転写表面改質シート(1)を熱転写表面改質シート(15)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-23)を製造した。
〔実施例C-20〕:積層部材(C-PPS-24)
 熱転写表面改質シート(1)を熱転写表面改質シート(16)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-24)を製造した。
〔実施例C-21〕:積層部材(C-PPS-25)
 熱転写表面改質シート(1)を熱転写表面改質シート(17)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-25)を製造した。
〔実施例C-22〕:積層部材(C-PPS-26)
 熱転写表面改質シート(1)を熱転写表面改質シート(18)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-26)を製造した。
〔実施例C-23〕:積層部材(C-PPS-27)
 熱転写表面改質シート(1)を熱転写表面改質シート(19)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-27)を製造した。
〔実施例C-24〕:積層部材(C-PPS-28)
 熱転写表面改質シート(1)を熱転写表面改質シート(20)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-28)を製造した。
〔実施例C-25〕:積層部材(C-PPS-29)
 熱転写表面改質シート(1)を熱転写表面改質シート(21)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-29)を製造した。
〔実施例C-26〕:積層部材(C-PPS-30)
 熱転写表面改質シート(1)を熱転写表面改質シート(22)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-30)を製造した。
〔実施例C-27〕:積層部材(C-PPS-31)
 熱転写表面改質シート(1)を熱転写表面改質シート(23)に変更し、加熱プレスを290℃×1分に変更した以外は、実施例C-1と同様にして、表面処理を行い、積層部材(C-PPS-31)を製造した。
〔実施例C-28〕:積層部材(C-PPS-32)
 樹脂(1)を樹脂(5)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-32)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-29〕:積層部材(C-PPS-33)
 樹脂(1)を樹脂(6)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-33)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-30〕:積層部材(C-PPS-34)
 樹脂(1)を樹脂(7)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-34)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-31〕:積層部材(C-PPS-35)
 樹脂(1)を樹脂(8)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-35)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-32〕:積層部材(C-PPS-36)
 樹脂(1)を樹脂(9)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-36)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-33〕:積層部材(C-PPS-37)
 樹脂(1)を樹脂(10)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-37)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-34〕:積層部材(C-PPS-38)
 樹脂(1)を樹脂(11)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-38)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-35〕:積層部材(C-PPS-39)
 樹脂(1)を樹脂(12)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-39)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-36〕:積層部材(C-PPS-40)
 樹脂(1)を樹脂(13)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-40)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-37〕:積層部材(C-PPS-41)
 樹脂(1)を樹脂(14)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-41)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-38〕:積層部材(C-PPS-42)
 樹脂(1)を樹脂(15)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-42)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-39〕:積層部材(C-PPS-43)
 樹脂(1)を樹脂(16)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-43)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-40〕:積層部材(C-PPS-44)
 樹脂(1)を樹脂(17)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-44)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-41〕:積層部材(C-PPS-45)
 樹脂(1)を樹脂(19)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-45)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-42〕:積層部材(C-PPS-46)
 樹脂(1)を樹脂(24)(東亜合成株式会社製、ARUFON(登録商標) UH-2041(水酸基含有アクリル系ポリマー))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-46)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-43〕:積層部材(C-PPS-47)
 樹脂(1)を樹脂(25)(東亜合成株式会社製、ARUFON(登録商標) UH-2170(水酸基含有アクリル系ポリマー))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-47)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-44〕:積層部材(C-PPS-48)
 樹脂(1)を樹脂(26)(東亜合成株式会社製、ARUFON(登録商標) UH-2190(水酸基含有アクリル系ポリマー))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-48)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-45〕:積層部材(C-PPS-49)
 樹脂(1)を樹脂(27)(東亜合成株式会社製、ARUFON(登録商標) UC-3000(カルボキシル基含有アクリル系ポリマー))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-49)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-46〕:積層部材(C-PPS-50)
 樹脂(1)を樹脂(28)(東亜合成株式会社製、ARUFON(登録商標) UC-3080(カルボキシル基含有アクリル系ポリマー))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-50)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-47〕:積層部材(C-PPS-51)
 樹脂(1)を樹脂(29)(東亜合成株式会社製、ARUFON(登録商標) UC-3150(カルボキシル基含有アクリル系ポリマー))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-51)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-48〕:積層部材(C-PPS-52)
 樹脂(1)を易接着層の材料(30)(株式会社日本触媒製、エポミン(登録商標) SP-200(ポリエチレンイミン))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-52)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-49〕:積層部材(C-PPS-53)
 樹脂(1)を易接着層の材料(31)(四国化成工業株式会社製、キュアゾール 2P4MHZ-PW(イミダゾール系エポキシ樹脂硬化剤))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-53)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-50〕:積層部材(C-PPS-54)
 樹脂(1)を易接着層の材料(32)(和光純薬工業株式会社製、ナフィオン)に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-54)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例C-51〕:積層部材(C-PPS-55)
 樹脂(1)を易接着層の材料(32)(四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤))に変更した以外は、比較例C-1と同様にして、表面処理を行って製造された積層部材を加熱プレス(290℃×1分)し、加熱処理を行い、表面処理を行い、積層部材(C-PPS-55)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例1〕:接合構造体(1)
 実施例B-1で得られた積層部材(G-PPS-1)の2つを(接合方法1)で接合し、接合構造体(1)を製造した。結果を表2に示した。
〔実施例2〕:接合構造体(2)
 実施例B-2で得られた積層部材(G-PPS-2)の2つを(接合方法1)で接合し、接合構造体(2)を製造した。結果を表2に示した。
〔実施例3〕:接合構造体(3)
 実施例B-3で得られた積層部材(G-PPS-3)の2つを(接合方法1)で接合し、接合構造体(3)を製造した。結果を表2に示した。
〔実施例4〕:接合構造体(4)
 実施例B-4で得られた積層部材(G-PPS-4)の2つを(接合方法1)で接合し、接合構造体(4)を製造した。結果を表2に示した。
〔実施例5〕:接合構造体(5)
 実施例C-1で得られた積層部材(C-PPS-1)の2つを(接合方法1)で接合し、接合構造体(5)を製造した。結果を表2に示した。
〔実施例6〕:接合構造体(6)
 実施例C-1´で得られた積層部材(C-PPS-1´)の2つを(接合方法1)で接合し、接合構造体(6)を製造した。結果を表2に示した。
〔実施例7〕:接合構造体(7)
 実施例C-1´´で得られた積層部材(C-PPS-1´´)の2つを(接合方法1)で接合し、接合構造体(7)を製造した。結果を表2に示した。
〔実施例8〕:接合構造体(8)
 実施例C-2で得られた積層部材(C-PPS-2)の2つを(接合方法1)で接合し、接合構造体(8)を製造した。結果を表2に示した。
〔実施例9〕:接合構造体(9)
 実施例C-3で得られた積層部材(C-PPS-3)の2つを(接合方法1)で接合し、接合構造体(9)を製造した。結果を表2に示した。
〔実施例10〕:接合構造体(10)
 実施例C-4で得られた積層部材(C-PPS-4)の2つを(接合方法1)で接合し、接合構造体(10)を製造した。結果を表2に示した。
〔実施例11〕:接合構造体(11)
 実施例C-2で得られた積層部材(C-PPS-2)の2つを(接合方法2)で接合し、接合構造体(11)を製造した。結果を表2に示した。
〔実施例12〕:接合構造体(12)
 実施例B-5で得られた積層部材(G-PPS-9)の2つを(接合方法1)で接合し、接合構造体(12)を製造した。結果を表2に示した。
〔実施例13〕:接合構造体(13)
 実施例B-6で得られた積層部材(G-PPS-10)の2つを(接合方法1)で接合し、接合構造体(13)を製造した。結果を表2に示した。
〔実施例14〕:接合構造体(14)
 実施例B-7で得られた積層部材(G-PPS-11)の2つを(接合方法1)で接合し、接合構造体(14)を製造した。結果を表2に示した。
〔実施例15〕:接合構造体(15)
 実施例B-8で得られた積層部材(G-PPS-12)の2つを(接合方法1)で接合し、接合構造体(15)を製造した。結果を表2に示した。
〔実施例16〕:接合構造体(16)
 実施例C-5で得られた積層部材(C-PPS-9)の2つを(接合方法1)で接合し、接合構造体(16)を製造した。結果を表2に示した。
〔実施例17〕:接合構造体(17)
 実施例C-5´で得られた積層部材(C-PPS-9´)の2つを(接合方法1)で接合し、接合構造体(17)を製造した。結果を表2に示した。
〔実施例18〕:接合構造体(18)
 実施例C-5´´で得られた積層部材(C-PPS-9´´)の2つを(接合方法1)で接合し、接合構造体(18)を製造した。結果を表2に示した。
〔実施例19〕:接合構造体(19)
 実施例C-6で得られた積層部材(C-PPS-10)の2つを(接合方法1)で接合し、接合構造体(19)を製造した。結果を表2に示した。
〔実施例20〕:接合構造体(20)
 実施例C-7で得られた積層部材(C-PPS-11)の2つを(接合方法1)で接合し、接合構造体(20)を製造した。結果を表2に示した。
〔実施例21〕:接合構造体(21)
 実施例C-8で得られた積層部材(C-PPS-12)の2つを(接合方法1)で接合し、接合構造体(21)を製造した。結果を表2に示した。
〔実施例22〕:接合構造体(22)
 実施例C-6で得られた積層部材(C-PPS-10)の2つを(接合方法2)で接合し、接合構造体(22)を製造した。結果を表2に示した。
〔比較例1〕:接合構造体(C1)
 ガラス繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、G-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法1)で接合し、接合構造体(C1)を製造した。結果を表3に示した。
〔比較例2〕:接合構造体(C2)
 比較例B-1で得られた積層部材(G-PPS-5)の2つを(接合方法1)で接合し、接合構造体(C2)を製造した。結果を表3に示した。
〔比較例3〕:接合構造体(C3)
 比較例B-2で得られた積層部材(G-PPS-6)の2つを(接合方法1)で接合し、接合構造体(C3)を製造した。結果を表3に示した。
〔比較例4〕:接合構造体(C4)
 比較例B-3で得られた積層部材(G-PPS-7)の2つを(接合方法1)で接合し、接合構造体(C4)を製造した。結果を表3に示した。
〔比較例5〕:接合構造体(C5)
 比較例B-4で得られた積層部材(G-PPS-8)の2つを(接合方法1)で接合し、接合構造体(C5)を製造した。結果を表3に示した。
〔比較例6〕:接合構造体(C6)
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法1)で接合し、接合構造体(C6)を製造した。結果を表3に示した。
〔比較例7〕:接合構造体(C7)
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法2)で接合し、接合構造体(C7)を製造した。結果を表3に示した。
〔比較例8〕:接合構造体(C8)
 比較例C-1で得られた積層部材(C-PPS-5)の2つを(接合方法1)で接合し、接合構造体(C8)を製造した。結果を表3に示した。
〔比較例9〕:接合構造体(C9)
 比較例C-2で得られた積層部材(C-PPS-6)の2つを(接合方法1)で接合し、接合構造体(C9)を製造した。結果を表3に示した。
〔比較例10〕:接合構造体(C10)
 比較例C-3で得られた積層部材(C-PPS-7)の2つを(接合方法1)で接合し、接合構造体(C10)を製造した。結果を表3に示した。
〔比較例11〕:接合構造体(C11)
 比較例C-4で得られた積層部材(C-PPS-8)の2つを(接合方法1)で接合し、接合構造体(C11)を製造した。結果を表3に示した。
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
〔実施例23〕:接合構造体(23)
 実施例C-9で得られた積層部材(C-PPS-13)の2つを(接合方法2)で接合し、接合構造体(23)を製造した。結果を表4に示した。
〔実施例24〕:接合構造体(24)
 実施例C-10で得られた積層部材(C-PPS-14)の2つを(接合方法2)で接合し、接合構造体(24)を製造した。結果を表4に示した。
〔実施例25〕:接合構造体(25)
 実施例C-11で得られた積層部材(C-PPS-15)の2つを(接合方法2)で接合し、接合構造体(25)を製造した。結果を表4に示した。
〔実施例26〕:接合構造体(26)
 実施例C-12で得られた積層部材(C-PPS-16)の2つを(接合方法2)で接合し、接合構造体(26)を製造した。結果を表4に示した。
〔実施例27〕:接合構造体(27)
 実施例C-13で得られた積層部材(C-PPS-17)の2つを(接合方法2)で接合し、接合構造体(27)を製造した。結果を表4に示した。
〔実施例28〕:接合構造体(28)
 実施例C-14で得られた積層部材(C-PPS-18)の2つを(接合方法2)で接合し、接合構造体(28)を製造した。結果を表4に示した。
〔実施例29〕:接合構造体(29)
 実施例C-15で得られた積層部材(C-PPS-19)の2つを(接合方法2)で接合し、接合構造体(29)を製造した。結果を表4に示した。
〔実施例30〕:接合構造体(30)
 実施例C-16で得られた積層部材(C-PPS-20)の2つを(接合方法2)で接合し、接合構造体(30)を製造した。結果を表4に示した。
〔実施例31〕:接合構造体(31)
 実施例C-17で得られた積層部材(C-PPS-21)の2つを(接合方法2)で接合し、接合構造体(31)を製造した。結果を表4に示した。
〔実施例32〕:接合構造体(32)
 実施例C-18で得られた積層部材(C-PPS-22)の2つを(接合方法2)で接合し、接合構造体(32)を製造した。結果を表4に示した。
〔実施例33〕:接合構造体(33)
 実施例C-19で得られた積層部材(C-PPS-23)の2つを(接合方法2)で接合し、接合構造体(33)を製造した。結果を表4に示した。
〔実施例34〕:接合構造体(34)
 実施例C-20で得られた積層部材(C-PPS-24)の2つを(接合方法2)で接合し、接合構造体(34)を製造した。結果を表4に示した。
〔実施例35〕:接合構造体(35)
 実施例C-21で得られた積層部材(C-PPS-25)の2つを(接合方法2)で接合し、接合構造体(35)を製造した。結果を表4に示した。
〔実施例36〕:接合構造体(36)
 実施例C-22で得られた積層部材(C-PPS-26)の2つを(接合方法2)で接合し、接合構造体(36)を製造した。結果を表4に示した。
〔実施例37〕:接合構造体(37)
 実施例C-23で得られた積層部材(C-PPS-27)の2つを(接合方法2)で接合し、接合構造体(37)を製造した。結果を表4に示した。
〔実施例38〕:接合構造体(38)
 実施例C-24で得られた積層部材(C-PPS-28)の2つを(接合方法2)で接合し、接合構造体(38)を製造した。結果を表4に示した。
〔実施例39〕:接合構造体(39)
 実施例C-25で得られた積層部材(C-PPS-29)の2つを(接合方法2)で接合し、接合構造体(39)を製造した。結果を表4に示した。
〔実施例40〕:接合構造体(40)
 実施例C-26で得られた積層部材(C-PPS-30)の2つを(接合方法2)で接合し、接合構造体(40)を製造した。結果を表4に示した。
〔実施例41〕:接合構造体(41)
 実施例C-27で得られた積層部材(C-PPS-31)の2つを(接合方法2)で接合し、接合構造体(41)を製造した。結果を表4に示した。
〔実施例42〕:接合構造体(42)
 実施例C-14で得られた積層部材(C-PPS-18)の2つを(接合方法1)で接合し、接合構造体(42)を製造した。結果を表4に示した。
〔実施例43〕:接合構造体(43)
 実施例C-14で得られた積層部材(C-PPS-18)の2つを(接合方法4)で接合し、接合構造体(43)を製造した。結果を表4に示した。
〔実施例44〕:接合構造体(44)
 実施例C-14で得られた積層部材(C-PPS-18)の2つを(接合方法5)で接合し、接合構造体(44)を製造した。結果を表4に示した。
〔実施例45〕:接合構造体(45)
 実施例C-14で得られた積層部材(C-PPS-18)の2つを(接合方法6)で接合し、接合構造体(45)を製造した。結果を表4に示した。
〔実施例46〕:接合構造体(46)
 実施例C-23で得られた積層部材(C-PPS-27)の2つを(接合方法1)で接合し、接合構造体(46)を製造した。結果を表4に示した。
〔実施例47〕:接合構造体(47)
 実施例C-23で得られた積層部材(C-PPS-27)の2つを(接合方法4)で接合し、接合構造体(47)を製造した。結果を表4に示した。
〔実施例48〕:接合構造体(48)
 実施例C-23で得られた積層部材(C-PPS-27)の2つを(接合方法5)で接合し、接合構造体(48)を製造した。結果を表4に示した。
〔実施例49〕:接合構造体(49)
 実施例C-14で得られた積層部材(C-PPS-27)の2つを(接合方法6)で接合し、接合構造体(49)を製造した。結果を表4に示した。
Figure JPOXMLDOC01-appb-T000004
〔実施例50〕:接合構造体(50)
 実施例C-28で得られた積層部材(C-PPS-32)の2つを(接合方法2)で接合し、接合構造体(50)を製造した。結果を表5に示した。
〔実施例51〕:接合構造体(51)
 実施例C-29で得られた積層部材(C-PPS-33)の2つを(接合方法2)で接合し、接合構造体(51)を製造した。結果を表5に示した。
〔実施例52〕:接合構造体(52)
 実施例C-30で得られた積層部材(C-PPS-34)の2つを(接合方法2)で接合し、接合構造体(52)を製造した。結果を表5に示した。
〔実施例53〕:接合構造体(53)
 実施例C-31で得られた積層部材(C-PPS-35)の2つを(接合方法2)で接合し、接合構造体(53)を製造した。結果を表5に示した。
〔実施例54〕:接合構造体(54)
 実施例C-32で得られた積層部材(C-PPS-36)の2つを(接合方法2)で接合し、接合構造体(54)を製造した。結果を表5に示した。
〔実施例55〕:接合構造体(55)
 実施例C-33で得られた積層部材(C-PPS-37)の2つを(接合方法2)で接合し、接合構造体(55)を製造した。結果を表5に示した。
〔実施例56〕:接合構造体(56)
 実施例C-34で得られた積層部材(C-PPS-38)の2つを(接合方法2)で接合し、接合構造体(56)を製造した。結果を表5に示した。
〔実施例57〕:接合構造体(57)
 実施例C-35で得られた積層部材(C-PPS-39)の2つを(接合方法2)で接合し、接合構造体(57)を製造した。結果を表5に示した。
〔実施例58〕:接合構造体(58)
 実施例C-36で得られた積層部材(C-PPS-40)の2つを(接合方法2)で接合し、接合構造体(58)を製造した。結果を表5に示した。
〔実施例59〕:接合構造体(59)
 実施例C-37で得られた積層部材(C-PPS-41)の2つを(接合方法2)で接合し、接合構造体(59)を製造した。結果を表5に示した。
〔実施例60〕:接合構造体(60)
 実施例C-38で得られた積層部材(C-PPS-42)の2つを(接合方法2)で接合し、接合構造体(60)を製造した。結果を表5に示した。
〔実施例61〕:接合構造体(61)
 実施例C-39で得られた積層部材(C-PPS-43)の2つを(接合方法2)で接合し、接合構造体(61)を製造した。結果を表5に示した。
〔実施例62〕:接合構造体(62)
 実施例C-40で得られた積層部材(C-PPS-44)の2つを(接合方法2)で接合し、接合構造体(62)を製造した。結果を表5に示した。
〔実施例63〕:接合構造体(63)
 実施例C-41で得られた積層部材(C-PPS-45)の2つを(接合方法2)で接合し、接合構造体(63)を製造した。結果を表5に示した。
〔実施例64〕:接合構造体(64)
 実施例C-42で得られた積層部材(C-PPS-46)の2つを(接合方法2)で接合し、接合構造体(64)を製造した。結果を表5に示した。
〔実施例65〕:接合構造体(65)
 実施例C-43で得られた積層部材(C-PPS-47)の2つを(接合方法2)で接合し、接合構造体(65)を製造した。結果を表5に示した。
〔実施例66〕:接合構造体(66)
 実施例C-44で得られた積層部材(C-PPS-48)の2つを(接合方法2)で接合し、接合構造体(66)を製造した。結果を表5に示した。
〔実施例67〕:接合構造体(67)
 実施例C-45で得られた積層部材(C-PPS-49)の2つを(接合方法2)で接合し、接合構造体(67)を製造した。結果を表5に示した。
〔実施例68〕:接合構造体(68)
 実施例C-46で得られた積層部材(C-PPS-50)の2つを(接合方法2)で接合し、接合構造体(68)を製造した。結果を表5に示した。
〔実施例69〕:接合構造体(69)
 実施例C-47で得られた積層部材(C-PPS-51)の2つを(接合方法2)で接合し、接合構造体(69)を製造した。結果を表5に示した。
〔実施例70〕:接合構造体(70)
 実施例C-48で得られた積層部材(C-PPS-52)の2つを(接合方法2)で接合し、接合構造体(70)を製造した。結果を表5に示した。
〔実施例71〕:接合構造体(71)
 実施例C-49で得られた積層部材(C-PPS-53)の2つを(接合方法2)で接合し、接合構造体(71)を製造した。結果を表5に示した。
〔実施例72〕:接合構造体(72)
 実施例C-50で得られた積層部材(C-PPS-54)の2つを(接合方法2)で接合し、接合構造体(72)を製造した。結果を表5に示した。
〔実施例73〕:接合構造体(73)
 実施例C-51で得られた積層部材(C-PPS-55)の2つを(接合方法2)で接合し、接合構造体(73)を製造した。結果を表5に示した。
Figure JPOXMLDOC01-appb-T000005
〔比較例C-5〕:積層部材(C-PPS-56)
 樹脂(1)を樹脂(6)に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-56)を製造した。
〔比較例C-6〕:積層部材(C-PPS-57)
 樹脂(1)を樹脂(19)に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-57)を製造した。
〔比較例C-7〕:積層部材(C-PPS-58)
 樹脂(1)を易接着層の材料(30)(株式会社日本触媒製、エポミン(登録商標) SP-200(ポリエチレンイミン))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-58)を製造した。
〔比較例C-8〕:積層部材(C-PPS-59)
 樹脂(1)を易接着層の材料(32)(和光純薬工業株式会社製、ナフィオン)に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-59)を製造した。
〔比較例C-9〕:積層部材(C-PPS-60)
 樹脂(1)を易接着層の材料(32)(四国化成工業株式会社製、キュアゾール C11Z-CN(イミダゾール系エポキシ樹脂硬化剤))に変更し、熱トルエン(60℃)をメタノール(常温)に変更した以外は、比較例C-1と同様にして、表面処理を行い、積層部材(C-PPS-60)を製造した。
〔比較例12〕:接合構造体(C12)
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法4)で接合し、接合構造体(C12)を製造した。結果を表6に示した。
〔比較例13〕:接合構造体(C13)
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法5)で接合し、接合構造体(C13)を製造した。結果を表6に示した。
〔比較例14〕:接合構造体(C14)
 炭素繊維強化ポリフェニレンサルファイド(日本テストパネル(株)製、C-PPS、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法6)で接合し、接合構造体(C14)を製造した。結果を表6に示した。
〔比較例15〕:接合構造体(C15)
 比較例C-5で得られた積層部材(C-PPS-56)の2つを(接合方法2)で接合し、接合構造体(C15)を製造した。結果を表6に示した。
〔比較例16〕:接合構造体(C16)
 比較例C-6で得られた積層部材(C-PPS-57)の2つを(接合方法2)で接合し、接合構造体(C16)を製造した。結果を表6に示した。
〔比較例17〕:接合構造体(C17)
 比較例C-7で得られた積層部材(C-PPS-58)の2つを(接合方法2)で接合し、接合構造体(C17)を製造した。結果を表6に示した。
〔比較例18〕:接合構造体(C18)
 比較例C-8で得られた積層部材(C-PPS-59)の2つを(接合方法2)で接合し、接合構造体(C18)を製造した。結果を表6に示した。
〔比較例19〕:接合構造体(C19)
 比較例C-9で得られた積層部材(C-PPS-60)の2つを(接合方法2)で接合し、接合構造体(C19)を製造した。結果を表6に示した。
Figure JPOXMLDOC01-appb-T000006
〔実施例A-24〕:熱転写表面改質シート(24)
 樹脂(33)(日油(株)製、モディパーA5400(エチレン/エチルアクリレート-グラフト-スチレン/アクリロニトリル共重合体)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 離型シート(日東電工(株)製、ニトフロンNo.900UL(厚み0.18mm))をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、易接着層を備えた離型シートである熱転写表面改質シート(24)を作製した。
〔実施例A-25〕:熱転写表面改質シート(25)
 樹脂(33)を樹脂(34)(日油(株)製、モディパーA6600(エチレン/酢酸ビニル--グラフト-変性メチルメタクリレート共重合体)に変更した以外は、実施例A-24と同様にして、易接着層を備えた離型シートである熱転写表面改質シート(25)を作製した。
〔実施例D-1〕:積層部材(PP-1/転写)
 PP板(寸法:幅25mm×長さ100mm×厚み2mm)の上に、熱転写表面改質シート(24)を易接着層側が内側になるように載せ、加熱プレス(120℃×10分)し、PP板表面に易接着層を熱溶着させ、離型シートを除去し、表面処理を行い、積層部材(PP-1/転写)を製造した。
〔実施例D-2〕:積層部材(PP-2/転写)
 熱転写表面改質シート(24)を熱転写表面改質シート(25)に変更した以外は、実施例D-1と同様にして、表面処理を行い、積層部材(PP-2/転写)を製造した。
〔比較例D-1〕:積層部材(PP-1/塗布)
 樹脂(33)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 PP板(寸法:幅25mm×長さ100mm×厚み2mm)をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、表面処理を行い、積層部材(PP-1/塗布)を製造した。
〔比較例D-2〕:積層部材(PP-2/塗布)
 樹脂(33)を樹脂(34)に変更した以外は、比較例D-1と同様にして、表面処理を行い、積層部材(PP-2/塗布)を製造した。
〔実施例D-3〕:積層部材(PP-1/塗布加熱)
 比較例D-1で製造した積層部材(PP-1/塗布)を加熱プレス(120℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(PP-1/塗布加熱)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例D-4〕:積層部材(PP-2/塗布加熱)
 比較例D-2で製造した積層部材(PP-2/塗布)を加熱プレス(120℃×10分)し、加熱処理を行い、表面処理を行い、積層部材(PP-2/塗布加熱)を製造した。加熱プレスの際には、プレス板と被着体(繊維強化樹脂)の間に離形シート(日東電工(株)製、ニトフロンNo.900UL、厚み0.18mm)を挟んで行った。
〔実施例74〕:接合構造体(74)
 実施例D-1で得られた積層部材(PP-1/転写)の2つを(接合方法3)で接合し、接合構造体(74)を製造した。結果を表7に示した。
〔実施例75〕:接合構造体(75)
 実施例D-2で得られた積層部材(PP-2/転写)の2つを(接合方法3)で接合し、接合構造体(75)を製造した。結果を表7に示した。
〔実施例76〕:接合構造体(76)
 実施例D-3で得られた積層部材(PP-1/塗布加熱)の2つを(接合方法3)で接合し、接合構造体(76)を製造した。結果を表7に示した。
〔実施例77〕:接合構造体(77)
 実施例D-4で得られた積層部材(PP-2/塗布加熱)の2つを(接合方法3)で接合し、接合構造体(77)を製造した。結果を表7に示した。
〔比較例20〕:接合構造体(C20)
 PP板(寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法3)で接合し、接合構造体(C20)を製造した。結果を表7に示した。
〔比較例21〕:接合構造体(C21)
 比較例D-1で得られた積層部材(PP-1/塗布)の2つを(接合方法3)で接合し、接合構造体(C21)を製造した。結果を表7に示した。
〔比較例22〕:接合構造体(C22)
 比較例D-2で得られた積層部材(PP-2/塗布)の2つを(接合方法3)で接合し、接合構造体(C22)を製造した。結果を表7に示した。
Figure JPOXMLDOC01-appb-T000007
〔実施例D-5〕:積層部材(G-PP-1)
 ガラス繊維強化ポリプロピレン(日本テストパネル(株)製、G-PP、寸法:幅25mm×長さ100mm×厚み2mm)の上に、熱転写表面改質シート(6)を易接着層側が内側になるように載せ、加熱プレス(170℃×1分)し、ガラス繊維強化PP表面に易接着層を熱溶着させ、離型シートを除去し、表面処理を行い、積層部材(G-PP-1)を製造した。
〔実施例D-6〕:積層部材(G-PP-2)
 熱転写表面改質シート(6)を熱転写表面改質シート(19)に変更した以外は、実施例D-5と同様にして、表面処理を行い、積層部材(G-PP-2)を製造した。
〔実施例D-7〕:積層部材(G-PP-3)
 熱転写表面改質シート(6)を熱転写表面改質シート(10)に変更した以外は、実施例D-5と同様にして、表面処理を行い、積層部材(G-PP-3)を製造した。
〔比較例D-3〕:積層部材(G-PP-4)
 樹脂(6)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 ガラス繊維強化ポリプロピレン(日本テストパネル(株)製、G-PP、寸法:幅25mm×長さ100mm×厚み2mm)をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、表面処理を行い、積層部材(G-PP-4)を製造した。
〔比較例D-4〕:積層部材(G-PP-5)
 樹脂(6)を樹脂(19)に変更した以外は、比較例D-3と同様にして、表面処理を行い、積層部材(G-PP-5)を製造した。
〔実施例78〕:接合構造体(78)
 実施例D-5で得られた積層部材(G-PP-1)の2つを(接合方法7)で接合し、接合構造体(78)を製造した。結果を表8に示した。
〔実施例79〕:接合構造体(79)
 実施例D-6で得られた積層部材(G-PP-2)の2つを(接合方法7)で接合し、接合構造体(79)を製造した。結果を表8に示した。
〔実施例80〕:接合構造体(80)
 実施例D-6で得られた積層部材(G-PP-2)の2つを(接合方法6)で接合し、接合構造体(80)を製造した。結果を表8に示した。
〔実施例81〕:接合構造体(81)
 実施例D-7で得られた積層部材(G-PP-3)の2つを(接合方法6)で接合し、接合構造体(81)を製造した。結果を表8に示した。
〔比較例23〕:接合構造体(C23)
 ガラス繊維強化ポリプロピレン(日本テストパネル(株)製、G-PP、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法7)で接合し、接合構造体(C23)を製造した。結果を表8に示した。
〔比較例24〕:接合構造体(C24)
 ガラス繊維強化ポリプロピレン(日本テストパネル(株)製、G-PP、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法6)で接合し、接合構造体(C24)を製造した。結果を表8に示した。
〔比較例25〕:接合構造体(C25)
 比較例D-3で得られた積層部材(G-PP-4)の2つを(接合方法7)で接合し、接合構造体(C25)を製造した。結果を表8に示した。
〔比較例26〕:接合構造体(C26)
 比較例D-4で得られた積層部材(G-PP-5)の2つを(接合方法7)で接合し、接合構造体(C26)を製造した。結果を表8に示した。
Figure JPOXMLDOC01-appb-T000008
〔実施例E-1〕:積層部材(C-PA6-1)
 炭素繊維強化ナイロン6(サンワトレーディング(株)製、C-PA6、寸法:幅25mm×長さ100mm×厚み2mm)の上に、熱転写表面改質シート(6)を易接着層側が内側になるように載せ、加熱プレス(225℃×1分)し、炭素繊維強化ナイロン6表面に易接着層を熱溶着させ、離型シートを除去し、表面処理を行い、積層部材(C-PA6-1)を製造した。
〔実施例E-2〕:積層部材(C-PA66-1)
 炭素繊維強化ナイロン66(サンワトレーディング(株)製、C-PA66、寸法:幅25mm×長さ100mm×厚み2mm)の上に、熱転写表面改質シート(6)を易接着層側が内側になるように載せ、加熱プレス(265℃×1分)し、炭素繊維強化ナイロン66表面に易接着層を熱溶着させ、離型シートを除去し、表面処理を行い、積層部材(C-PA66-1)を製造した。
〔実施例E-3〕:積層部材(C-PA6-2)
 熱転写表面改質シート(6)を熱転写表面改質シート(19)に変更した以外は、実施例E-1と同様にして、表面処理を行い、積層部材(C-PA6-2)を製造した。
〔実施例E-4〕:積層部材(C-PA66-2)
 熱転写表面改質シート(6)を熱転写表面改質シート(19)に変更した以外は、実施例E-2と同様にして、表面処理を行い、積層部材(C-PA66-2)を製造した。
〔比較例E-1〕:積層部材(C-PA6-3)
 樹脂(6)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 炭素繊維強化ナイロン6(サンワトレーディング(株)製、C-PA6、寸法:幅25mm×長さ100mm×厚み2mm)をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、表面処理を行い、積層部材(C-PA6-3)を製造した。
〔比較例E-2〕:積層部材(C-PA66-3)
 樹脂(6)を熱トルエン(60℃)に溶解後、室温に冷却して、5重量%溶液を作製した。
 炭素繊維強化ナイロン66(サンワトレーディング(株)製、C-PA66、寸法:幅25mm×長さ100mm×厚み2mm)をその5重量%溶液にてディッピング処理、風乾した後、恒温乾燥器にて100℃×1分間さらに乾燥させ、表面処理を行い、積層部材(C-PA66-3)を製造した。
〔比較例E-3〕:積層部材(C-PA6-4)
 樹脂(6)を樹脂(19)に変更した以外は、比較例E-1と同様にして、表面処理を行い、積層部材(C-PA6-4)を製造した。
〔比較例E-4〕:積層部材(C-PA66-4)
 樹脂(6)を樹脂(19)に変更した以外は、比較例E-2と同様にして、表面処理を行い、積層部材(C-PA66-4)を製造した。
〔実施例82〕:接合構造体(82)
 実施例E-1で得られた積層部材(C-PA6-1)の2つを(接合方法2)で接合し、接合構造体(82)を製造した。結果を表9に示した。
〔実施例83〕:接合構造体(83)
 実施例E-2で得られた積層部材(C-PA66-1)の2つを(接合方法2)で接合し、接合構造体(83)を製造した。結果を表9に示した。
〔実施例84〕:接合構造体(84)
 実施例E-3で得られた積層部材(C-PA6-2)の2つを(接合方法2)で接合し、接合構造体(84)を製造した。結果を表9に示した。
〔実施例85〕:接合構造体(85)
 実施例E-4で得られた積層部材(C-PA66-2)の2つを(接合方法2)で接合し、接合構造体(85)を製造した。結果を表9に示した。
〔比較例27〕:接合構造体(C27)
 炭素繊維強化ナイロン6(サンワトレーディング(株)製、C-PA6、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法2)で接合し、接合構造体(C27)を製造した。結果を表9に示した。
〔比較例28〕:接合構造体(C28)
 炭素繊維強化ナイロン66(サンワトレーディング(株)製、C-PA66、寸法:幅25mm×長さ100mm×厚み2mm)の2つを(接合方法2)で接合し、接合構造体(C28)を製造した。結果を表9に示した。
〔比較例29〕:接合構造体(C29)
 比較例E-1で得られた積層部材(C-PA6-3)の2つを(接合方法2)で接合し、接合構造体(C29)を製造した。結果を表9に示した。
〔比較例30〕:接合構造体(C30)
 比較例E-2で得られた積層部材(C-PA66-3)の2つを(接合方法2)で接合し、接合構造体(C30)を製造した。結果を表9に示した。
〔比較例31〕:接合構造体(C31)
 比較例E-3で得られた積層部材(C-PA6-4)の2つを(接合方法2)で接合し、接合構造体(C31)を製造した。結果を表9に示した。
〔比較例32〕:接合構造体(C32)
 比較例E-4で得られた積層部材(C-PA66-4)の2つを(接合方法2)で接合し、接合構造体(C32)を製造した。結果を表9に示した。
Figure JPOXMLDOC01-appb-T000009
≪シミュレーション≫
(方法)
 ダッソーシステムバイオビア社のソフトウエア(Materials Studio2017)と分子動力学シミュレーター(LAMMPS)を使い、エチレン-グリシジルメタクリレート共重合体とポリフェニレンサルファイドが接触した界面におけるそれぞれの分子の相互拡散構造を下記の方法で解析した。なお、シミュレーションに使用したそれぞれのポリマーの原子数は5100~5150(PPSの分子量換算では約5万)とし、エチレン-グリシジルメタクリレート共重合体モデルはエチレンユニット81重量%、グリシジルメタクリレートユニット19重量%から成るランダム共重合体とした。
 はじめに、ソフトウエア(Materials Studio2017)を使用し、それぞれのポリマーについて、COMPASS力場を使用したNVTアンサンブルの分子動力学計算を300℃で3ns実施し、凝集状態のポリマーモデルを作成した。これらポリマーモデルを直方体のユニットセル(セルパラメータ:a=b=4.9nm、c=16nm、α=β=γ=90°)にそれぞれが接触しないようにc軸方向に重ねて挿入し、COMPASS力場を使った分子力学法による構造最適化計算を行い、三次元境界条件でユニットセルを徐々に圧縮して密度0.5g/cmのモデルを得た。次に、このユニットセルモデルについて、分子動力学シミュレーター(LAMMPS)を使用し、25℃、1atm~100atm条件のNPTアンサンブルの分子動力学計算を10ns以上実施し、最終的にエチレン-グリシジルメタクリレート共重合体とポリフェニレンサルファイドが25℃、1atm条件下でまんべんなく接触したエネルギー的に安定な界面モデルを得た。次に、この界面モデルについてLAMMPSを使用し、300℃のNVTアンサンブルの分子動力学計算を90ns~100ns実施し、25℃から300℃加熱による界面構造の変化を解析した。なお、上述のLAMMPSによる計算では、分子力場にDreidingを使用した。
(結果1)
 300℃で10ns加熱した場合、エチレン-グリシジルメタクリレート共重合体とポリフェニレンサルファイドの混合層の厚みは1.5nmであった。
(結果2)
 300℃で100ns加熱した場合、エチレン-グリシジルメタクリレート共重合体とポリフェニレンサルファイドの混合層の厚みは2.0nmであった。
(結果3)
 25℃で10ns加熱した場合、エチレン-グリシジルメタクリレート共重合体とポリフェニレンサルファイドの混合層の厚みは0.8nmであった。
(結果4)
 25℃で100ns加熱した場合、エチレン-グリシジルメタクリレート共重合体とポリフェニレンサルファイドの混合層の厚みは0.9nmであった。
(考察)
 結果1と結果2より、300℃の加熱においては、加熱時間を長くすると、混合層の厚みが有意に大きくなる(1.5nmから2.0nm)ことが判った。他方、結果3と結果4より、25℃の加熱においては、加熱時間を長くしても、混合層の厚みに有意差が観察されない(0.8nmから0.9nmという僅か0.1nmの差であり、熱の揺らぎの範囲であった)ことが判った。
 本発明の表面改質熱可塑性樹脂の製造方法、接合構造体の製造方法、接合構造体、熱転写表面改質シート、熱転写表面改質シート付熱可塑性樹脂、および、表面改質熱可塑性樹脂は、例えば、鉄道車両、航空機、船舶、自動車などの輸送機器の分野に好適に用い得る。
10   易接着層
20   離型シート
100  熱可塑性樹脂
200  熱転写表面改質シート
300  接着剤層
500  表面改質熱可塑性樹脂
800  熱転写表面改質シート付熱可塑性樹脂
1000 接合構造体

 

Claims (22)

  1.  融点がT℃の熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法であって、
     熱可塑性樹脂の表面の少なくとも一部に易接着層を設け、(T-50)℃以上の温度で加熱溶着を行う、
     表面改質熱可塑性樹脂の製造方法。
  2.  前記加熱溶着が加熱プレスによって行われる、請求項1に記載の製造方法。
  3.  前記加熱プレスによって前記熱可塑性樹脂の成型加工がなされる、請求項2に記載の製造方法。
  4.  離型シートと易接着層の積層体である熱転写表面改質シートの該易接着層側を、前記熱可塑性樹脂の表面の少なくとも一部に載置することにより易接着層を設ける、請求項1から3までのいずれかに記載の製造方法。
  5.  前記加熱溶着の後、離型シートが除去される、請求項4に記載の製造方法。
  6.  熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂の製造方法であって、
     熱可塑性樹脂の表面の少なくとも一部を溶融状態とした後、該熱可塑性樹脂の溶融状態の表面に易接着層を設ける、
     表面改質熱可塑性樹脂の製造方法。
  7.  前記易接着層がポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットとを有する、請求項1から6までのいずれかに記載の製造方法。
  8.  前記ポリマー成分が、メトキシメチル基含有ポリマー、水酸基含有ポリマー、カルボキシル基含有ポリマー、アミノ基含有ポリマーから選ばれる少なくとも1種である、請求項7に記載の製造方法。
  9.  前記易接着層が、3級アミン含有化合物、強酸から選ばれる少なくとも1種を含む、請求項1から8までのいずれかに記載の製造方法。
  10.  請求項1から9までのいずれかに記載の製造方法で得られる表面改質熱可塑性樹脂(A)を、接着剤層を介して被着体に積層させた接合構造体の製造方法であって、
     表面改質熱可塑性樹脂(A)の易接着層側の面に接着剤層を設けて被着体に接合させる、
     接合構造体の製造方法。
  11.  前記接着剤層の成分が極性基と反応する官能基を有する、請求項10に記載の製造方法。
  12.  前記被着体が、請求項1から9までのいずれかに記載の製造方法で得られる表面改質熱可塑性樹脂(B)であり、該被着体である該表面改質熱可塑性樹脂(B)における易接着層側の面に接着剤層を積層させる、請求項10または11に記載の製造方法。
  13.  前記表面改質熱可塑性樹脂(A)を構成する熱可塑性樹脂が、前記表面改質熱可塑性樹脂(B)を構成する熱可塑性樹脂と異なる、請求項12に記載の製造方法。
  14.  熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、接着剤層と、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、をこの順に有する接合構造体であって、
     該2つの表面改質熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP(Pa)とし、該表面改質熱可塑性樹脂を構成する熱可塑性樹脂と接着剤層と該表面改質熱可塑性樹脂を構成する熱可塑性樹脂とをこの順に有する接合構造体における該2つの熱可塑性樹脂同士の25℃、引張速度5mm/minにおける引っ張りせん断接着力をP0(Pa)としたときに、P/P0>2である、
     接合構造体。
  15.  熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、接着剤層と、熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂と、をこの順に有する接合構造体であって、
     該2つの表面改質熱可塑性樹脂同士を25℃、引張速度5mm/minにおいて引張り、接合構造体を破壊した際に、該接着剤層および該2つの表面改質熱可塑性樹脂の少なくとも1つで破壊が生じる、
     接合構造体。
  16.  離型シートと易接着層の積層体である熱転写表面改質シート。
  17.  請求項4に記載の製造方法で用いられる、請求項16に記載の熱転写表面改質シート。
  18.  前記易接着層がポリマー成分を含み、該ポリマー成分が非極性ユニットと極性基を備える極性ユニットを有する、請求項16または17に記載の熱転写表面改質シート。
  19.  前記ポリマー成分が、メトキシメチル基含有ポリマー、水酸基含有ポリマー、カルボキシル基含有ポリマー、アミノ基含有ポリマーから選ばれる少なくとも1種である、請求項18に記載の熱転写表面改質シート。
  20.  前記易接着層が、3級アミン含有化合物、強酸から選ばれる少なくとも1種を含む、請求項16から19までのいずれかに記載の熱転写表面改質シート。
  21.  請求項16から20までのいずれかに記載の熱転写表面改質シートの易接着層側が熱可塑性樹脂の表面側になるように該熱転写表面改質シートが該熱可塑性樹脂の表面に載置された、熱転写表面改質シート付熱可塑性樹脂。
  22.  熱可塑性樹脂に易接着層が積層された表面改質熱可塑性樹脂であって、
     熱可塑性樹脂と易接着層との間に、該熱可塑性樹脂と該易接着層とが混合した混合層を備え、
     該混合層の厚さが1.5nm以上である、
     表面改質熱可塑性樹脂。
     
     

     
PCT/JP2017/001066 2016-01-14 2017-01-13 表面改質熱可塑性樹脂の製造方法、接合構造体の製造方法、接合構造体、熱転写表面改質シート、熱転写表面改質シート付熱可塑性樹脂、および、表面改質熱可塑性樹脂 WO2017122797A1 (ja)

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