WO2023054532A1

WO2023054532A1 - Surface modification sheet, multilayer body, surface-modified member, coated article, method for producing surface-modified member, and method for producing coated article

Info

Publication number: WO2023054532A1
Application number: PCT/JP2022/036308
Authority: WO
Inventors: 涼平大幡; 明日香遠藤; 佳世下川; 繁樹石黒
Original assignee: 日東電工株式会社
Priority date: 2021-09-29
Filing date: 2022-09-28
Publication date: 2023-04-06
Also published as: JPWO2023054532A1; KR20240073880A; TW202330268A; CN118055857A

Abstract

The present invention provides a surface modification sheet which comprises a mold release sheet and a surface modification layer, wherein: the surface modification layer has a storage elastic modulus of 5.0 × 10³ to 1.0 × 10⁸ Pa at 160°C; the surface modification layer has a surface tension of 38 mN/m or more; the surface modification layer comprises a crystalline polyamide component and a filler that contains a polar group; and the content of the filler is 3 to 40 parts by mass relative to 100 parts by mass of the crystalline polyamide component.

Description

SURFACE-MODIFIED SHEET, LAMINATE, SURFACE-MODIFIED MEMBER, COATED PRODUCT, METHOD FOR MANUFACTURING SURFACE-MODIFIED MEMBER, AND METHOD FOR MANUFACTURING COATED PRODUCT

The present invention relates to a surface-modified sheet, a laminate, a surface-modified member, a coated article, a method for producing the surface-modified member, and a method for producing a coated article.

In recent years, resins, which are lightweight and have excellent impact resistance, are used for parts such as transportation equipment such as railway vehicles, aircraft, ships, and automobiles, electronic equipment, and housing equipment. is joined. Coating films having various functions are formed on the resin member.

When joining resin components to metals or other resins, it is necessary to have sufficient adhesion. Rubber-epoxy-based curable resin compositions are conventionally known as such adhesives.

However, resin members are difficult to blend with adhesives, and sufficient adhesive strength cannot be obtained even with conventional adhesives or adhesive sheets. In addition, resin members such as carbon fiber composite materials (CFRP) having excellent strength are required to have a high level of adhesive strength.

For this reason, the bonding of resin members requires the application of a primer solution, and various surface treatments such as sandblasting, corona treatment, and plasma treatment as pretreatments prior to the application of the primer solution.

For example, as a means for obtaining sufficient adhesive strength, there is a technique of applying a suitable primer solution to modify the surface of a thermoplastic resin member, but resins with high solvent resistance (such as PPS, PA, PP, etc.), there is a problem that sufficient adhesive strength cannot be exhibited. In addition, in such a surface treatment method, a surface treatment step and a drying step must be provided, which increases the number of steps and lowers productivity, which also poses a problem in terms of cost.

Further, as one of the means for imparting sufficient adhesive strength by subjecting a resin member to an easy-adhesion treatment, there is a technique using a surface-modified sheet.
For example, Patent Literature 1 describes a surface-modified sheet capable of imparting sufficient adhesive strength to a thermoplastic resin.

Furthermore, a technology for manufacturing a surface-modified member having a smooth surface using a surface-modified sheet (Patent Document 2), and a technology for suppressing wrinkles in the surface-modified member using a low linear expansion release sheet. (Patent Document 3) is also being studied.

Japanese Patent Application Laid-Open No. 2017-128722 Japanese Patent Application Laid-Open No. 2019-194016 Japanese Patent Application Laid-Open No. 2020-163831

However, in the techniques described in Patent Documents 1 to 3, when the resin member constituting the surface modification member contains a reinforcing material such as carbon fiber or glass fiber, for example, the surface modification sheet is used to make the resin Although the adhesion between the member and the coating film is improved, the appearance may change over time in a high-temperature, high-humidity environment. Moreover, Patent Documents 1 to 3 do not discuss the elongation at break of the surface-modified layer used in the surface-modified sheet.

The present invention has been made in view of the above-mentioned conventional circumstances, and provides a surface-modified sheet having a surface-modified layer that can suppress changes in appearance even in a high-temperature and high-humidity environment and has improved elongation at break. This is an issue that should be resolved.

In the present invention, the surface-modified layer with improved elongation at break means a surface-modified layer with improved elongation until breakage due to stress.

As a result of extensive studies aimed at achieving the above object, the present inventors have found that the following surface-modified sheet can solve the above problems, and have completed the present invention.

That is, the present invention relates to the following <1> to <16>.
<1> A surface-modified sheet comprising a release sheet and a surface-modified layer,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 ³ to 1.0×10 ⁸ Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The surface-modified sheet, wherein the content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component.
<2>
The surface of the filler is untreated, or the functional groups on the surface of the filler are at least one selected from the group consisting of silanol groups, hydroxyl groups, amino groups, mercapto groups, carboxyl groups, isocyanate groups, and epoxy groups. The surface-modified sheet according to <1>, which is a group of
<3>
The surface-modified sheet according to <1>, wherein the filler is silica particles.
<4>
The surface-modified sheet according to <1>, wherein the filler has an average primary particle size of 5 nm to 1 μm.
<5>
The surface-modified sheet according to <1>, wherein the surface-modified layer has an average thickness of 0.1 to 2000 μm.
<6>
A laminate comprising the surface-modified sheet according to any one of <1> to <5> and a resin material,
A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
<7>
The laminate according to <6>, wherein the resin material is a prepreg.
<8>
A laminate comprising a surface-modified layer and a resin material,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 ³ to 1.0×10 ⁸ Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component,
A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
<9>
A surface-modified member comprising the surface-modified sheet according to any one of <1> to <5> and a resin member,
A surface-modified member, wherein the surface-modified layer is laminated on at least part of the surface of the resin member.
<10>
The surface modified member according to <8>, wherein the resin member contains a thermosetting epoxy resin.
<11>
A coated article comprising a coating film on at least a part of the surface modifying member according to <9>,
A coated article, wherein the coating film is at least one selected from the group consisting of a coating, a printed layer, a deposited layer, and a plated layer.
<12>
A method for producing a surface-modified member using the surface-modified sheet according to any one of <1> to <5>,
A method for manufacturing a surface-modified member, comprising a lamination step of laminating the surface-modified layer on a resin member by thermocompression bonding.
<13>
The method for producing a surface-modified member according to <12>, wherein the resin member contains a thermosetting epoxy resin.
<14>
A method for manufacturing a surface-modified member using the laminate according to <8>, wherein the surface-modified layer is laminated on a resin member by thermocompression bonding using a release-treated mold and molded. A method for manufacturing a surface-modified member, comprising steps.
<15>
A method for producing a coated object using the surface-modified sheet according to any one of <1> to <5>,
a step of laminating the surface-modified layer on a resin member by thermocompression bonding to manufacture a surface-modified member;
forming a coating film on the surface modification layer side of the surface modification member;
A method for producing a painted object.
<16>
The method for producing a coated object according to <15>, wherein the resin member contains a thermosetting epoxy resin.

The surface-modified sheet of the present invention has a surface-modified layer that has excellent adhesive strength, can suppress changes in appearance even in a high-temperature and high-humidity environment, and has improved elongation at break. In addition, by using the surface-modified sheet of the present invention, it is possible to form a smooth surface-modified layer with a uniform thickness while preventing the occurrence of unevenness. Integral molding with a resin member is possible.

1 is a schematic cross-sectional view showing an example of a surface modifying member; FIG. It is a schematic sectional drawing which shows an example of a surface modification sheet. FIG. 4 is a schematic cross-sectional view showing a configuration in which the surface modified layer side of a surface modified sheet, which is a laminate of a release sheet and a surface modified layer, is placed on at least part of the surface of a resin material. It is a schematic sectional drawing which shows an example of a coated article.

Hereinafter, embodiments of the present invention will be described in detail.

A surface-modified sheet according to an embodiment of the present invention is a surface-modified sheet comprising a release sheet and a surface-modified layer,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 ³ to 1.0×10 ⁸ Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component.

Since the surface-modified sheet according to the embodiment of the present invention has a sheet-like surface-modified layer, it is not coated on the surface of the resin member, but is placed on the resin material and heat-treated, so that integral molding can be performed. can. Therefore, it is possible to prevent unevenness due to repelling or the like, and to form a surface modified layer with a uniform thickness on the surface of the resin member. In addition, when the surface modification layer is provided on a part of the surface of the resin member, it is possible to suppress a decrease in yield due to protrusion or the like. Furthermore, by setting the storage elastic modulus of the surface modified layer to 5.0×10 ³ to 1.0×10 ⁸ Pa at 160° C., deformation in a high humidity and heat environment is suppressed, and the surface of the surface modified layer By setting the tension to 38 mN/m or more, the activity of the surface-modifying layer can be enhanced and adhesion to the coating film can be imparted. Therefore, when the surface-modified member is formed, it is possible to suppress changes in appearance even in a high-temperature and high-humidity environment, and to impart adhesion to the coating film.

When the resin member that constitutes the surface modification member contains reinforcing materials such as carbon fiber and glass fiber, the appearance may change over time in a high-temperature and high-humidity environment. It is presumed that the reinforcing material moved to the surface modification layer because the elasticity of the surface modification layer became low due to the high-temperature and high-humidity environment.

In the surface-modified sheet according to the embodiment of the present invention, the storage elastic modulus of the surface-modified layer at 160° C. is 5.0×10 ³ to 1.0×10 ⁸ Pa, and the surface tension of the surface-modified layer is By setting it to 38 mN/m or more, even if the formed surface-modified member is exposed to a high-temperature and high-humidity environment, the flow of the surface-modified layer is suppressed, and the reinforcing material in the resin member moves to the surface-modified layer. In order to prevent this, it has become possible to suppress changes in appearance.

[Surface modification layer]
In the surface-modified sheet according to the embodiment of the present invention, the surface-modified layer has a storage modulus of 5.0×10 ³ to 1.0×10 ⁸ Pa at 160° C., and a surface tension of It is 38 mN/m or more.

By setting the storage elastic modulus of the surface modified layer to 5.0×10 ³ Pa or more at 160° C., there is an advantage that the fluidity of the surface modified layer is suppressed.

Further, by setting the storage elastic modulus of the surface modified layer to 1.0×10 ⁸ Pa or less at 160° C., there is an advantage that it can follow a curved surface.

The storage modulus of the surface-modified layer at 160° C. is preferably 1.0×10 ⁶ Pa or less, more preferably 5.0×10 ⁵ Pa or less, and still more preferably 1.0×10 ⁵ Pa. It is below. Also, it is preferably 1.0×10 ⁴ Pa or more, more preferably 3.0×10 ⁴ Pa or more, and still more preferably 5.0×10 ⁴ Pa or more.

If the storage elastic modulus of the surface modified layer at 160° C. is more than 1×10 ⁸ Pa, the storage elastic modulus is higher than that of the release sheet, resulting in inferior curved surface followability. Further, when the storage elastic modulus at 160°C is less than 5.0 × 10 ³ Pa, the uniformity of the thickness of the surface modified layer is impaired, and the fluidity of the surface modified layer increases under high temperature and high humidity. , the aesthetic appearance is degraded.

The storage elastic modulus refers to the storage elastic modulus measured by the following method, using a laminate obtained by laminating a surface-modified layer of 500 μm, which constitutes the part to be measured, as a measurement sample. Specifically, the laminate is cut to a diameter of 8 mm to prepare a test piece. Using a jig with a diameter of 8 mm, temperature dispersion is performed at 25 to 200° C. with a viscoelasticity apparatus ARES-G2 manufactured by TA Instruments. At that time, the temperature increase rate is 5° C./min, and the frequency is 1 Hz. Let the elastic modulus in 160 degreeC at this time be a storage elastic modulus.

In the surface modified sheet according to the embodiment of the present invention, the surface tension of the surface modified layer must be 38 mN/m or more. By setting the surface tension to 38 mN/m or more, adhesion to the coating film can be obtained. The surface tension of the surface-modified layer is preferably 41 mN/m or more, more preferably 44 mN/m or more, still more preferably 48 mN/m or more. Although the upper limit of the surface tension of the surface modified layer is not particularly limited, it can be 73 mN/m or less.

The surface tension of the surface modified layer can be measured, for example, by the wet tension test method (JIS K6768). Specifically, the surface tension of the surface modified layer can be measured by the method described in Examples.

The average thickness of the surface-modified layer is not particularly limited, preferably 0.1 to 2000 μm, more preferably 1 to 1000 μm, still more preferably 3 to 200 μm, particularly preferably 5 to 30 μm. .

The average thickness of the surface-modified layer is obtained by measuring the thickness of the surface-modified sheet with a dial thickness gauge (eg, Peacock GC-9), and measuring the thickness of the release sheet after removing the surface-modified layer at that point. The difference can be measured as the thickness of the surface modification layer.
The average thickness of the surface modified layer is the average value obtained by measuring 10 points.

The surface modification layer (which may be the material of the surface modification layer) has a crystalline polyamide component.
The content of the crystalline polyamide component in the surface-modified layer is preferably 50% by mass to 98% by mass, more preferably 70% by mass to 98% by mass, and still more preferably 80% by mass to 98% by mass. , particularly preferably 85% to 98% by mass, most preferably 90% to 98% by mass.

Crystalline polyamide resins constituting the crystalline polyamide component include, for example, aliphatic polyamide resins such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12, and hexamethylene terephthalamide. Aromatic polyamide resins containing aromatic components such as terephthalic acid such as hexamethylene isophthalamide and metaxylylene adipamide, isophthalic acid, and metaxylylenediamine, and copolyamides and mixed polyamides having these as main constituents can be exemplified.

In the present invention, the "crystalline polyamide component" is a polyamide-based resin having a melting point, and the melting point can be confirmed by DSC measurement or dynamic viscoelasticity measurement.

Any appropriate crystalline polyamide-based resin can be selected as the crystalline polyamide-based resin within a range that does not impair the effects of the present invention. Examples of crystalline polyamide-based resins include aliphatic polyamide-based resins, alicyclic polyamide-based resins, semi-aromatic polyamide-based resins, aromatic polyamide-based resins, and fatty acid-modified polyamide-based resins.

Among these, crystalline polyamide resins suitable for the present invention include, for example, methoxymethyl group-containing polyamide resins and polyamide copolymer resins.

A commercially available product may be employed as the methoxymethyl group-containing polyamide resin. Examples of such commercially available products include the "Fine Resin" (registered trademark) series (manufactured by Narimichi Co., Ltd.).
Only one type of methoxymethyl group-containing polyamide resin may be used, or two or more types may be used.

The methoxymethyl group-containing polyamide resin has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and still more preferably 5,000, in that the effects of the present invention can be more expressed. ~100000.

In addition, in the present invention, the weight average molecular weight (Mw) uses the PMMA equivalent molecular weight in GPC measurement.

A commercially available product may be used as the polyamide copolymer resin. Examples of such commercial products include "Amilan CM8000" (manufactured by Toray Industries, Inc.).
Only one kind of polyamide copolymer resin may be used, or two or more kinds thereof may be used.

The polyamide copolymer resin has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and still more preferably 5,000 to 200,000, in that the effects of the present invention can be further expressed. , particularly preferably 10,000 to 100,000, and most preferably 20,000 to 70,000.

The surface modification layer (which may be the material of the surface modification layer) has fillers containing polar groups.
When the surface-modified layer contains a filler containing a polar group, the heat of cold crystallization of the polyamide resin is reduced, the polyamide resin is less likely to crystallize, and the amount of crystals can be reduced, so that the elongation at break of the surface-modified layer is improved. Conceivable. Moreover, it is thought that the interaction between the filler containing the polar group and the polyamide resin at the interface acts to prevent breakage and improve the elongation at break of the surface-modified layer.

The content of the polar group-containing filler is 3 to 40 parts by mass, preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass, based on 100 parts by mass of the crystalline polyamide component. If the content is less than 3 parts by mass, it is difficult to improve the breaking elongation of the surface modified layer. If the content exceeds 40 parts by mass, the proportion of the resin as a binder will decrease and the surface modified layer will become fragile.

The filler containing a polar group may be fibrous, plate-like, needle-like, non-particulate such as amorphous, fine particles, or secondary particles (aggregates) of fine particles.

In addition, the surface of the filler containing a polar group may be untreated or surface-treated. The functional group on the surface of the filler is preferably at least one group selected from the group consisting of silanol groups, hydroxyl groups, amino groups, mercapto groups, carboxyl groups, isocyanate groups, and epoxy groups.

Examples of fillers containing polar groups include silica particles such as fumed silica, colloidal silica, and precipitated silica, and silica-based fillers such as silica gel, silica airgel, quartz glass, and glass fiber. Among these, from the viewpoint of improving elongation at break, the filler containing a polar group is preferably silica particles, and particularly preferably fumed silica or colloidal silica.

The average primary particle size of the polar group-containing filler is preferably 5 nm to 1 μm, more preferably 7 nm to 50 nm, still more preferably 10 nm to 22 nm. The average primary particle size can be measured by, for example, SEM (scanning electron microscope), TEM (transmission electron microscope), DLS (dynamic light scattering), static light scattering, and the like.

The surface modification layer (which may be the material of the surface modification layer) may further contain a cross-linking agent as an additive.
The cross-linking agent may be contained in the surface modification layer in the form after the cross-linking reaction, the form before the cross-linking reaction, the form in which the cross-linking reaction is partially performed, an intermediate form or a composite form thereof, and the like.

[Release sheet]
The release sheet is not particularly limited, but preferably has a heat resistance of 100° C. or higher and a tensile elastic modulus at 100° C. of 1 GPa or lower. In addition, it may be a non-silicone resin sheet or a silicone resin sheet, but it is preferably a non-silicone resin sheet. manufactured by Nitoflon), polyester-based resin sheet, polymethylpentene-based resin sheet (manufactured by Mitsui Chemicals Tohcello, Opulan (registered trademark)), polystyrene-based resin sheet (manufactured by Kurabo Industries, Oidis (registered trademark)), polyamide-based A resin sheet, a polyolefin-based resin sheet, and the like are included.

More specifically, the release sheet that can be used for the surface-modified sheet includes, for example, unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide 66, biaxially stretched polypropylene, and biaxially stretched polyethylene. Terephthalate, biaxially oriented polybutylene terephthalate, easily moldable polyethylene terephthalate, cast polytetrafluoroethylene, unstretched extruded tetrafluoroethylene-ethylene copolymer (ETFE), unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer Examples include polymer (PFA), unstretched extruded tetrafluoroethylene-hexafluoropropylene joint (FEP), laminates having these as main layers, and the like.

The thickness of the release sheet is preferably 1 μm to 1000 μm, more preferably 10 μm to 200 μm, still more preferably 15 μm to 100 μm, and particularly preferably 20 μm to 50 μm, from the viewpoint of conformability.
In addition, if necessary, the surface of the release sheet on the surface modification layer side or both surfaces may be subjected to a release treatment with an appropriate release agent such as silicone.

In addition, using a laminate (second laminate described later) having a configuration obtained by peeling a release sheet from a laminate (first laminate described later) including a surface-modified sheet and a resin material When producing a surface-modified member (i.e., when the release sheet is peeled off before molding the surface-modified member), the release sheet included in the surface-modified sheet is not particularly limited, but has a heat resistance of 100°C. 1 MPa or more and preferably 1 GPa or less at 100°C. Moreover, it may be a non-silicone resin sheet or a silicone resin sheet. In the case of a non-silicone resin sheet, for example, fluorine resin sheet film (Nitto Denko Co., Ltd., Nitoflon), polyester resin sheet, polymethylpentene resin sheet (Mitsui Chemicals Tohcello, Opulan (registered trademark)), a polystyrene resin sheet (Oidis (registered trademark) manufactured by Kurabo Industries), a polyamide resin sheet, a polyolefin resin sheet, and the like.

When the release sheet is peeled off before molding the surface-modified member, the release sheet that can be used for the surface-modified sheet more specifically includes, for example, unstretched polyamide 6, unstretched polyamide 66, and biaxially stretched polyamide 6. , biaxially oriented polyamide 66, biaxially oriented polypropylene, biaxially oriented polyethylene terephthalate, biaxially oriented polybutylene terephthalate, easily moldable polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, cast molded polytetrafluoroethylene, unstretched extruded tetrafluoro Ethylene-ethylene copolymer (ETFE), unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), unstretched extruded tetrafluoroethylene-hexafluoropropylene joint (FEP), the main layer and laminated products.

When the release sheet is peeled off before molding the surface-modified member, the thickness of the release sheet is preferably 1 μm to 1000 μm, more preferably 10 μm to 200 μm, still more preferably 10 μm to 200 μm, from the viewpoint of conformability. 15 μm to 100 μm, particularly preferably 20 μm to 75 μm.
In addition, if necessary, the surface of the release sheet on the surface modification layer side or both surfaces may be subjected to a release treatment with an appropriate release agent such as silicone.

[Production of surface-modified sheet]
A surface-modified sheet may be manufactured by any suitable method. For example, a method of dipping a release sheet in a solution (surface-modifying composition) containing a material for the surface-modifying layer and a solvent (surface-modifying composition) followed by drying as necessary, and a method of applying the material for the surface-modifying layer to the surface of the release sheet. A method of drying if necessary after applying a solution containing a solvent and a brush, and a method of drying if necessary after applying a solution containing the material of the surface modification layer and a solvent to the surface of the release sheet with various coaters. , a method of spray coating a solution containing the material for the surface-modifying layer and a solvent onto the surface of the release sheet, followed by drying as necessary.

Examples of the surface-modifying composition include a solution obtained by dissolving the material of the surface-modifying layer in a solvent.
Examples of solvents include water; alcohols such as methanol, ethanol, and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic, and aromatic hydrocarbons; halogenated hydrocarbons; sulfoxides such as dimethyl sulfoxide; ethers such as dimethyl ether and tetrahydrofuran; and the like. Ethanol or a mixed solvent of ethanol, isopropyl alcohol and water is preferable in order to suppress the formation of gelled substances. Only one kind of solvent may be used, or two or more kinds thereof may be used.

The solid content concentration in the surface-modifying composition can be appropriately set according to the purpose. From the viewpoint of the thickness accuracy of the surface-modified layer, the solid content concentration in the surface-modified composition is preferably 1% by mass to 40% by mass, more preferably 10% by mass to 35% by mass, and still more preferably It is 15% by mass to 30% by mass.

If necessary, the surface modification composition may contain a pH adjuster, a cross-linking agent, a viscosity adjuster (thickener, etc.), a leveling agent, a release adjuster, a plasticizer, a softening agent, a filler, a coloring agent (pigment , dyes, etc.), surfactants, antistatic agents, preservatives, anti-aging agents, UV absorbers, antioxidants, light stabilizers, and other additives.

For example, by adding a coloring agent, the surface modified layer can be visualized, making it easy to determine whether the surface of the resin member has already been modified, which is advantageous in terms of process control.
Colorants include, for example, dyes and pigments. Further, the colorant may be a fluorescent material that can be visually recognized under black light.

[Laminate and surface-modified prepreg]
(First embodiment)
A laminate according to a first embodiment of the present invention is a laminate comprising a surface-modified sheet and a resin material, wherein the surface-modified layer of the surface-modified sheet covers at least part of the surface of the resin material. It is a laminated body (hereinafter also referred to as a first laminated body).
The resin material may be prepreg.

A surface-modified prepreg according to a first embodiment of the present invention is a prepreg with a surface-modified sheet in which the surface-modified layer of the surface-modified sheet is laminated on at least part of the surface of a resin material.
The first laminate, which is the resin material with the surface-modified sheet in the embodiment of the present invention, is manufactured by laminating the surface-modified layer side of the surface-modified sheet on at least part of the surface of the resin material before molding. can do.

The resin contained in the resin material may be a thermoplastic resin or a thermosetting resin.
Examples of thermoplastic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), POM (polyacetal), PEEK ( polyether ether ketone), PC (polycarbonate), PES (polyether sulfide), EP (epoxy), and the like. Among these resins, PPS (polyphenylene sulfide), PA (polyamide), PES (polyether sulfide), and EP (epoxy) are exemplified as thermoplastic resins that can advantageously exhibit the effects of the present invention.

A fiber reinforced thermoplastic (FRTP) may be employed as the thermoplastic.
Fiber reinforced thermoplastic resins (FRTP) include, for example, carbon fiber reinforced thermoplastic resins (CFRTP) and glass fiber reinforced thermoplastic resins (GFRTP).

Carbon fiber reinforced thermoplastic resins (CFRTP) include, for example, PPS carbon fiber reinforced thermoplastic resins, PA carbon fiber reinforced thermoplastic resins, PES carbon fiber reinforced thermoplastic resins, EP carbon fiber reinforced thermoplastic resins, A PP-based carbon fiber reinforced thermoplastic resin and the like are included.

Examples of glass fiber reinforced thermoplastic resins (GFRTP) include PPS glass fiber reinforced thermoplastic resins, PA glass fiber reinforced thermoplastic resins, and PP glass fiber reinforced thermoplastic resins.

Examples of thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy resins, melamine resins, phenol resins, urethane resins, polyisocyanate resins, polyisocyanurate resins, and polyimide resins. Among these, epoxy resins are preferred.

Examples of the shape of the resin material include a plate shape having a flat surface, a plate shape having a curved surface, a sheet shape, a film shape, and the like.
The thickness of the resin material is, for example, 0.001 mm to 10 mm.

"At least part of the surface of the resin material" means at least part of all the surfaces of the resin material. For example, when the resin material is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.

As for the surface-modified sheet and the surface-modified layer, the above description can be used as it is.

Here, a prepreg is made by impregnating a reinforcing material such as carbon fiber or glass fiber with a resin mixed with additives such as a curing agent and heating or drying it to a semi-cured state.

(Second embodiment)
A laminate according to a second embodiment of the present invention is a laminate comprising a surface-modified layer and a resin material,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 ³ to 1.0×10 ⁸ Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component,
The surface modification layer is laminated on at least part of the surface of the resin material.
The resin material may be prepreg.

A surface-modified prepreg according to a second embodiment of the present invention is a prepreg with a surface-modified layer, in which the surface-modified layer is laminated on at least part of the surface of a resin material.
The second laminate, which is the resin material with a surface-modified layer in the embodiment of the present invention, can be obtained, for example, by peeling off the release sheet from the first laminate, which is the resin material with the surface-modified sheet. can be manufactured.

As for the surface modification layer, the resin material, and the prepreg, the description in the above-mentioned first embodiment can be used as it is.

[Surface modification member]
A surface-modified member according to an embodiment of the present invention has a surface-modified layer laminated on at least part of the surface of a resin member.
A surface-modified member according to a first embodiment of the present invention is a surface-modified member including a surface-modified sheet and a resin member, wherein the surface-modified layer of the surface-modified sheet is formed on the surface of the resin member. It is laminated at least partially (hereinafter also referred to as a first surface-modifying member). A surface-modified member according to a first embodiment of the present invention is obtained by molding a resin material with a surface-modified sheet (that is, the above-described first laminate), and comprises a resin member and a surface-modified layer. A mixed layer in which the resin member and the surface-modified layer are mixed is provided between them.

As for the surface-modified sheet, the surface-modified layer, and the resin material, the above descriptions can be used as they are. A resin member is obtained by molding a resin material.
The resin contained in the resin member may be either a thermosetting resin or a thermoplastic resin, preferably a thermosetting resin, and particularly preferably a thermosetting epoxy resin.

The mixed layer is a layer in which the resin member and the surface-modified layer are mixed. It is a layer of a mixed part obtained by fusion-bonding or chemical bonding of the interfaces of members. The formation of the mixed layer improves the adhesive strength between the resin member and the surface modified layer. In the mixed layer, it is preferable that the resin contained in the resin member and the crystalline polyamide component constituting the surface modified layer are bonded by chemical reaction such as covalent bond. The interface between the resin member and the surface modified layer disappears due to a chemical reaction such as covalent bonding, and the resin member and the surface modified layer are integrated with each other, resulting in higher adhesive strength.

The thickness of the mixed layer can be appropriately determined according to the conditions of thermoforming and the type of the resin member and surface modification layer. The thickness of the mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more.

The thermoforming may be performed simultaneously with lamination of the resin material and the surface-modified sheet, or may be performed after lamination of the surface-modified sheet on the resin material.
By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost. The method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (resin surface treatment method).

A surface-modified member according to a second embodiment of the present invention is a surface-modified member including a surface-modified layer and a resin member, wherein the surface-modified layer is laminated on at least part of the surface of the resin member. (hereinafter also referred to as a second surface-modified member). The second surface modification member does not include a release sheet in its configuration. The surface-modified member according to the second embodiment of the present invention, for example, uses a mold in which a resin material with a surface-modified layer (that is, the second laminate described above) is subjected to a release treatment, and the surface is A mixed layer is provided between the resin member and the surface-modified layer, and is obtained by laminating the modified layer on the resin member by thermocompression bonding. The surface modified member according to the second embodiment of the present invention can also be obtained by peeling off the release sheet from the first surface modified member described above.

As for the surface modified layer, the resin material, the resin member, and the mixed layer, the above descriptions can be used as they are. The mixed layer is formed, for example, by heat-molding the resin material with the surface-modified layer using a release-treated mold.

In the surface modified member according to the embodiment of the present invention, the surface tension of the surface modified layer must be 38 mN/m or more. By setting the surface tension to 38 mN/m or more, adhesion to the coating film can be obtained. The surface tension of the surface-modified layer is preferably 41 mN/m or more, more preferably 44 mN/m or more, still more preferably 48 mN/m or more. Although the upper limit of the surface tension of the surface modified layer is not particularly limited, it can be 73 mN/m or less.

The surface tension of the surface-modified layer in the surface-modified member can be measured by the same method as the surface tension of the surface-modified layer in the surface-modified sheet described above.

<Method for producing surface-modified member>
The method for producing the surface-modified member according to the embodiment of the present invention is not particularly limited. The surface-modified member can be produced by placing the surface-modified layer side of the above and performing heat molding.

By heat molding, the crystalline polyamide component contained in the surface modified layer melts and mixes or reacts with the resin contained in the resin material to chemically bond, so that the interface between the surface modified layer and the resin material melts and contacts. It can be weld mixed or chemically bonded to form the surface modification member.

Heat molding may be performed at the same time as placing the surface-modified sheet, or may be performed after placing the surface-modified sheet.

By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost. The method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (method for surface treatment of a resin member).

As for the resin member, the surface-modified sheet, the release sheet, and the surface-modified layer, the above descriptions can be used as they are.

"At least part of the surface of the resin member" means at least part of all the surfaces of the resin member. For example, when the resin member is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.

In the production of the surface-modified member, when the resin contained in the resin member is a thermoplastic resin, when the melting point of the thermoplastic resin is T ₁ ° C., at least a part of the surface of the thermoplastic resin is surface-modified. It is preferable to provide a layer and perform heat welding at a temperature of (T ₁ -50)° C. or higher. The temperature of this heat welding is preferably (T ₁ -50)° C. to (T ₁ +150)° C., more preferably (T ₁ -25)° C. to (T ₁ +100)° C., still more preferably ( T ₁ -10)°C to (T ₁ +75)°C, particularly preferably (T ₁ )°C to (T ₁ +50)°C. By setting the heat molding temperature, that is, the molding temperature within the above range and performing the surface treatment of the resin member by the method described above, the interface between the surface modified layer and the thermoplastic resin member melts and contacts and is welded and mixed, resulting in thermoplasticity. Sufficient adhesive strength can be imparted to the resin member. Such application can be performed with high productivity and low cost.

When a thermoplastic resin is used as the resin in the resin member, after at least part of the surface of the thermoplastic resin member is in a molten state, a surface modification layer can be provided on the surface of the thermoplastic resin member in the molten state. By providing the surface modification layer on the surface of the thermoplastic resin member in a molten state, the surface modification layer is welded and mixed by the heat of the surface of the thermoplastic resin member, thereby imparting sufficient adhesive strength to the thermoplastic resin member. can be done.

In the production of the surface-modified member, when the resin contained in the resin member is a thermosetting resin, when the curing temperature of the thermosetting resin is T ₂ ° C., at least part of the surface of the thermosetting resin It is preferable to provide a surface-modified layer on the surface and perform heat molding at a temperature of (T ₂ -50)° C. or higher. The curing temperature is the peak temperature of the exothermic curve measured by DSC.

The thermoforming temperature is preferably (T ₂ −50)° C. to (T ₂ +50)° C., more preferably (T ₂ −40)° C. to (T ₂ +40)° C., still more preferably (T ₂ -30)°C to (T ₂ +30)°C, particularly preferably (T ₂ -20)°C to (T ₂ +20)°C.

By carrying out the surface treatment of the resin member by the method described above while setting the heat molding temperature within the above range, the interface between the surface modified layer and the resin member melts and contacts and is welded and mixed or chemically bonded to the resin member. Adhesive strength can be imparted. And such provision can be performed with high productivity and low cost.

After at least part of the surface of the resin member is melted or softened, a surface modification layer can be provided on the surface of the resin member in the melted or softened state. By providing a surface modification layer on the surface of a resin member in a molten or softened state, the surface modification layer is welded and mixed or chemically bonded by the heat of the surface of the resin member, thereby imparting sufficient adhesive strength to the resin member. can be done.

The "melted state" is a state in which at least a portion of the surface of the resin member is melted, preferably by heating the resin member to a temperature equal to or higher than its melting point.

The "softened state" is a state in which at least a portion of the surface of the resin member is softened, preferably by heating the resin member to a temperature equal to or higher than its softening temperature.

A "chemical bond" can be formed by chemically forming a covalent bond between the resin member and the material of the surface modification layer.

The heat molding method includes, for example, oven heating, infrared heating, high-frequency heating, thermocompression bonding, etc. Resin molding is preferable, and thermocompression bonding (press molding) is more preferable.
The heat molding time is preferably 1 second to 2 hours.

A method for manufacturing a surface-modified member according to an embodiment of the present invention is a method for manufacturing a surface-modified member using a surface-modified sheet, and includes a lamination step of laminating the surface-modified layer on a resin member by thermocompression bonding. may contain Here, the resin contained in the resin member may be a thermosetting resin or a thermoplastic resin, preferably a thermosetting resin, and particularly preferably a thermosetting epoxy resin.

As thermocompression bonding, for example, in a molding machine (for example, a press machine), the surface-modified layer side of the surface-modified sheet is placed on at least a part of the surface of the resin member, and molding processing accompanied by heating ( For example, it is a mode in which integral molding by thermocompression bonding is performed. According to this aspect, since molding of the resin member can be performed simultaneously with the surface treatment of the resin member, high productivity and low cost can be provided. Molding of the resin member may be injection molding, SMC molding, BMC molding, internal pressure molding, or autoclave molding.

"Molding" means processing a material into a predetermined shape regardless of whether a mold is used, and "molding" means processing a material into a predetermined shape using a mold. means

For injection molding, for example, an injection molding machine equipped with a movable mold and a fixed mold can be used. For example, the surface modified sheet is accommodated in the concave portion of the cavity of the movable side mold so that the release sheet faces the cavity, and the movable side mold and the fixed side mold are clamped. Then, the melted resin is injected into the cavity.

Then, after cooling and solidifying the resin in the mold, the movable side mold and the fixed side mold are separated. Thus, a surface-modified member in which the surface-modified sheet and the resin member are integrated is obtained.

Further, by peeling off the release sheet from the surface-modified member, a surface-modified member having a surface-modified surface provided with the surface-modified layer can be obtained. Peeling of the release sheet is not particularly limited, and may be performed manually, using a dedicated peeling equipment, or the like.

The surface-modified layer side of the surface-modified sheet, which is a laminate of the release sheet and the surface-modified layer, is placed on at least a part of the surface of the resin member, and after heat molding, the release sheet is preferably removed. be done.
That is, after manufacturing the above-mentioned first surface-modified member, the above-described second surface-modified member is obtained by removing the release sheet.

By removing the release sheet in this way, the surface-modified layer is transferred to the surface of the resin member, and a surface-modified member (sometimes referred to as a laminated member of the resin member and the surface-modified layer) is obtained. .

As described above, preferably, a mixed layer in which the resin and the surface-modified layer are mixed is provided between the resin member and the surface-modified layer.

By the above manufacturing method, as shown in FIG. 1, the surface modified layer 10 is provided on the surface of the resin member 100 to obtain the surface modified member. In FIG. 1, the surface modified layer 10 is laminated on the surface of the resin member 100. Preferably, between the resin member 100 and the surface modified layer 10, the resin member and the surface modified layer 10 are laminated. It has a mixed layer (not shown) in which the layers are mixed.

The surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is a surface-modified sheet 200, which is a laminate of a release sheet 20 and a surface-modified layer 10, as shown in FIG.

In the method for producing a surface-modified member according to the embodiment of the present invention, the surface-modified layer side of the surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is at least part of the surface of the resin member. 3, the surface-modified sheet 200 is placed on the surface-modified sheet 200 so that the surface-modified layer 10 side of the surface-modified sheet 200 faces the surface side of the resin material 400. is placed on the surface of the resin material 400 .

(Second embodiment)
A method for producing a surface-modified member according to a second embodiment of the present invention is a method for producing a surface-modified member using the above-described second laminate, which is a resin material with a surface-modified layer. A method for manufacturing a surface-modified member, comprising the step of laminating and molding the surface-modified layer on a resin member by thermocompression using a mold that has undergone mold treatment. Here, the resin contained in the resin member may be a thermosetting resin or a thermoplastic resin, preferably a thermosetting resin, and particularly preferably a thermosetting epoxy resin.

Examples of the mold release treatment include placing a mold release sheet on the mold surface, applying a hardening mold release agent to the mold surface, and peeling the mold surface.

・Installation of the mold release sheet The mold release sheet that can be used when installing the mold release sheet on the mold surface is not particularly limited, and can be used, for example, as the surface-modified sheet described above. It may be a non-silicone resin sheet or a silicone resin sheet.

As a method for installing the mold release sheet on the mold surface, for example, the mold release sheet is placed on the mold, and the mold release sheet is vacuum-sucked from the suction port provided in the mold. By doing so, the mold release sheet follows the mold and is shaped.

- Application of curable mold release agent Although the curable mold release agent used for mold surface treatment is not particularly limited, examples thereof include a silicone-based curable type, a fluorine-based curable type, and a boron nitride type. Specifically, Chemlease HT-S: silicone-based baking curing type (manufactured by Chemtrend Japan Co., Ltd.), Fine Dry FB-4: hexagonal boron nitride type (manufactured by Fine Chemical Japan Co., Ltd.), Fluorosurf FG-5905: Fluororesin reaction coating type (manufactured by Fluoro Technology Co., Ltd.) and the like.

There are no particular restrictions on the method of applying the curable release agent, and general methods such as brush coating, roller coating, spray coating, and various coater coatings can be used, and the coating amount is not particularly limited.
After applying the release agent, heating is performed as necessary to cure the coating film. The heating time, temperature, and the like can be appropriately determined depending on the release agent to be used, the coating amount, and the like. For example, when Chemrease HT-S is used, the mold can be spray-coated and heated at 100° C. for 5 minutes to cure the coating film.

・Peeling treatment of the surface of the mold The peeling treatment of the surface of the mold is not particularly limited, but includes fluorine processing, ceramic processing, and inorganic processing. It is sufficient to use a commercially available mold.

The mold release treatment includes placing a mold release sheet on the mold surface, applying a hardening mold release agent to the mold surface, ceramic-based processing of the mold surface, and inorganic treatment of the mold surface. Preferably, it is at least one of the system processing treatments.
The mold release treatment may be applied to the surface of the mold facing the surface modified layer when the resin material with the surface modified layer is placed in the mold. may be applied.

If the mold release treatment is insufficient, the mold release component applied to the mold may be transferred to the surface modified layer, resulting in poor adhesion to the coating film. Therefore, the mold release treatment is preferably performed so that the surface tension of the surface-modified layer in the surface-modified member to be obtained is within the above range.

In the method for manufacturing a surface-modified member according to the second embodiment, the surface-modified layer is removed using a mold in which the above-described second laminate, which is a resin material with a surface-modified layer, is subjected to mold release treatment. It is molded by being laminated on a resin member by thermocompression.
In the above molding, the resin material with the surface modification layer is placed in the mold that has been subjected to mold release treatment so that the surface modification layer faces it, and the molding process that involves heating (integration by thermocompression) molding).

By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost.

The molding temperature may be in the same range as the thermal molding temperature in the first embodiment. By surface-treating the resin member by the above-described method, the interface between the surface-modified layer and the resin member melts and contacts to weld and mix, and sufficient adhesive strength can be imparted to the resin member.
Thus, a surface-modified member in which the surface-modified layer and the resin member are integrated is obtained. The surface-modified member obtained in this embodiment is the above-described second surface-modified member including the surface-modified layer and the resin member.

[Painted object]
A coated object according to an embodiment of the present invention is a coated object having a coating film on at least a portion of a surface-modifying member, and the coating film is formed on at least a portion of the surface of the surface-modifying member on the surface-modifying layer side. It is preferably provided. The coating film is at least one selected from coating, printing layer, vapor deposition layer, and plating layer.

As an example of a coated object according to an embodiment of the present invention, a coating film 30 is provided on the surface of the surface-modified member on the surface-modified layer side of the surface-modified member in which the surface-modified layer 10 is provided on the surface of the resin member 100 shown in FIG. 3 shows a painted object 300. FIG.

Because the surface modification layer is formed using a sheet-like surface modification sheet instead of coating it on the surface of the member, it is possible to prevent the occurrence of unevenness due to repelling. Therefore, the surface modified layer can be formed with a uniform thickness on the surface of the resin member, and the coating film can be applied with a uniform thickness. Further, by providing the surface modified layer on the surface of the resin member in a molten or softened state, the surface modified layer is welded and mixed or chemically bonded by the heat of the surface of the resin member, and the surface modified layer and the resin member are bonded together. Since the adhesive strength is high, a coating film with excellent adhesion can be formed. Furthermore, since it is possible to integrally mold the surface modified layer and the resin member when forming the coated object, a cleaning treatment process using an organic solvent to remove the mold release agent before forming the coating film and polishing are performed. It does not require a treatment process, is highly safe, and can reduce the environmental load and workload.

The coating film is not particularly limited, and examples thereof include various coating films such as epoxy-based, polyester-melamine-based, alkyd-melamine-based, acrylic-melamine-based, acrylic-urethane-based, and acrylic-polyacid curing agent-based coatings. .

The thickness of the coating film is not particularly limited, and is, for example, 1 to 1000 µm, more preferably 3 to 300 µm, even more preferably 5 to 100 µm, and particularly preferably 10 to 50 µm.

There are no particular restrictions on the coating method of the coating film, and general methods such as brush coating, roller coating, spray coating, and various coater coatings can be used, and the coating amount is not particularly limited. In addition, the time and temperature for heating the coating film can be appropriately determined depending on the coating material to be used, the coating amount, and the like.

[Method for manufacturing a coated object according to the first embodiment]
A method for producing a coated article according to the first embodiment of the present invention is a method for producing a coated article using the surface-modified sheet according to the embodiment of the present invention, wherein the surface-modified layer is bonded to a resin member by thermocompression bonding. and a step of forming a coating film on the surface modified layer side of the surface modified member.

The resin contained in the resin member may be either a thermosetting resin or a thermoplastic resin, preferably a thermosetting resin, and particularly preferably a thermosetting epoxy resin.
Examples of thermosetting resins include vinyl ester resins, unsaturated polyester resins, epoxy resins, melamine resins, phenol resins, phenol resins, urethane resins, polyisocyanate resins, polyisocyanurate resins, and polyimide resins.

Also, the surface-modified member may be formed by resin molding, and examples of resin molding include injection molding and press molding.

As for the resin member, the thermoplastic resin, the thermosetting resin, the surface-modified sheet, the surface-modified layer, and the surface-modified member, the above descriptions can be used as they are.

The coating film is not particularly limited, and examples thereof include acrylic, urethane, epoxy, fluorine, silicone, polyester/melamine, alkyd/melamine, acrylic/melamine, acrylic/urethane, acrylic/multilayer. Various coatings such as those based on acid curing agents are included.

The step of laminating the surface modified layer on the resin member by thermocompression bonding to form the surface modified member includes laminating the surface modified layer of the surface modified sheet on the resin member by thermocompression bonding to form the surface modified member. Forming mode (that is, the method for manufacturing the surface-modified member according to the first embodiment described above) can be adopted. Instead of this, the release sheet is peeled off from the above-mentioned first laminate, which is a resin material with a surface-modified sheet, to obtain a second laminate, and the second laminate is released from the mold. (that is, the method for manufacturing a surface-modified member according to the second embodiment described above) may be employed.

[Method for manufacturing a coated object according to the second embodiment]
A method for manufacturing a coated article according to a second embodiment of the present invention includes a coating film on at least a part of a surface-modified member in which a surface-modified layer according to an embodiment of the present invention is laminated on a resin member, A method for manufacturing a coated article, wherein the resin contained in the resin member is a thermoplastic resin having a melting point of T ₁ ° C., a surface modification layer is provided on at least a part of the surface of the resin member, and (T ₁ -50) C. or higher to form a surface-modifying member, and forming a coating film on the surface-modifying layer side of the surface-modifying member.

In the method for manufacturing a coated object according to the second embodiment of the present invention, a high adhesive strength can be obtained and, preferably, the conventional surface treatment process can be eliminated. Further, in one embodiment of the method for manufacturing a coated article according to the second embodiment of the present invention, the surface treatment is performed at the same time as the molding process, so that the use of a release agent becomes unnecessary, and the release agent removal step (sandblasting, degreasing, etc.) can be reduced.

In the method for manufacturing a coated object according to the second embodiment of the present invention, when the melting point of the thermoplastic resin contained in the resin member is T ₁ ° C., the resin member (thermoplastic resin member) containing the thermoplastic resin A surface modification layer is provided on at least part of the surface, and heat welding is performed at a temperature of (T ₁ -50)° C. or higher. By surface-treating the thermoplastic resin member by such a method, it is possible to impart sufficient adhesive strength to the thermoplastic resin member, and preferably such imparting can be performed with high productivity and low cost. can be done.

The temperature of this heat welding is preferably (T ₁ -50)° C. to (T ₁ +150)° C., more preferably (T ₁ -25)° C. to (T ₁ +100)° C., still more preferably ( T ₁ -10)°C to (T ₁ +75)°C, particularly preferably (T ₁ )°C to (T ₁ +50)°C. By performing the surface treatment of the thermoplastic resin member with the heat welding temperature within the above range, the interface between the surface modified layer and the thermoplastic resin member is melt-contacted and welded and mixed to form the thermoplastic resin. Sufficient adhesive strength can be imparted to the member, and preferably such impartation can be performed with high productivity and low cost.

The thermoplastic resin contained in the resin member according to the embodiment of the present invention includes, for example, PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polyethylene butylene terephthalate), POM (polyacetal), PEEK (polyetheretherketone), PC (polycarbonate), and the like. Among these resins, PPS (polyphenylene sulfide), PA (polyamide), and PP (polypropylene) are examples of thermoplastic resins that can advantageously exhibit the effects of the present invention.

As the thermoplastic resin, fiber reinforced thermoplastic resin (FRTP) can be adopted.

Examples of fiber reinforced thermoplastic resins (FRTP) include carbon fiber reinforced thermoplastic resin (CFRTP) and glass fiber reinforced thermoplastic resin (GFRTP).

Examples of carbon fiber reinforced thermoplastic resins (CFRTP) include PPS carbon fiber reinforced thermoplastic resins, PA carbon fiber reinforced thermoplastic resins, PP carbon fiber reinforced thermoplastic resins, and the like.

As for the surface modification layer, the above description can be used as it is.
As for the coating film and the coating method of the coating film, the description in the section [Method for producing a coated object according to the first embodiment] can be used as it is.

[Method for manufacturing a coated object according to the third embodiment]
A method for manufacturing a coated article according to a third embodiment of the present invention includes a surface-modified member in which a surface-modified layer according to an embodiment of the present invention is laminated on a resin member, and a coating film is provided on at least a part of the surface-modified member. A method for manufacturing a coated article, wherein the resin contained in the resin member is a thermosetting resin having a curing temperature of T ₂ ° C., a surface modification layer is provided on at least a part of the surface of the resin member, and the resin member has a curing temperature of T ₂ ° C. or higher. It includes a step of forming a surface-modified member by heat molding at a temperature, and a step of forming a coating film on the surface-modified layer side of the surface-modified member.

In the method for manufacturing a coated object according to the third embodiment of the present invention, a high adhesive strength can be obtained and, preferably, the conventional surface treatment process can be eliminated. Further, in one embodiment of the method for manufacturing a coated article according to the third embodiment of the present invention, the surface treatment is performed simultaneously with the molding process, so that the use of a release agent becomes unnecessary, and the release agent removal step is performed. (sandblasting, degreasing, etc.) can be reduced.

In the method for manufacturing a coated object according to the third embodiment of the present invention, when the curing temperature of the thermosetting resin contained in the resin member is T ₂ ° C., at least the surface of the resin member (thermosetting resin member) A surface-modified layer is partially provided, and heat molding is performed at a temperature of _T2 °C or higher. By surface-treating the thermosetting resin member by such a method, it is possible to impart sufficient adhesive strength to the thermosetting resin member. It can be carried out.

The temperature of this hot molding is preferably (T ₂ -50)° C. to (T ₂ +50)° C., more preferably (T ₂ -40)° C. to (T ₂ +40)° C., and still more preferably ( T ₂ -30)°C to (T ₂ +30)°C, particularly preferably (T ₂ -20)°C to (T ₂ +20)°C. By carrying out the surface treatment of the thermosetting resin member by the method described above with the heat molding temperature within the above range, the interface between the surface modified layer and the thermosetting resin member is softened by heating and mixed or chemically bonded. However, it is possible to impart sufficient adhesive strength to the thermosetting resin member, and preferably, such impartation can be performed with high productivity and low cost.

The thermosetting resin contained in the resin member according to the embodiment of the present invention includes unsaturated polyester resin, vinyl ester resin, epoxy resin, melamine resin, phenol resin, urethane resin, polyisocyanate resin, polyisocyanurate resin, and polyimide resin. etc.

The thermosetting resin may be a fiber-reinforced thermosetting resin.

Examples of fiber-reinforced thermosetting resins include carbon fiber-reinforced curable plastic resins and glass fiber-reinforced thermosetting resins.

"At least part of the surface of the thermoplastic resin member" and "at least part of the surface of the thermosetting resin member" refer to at least a part of all the surfaces of the thermoplastic resin member or the thermosetting resin member. means For example, when the thermoplastic resin member or the thermosetting resin member is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.

The shape of the thermoplastic resin member and the thermosetting resin member includes, for example, a plate shape having a flat surface, a plate shape having a curved surface, a sheet shape, a film shape, and the like.

The thickness of the thermoplastic resin member and thermosetting resin member is, for example, 0.001 mm to 10 mm.

In the method for manufacturing a coated object according to the second embodiment of the present invention or the method for manufacturing a coated object according to the third embodiment, at least part of the surface of the thermoplastic resin member or the thermosetting resin member is surface-modified. As a method for providing the layer, for example, a method of applying a solution containing a material for the surface modification layer and a solvent to at least part of the surface of a thermoplastic resin member or a thermosetting resin member, a method of applying a solution containing a material for the surface modification layer and a solvent, Examples include a method of melt extruding a surface modified layer on at least a portion of the surface of a resin member, a method of laminating a sheet-shaped surface modified layer on at least a portion of the surface of a thermoplastic resin member or a thermosetting resin member, and the like. be done.

As a method of applying the solution containing the material of the surface modification layer and the solvent according to the embodiment of the present invention, for example, a thermoplastic resin member or a thermosetting resin member is applied to the solution containing the material of the surface modification layer and the solvent. dipping, brushing a solution containing the material of the surface modification layer and a solvent to at least part of the surface of the thermoplastic resin member or thermosetting resin member, at least the surface of the thermoplastic resin member or thermosetting resin member Applying a solution containing the material for the surface modification layer and a solvent to a part of the surface using various coaters, or applying a solution containing the material for the surface modification layer and the solvent to at least a part of the surface of the thermoplastic resin member or the thermosetting resin member. and spray coating.

Examples of the solution containing the material for the surface modification layer and the solvent include a surface modification composition in which the material for the surface modification layer is dissolved in any appropriate solvent within the range that does not impair the effects of the present invention.

As for the surface-modified layer and the surface-modified composition, the above explanations can be used as they are.

When the solution containing the material for the surface modification layer and the solvent is applied to at least part of the surface of the thermoplastic resin member or thermosetting resin member, then at least part of the solvent is removed by drying. In such drying, at least part of the solvent may be removed, but it is preferable that 50% by mass or more of the solvent is removed, and more preferably 80% by mass or more of the solvent is removed. More preferably, 90% by weight or more of the solvent is removed, particularly preferably 95% by weight or more of the solvent is removed, and most preferably all solvent is removed.

As the drying method, any appropriate method, such as oven heating, infrared heating, or high-frequency heating, can be adopted as long as it can remove the solvent, as long as it does not impair the effects of the present invention. Moreover, as the drying temperature, any appropriate temperature can be appropriately set according to the boiling point of the solvent to be used.

As a method of melt extruding the surface modified layer, for example, a method of melt extruding the material of the surface modified layer onto at least a part of the surface of a thermoplastic resin member or a thermosetting resin member using a melt extruder or the like. is mentioned.

As a method for laminating the surface modified layer in the form of a sheet, for example, the method for manufacturing the surface modified member according to the embodiment of the present invention is applied to at least a part of the surface of the thermoplastic resin member or the thermosetting resin member. and the method of laminating the surface-modified layer side of the surface-modified sheet (laminate of the release sheet and the surface-modified layer) as described above.

Examples of heat molding methods include oven heating, infrared heating, high-frequency heating, and thermocompression bonding, with thermocompression bonding being preferred.

The heat molding time is preferably 1 second to 2 hours.

A surface modified layer is provided on the surface of a thermoplastic resin member or a thermosetting resin member by the method for manufacturing a coated object according to the second embodiment or the method for manufacturing a coated object according to the third embodiment of the present invention. , a surface-modified member (sometimes referred to as a laminated member of a thermoplastic resin member or a thermosetting resin member and a surface-modified layer) is obtained, and a coating film is formed on the surface-modified layer side of the surface-modified member. and a coated product is obtained. Preferably, a mixed layer in which the thermoplastic resin member or thermosetting resin member and the surface modifying layer are mixed is provided between the thermoplastic resin member or thermosetting resin member and the surface modifying layer. The thickness of this mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more.

The average thickness of the surface modified layer is preferably 0.1 to 2000 µm, more preferably 1 to 1000 µm, still more preferably 3 to 200 µm, and particularly preferably 5 to 30 µm.

As for the coating film and the coating method of the coating film, the description in the section [Method for manufacturing a coated object according to the first embodiment] can be used as it is.

[Method for manufacturing a coated object according to the fourth embodiment]
A method for manufacturing a coated object according to a fourth embodiment of the present invention is a method for manufacturing a coated object in which a coating film is formed on the surface modified layer side of a surface modified member in which a surface modified layer is laminated on a resin member. be.
In the method for manufacturing a coated object according to the fourth embodiment of the present invention, after at least a part of the surface of the resin member is in a molten state or a softened state, the surface of the resin member in the molten state or in the softened state A modified layer is provided. By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and preferably, such impartation can be performed with high productivity and low cost.

In the method for manufacturing a coated object according to the fourth embodiment of the present invention, at least part of the surface of the resin member is melted or softened, and a surface modification layer is provided on the surface.

As for "at least part of the surface of the resin member", the description in the section [Manufacturing method of coated object according to first embodiment] can be used as it is.

As for the resin member, the description in the section [Manufacturing method of coated object according to first embodiment] can be used as it is.

In the method for manufacturing a coated object according to the fourth embodiment of the present invention, after at least a part of the surface of the resin member is in a molten state or in a softened state, the surface of the resin member in a molten state or in a softened state is subjected to surface reforming. Create a quality layer. By providing the surface modified layer on the surface of the resin member in a molten or softened state, the surface modified layer is welded and mixed by the heat of the surface of the resin member, and sufficient adhesive strength can be imparted to the resin member. Preferably, such application can be performed with high productivity and low cost.

As for the surface modification layer, the coating film, and the coating method of the coating film, the description in the section [Method for producing a coated object according to the first embodiment] can be used as it is.

In the method for producing a coated article according to the fourth embodiment of the present invention, as a method of providing a surface modified layer on the surface of a resin member in a molten state or a softened state, for example, lamination of a release sheet and a surface modified layer A method of placing the surface-modified layer side of the surface-modified sheet, which is the body, on the surface of the resin member in a molten state or a softened state can be used. By such a method, sufficient adhesive strength can be imparted to the resin member, and preferably such impartation can be performed with high productivity and low cost.

[Process control method]
In the production of the surface-modified sheet, the surface-modified member, and the coated article according to the embodiment of the present invention, for example, the surface-modifying composition or the surface-modifying layer may contain a dye, a pigment, or a crystalline substance. By containing such additives, the surface modified layer is visualized, making it easier to manage the manufacturing process.

As for the surface-modifying composition, the surface-modifying sheet, the coated article, and the additive, the above descriptions can be used as they are.

As a process control method, for example, there is a method of visually confirming the surface-treated and colored part, or a method of recognizing and discriminating images taken with a camera.

As explained above, the following matters are disclosed in this specification.

[1]
A surface-modified sheet comprising a release sheet and a surface-modified layer,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 ³ to 1.0×10 ⁸ Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The surface-modified sheet, wherein the content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component.
[2]
The surface of the filler is untreated, or the functional groups on the surface of the filler are at least one selected from the group consisting of silanol groups, hydroxyl groups, amino groups, mercapto groups, carboxyl groups, isocyanate groups, and epoxy groups. The surface-modified sheet according to [1], which is a group of
[3]
The surface-modified sheet according to [1] or [2], wherein the filler is silica particles.
[4]
The surface-modified sheet according to any one of [1] to [3], wherein the filler has an average primary particle size of 5 nm to 1 μm.
[5]
The surface-modified sheet according to any one of [1] to [4], wherein the surface-modified layer has an average thickness of 0.1 to 2000 μm.
[6]
A laminate comprising the surface-modified sheet according to any one of [1] to [5] and a resin material,
A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
[7]
The laminate according to [6], wherein the resin material is a prepreg.
[8]
A laminate comprising a surface-modified layer and a resin material,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 ³ to 1.0×10 ⁸ Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component,
A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
[9]
A surface-modified member comprising the surface-modified sheet according to any one of [1] to [5] and a resin member,
A surface-modified member, wherein the surface-modified layer is laminated on at least part of the surface of the resin member.
[10]
The surface modified member according to [9], wherein the resin member contains a thermosetting epoxy resin.
[11]
A coated article comprising a coating film on at least part of the surface-modified member according to [9] or [10],
A coated article, wherein the coating film is at least one selected from the group consisting of a coating, a printed layer, a deposited layer, and a plated layer.
[12]
A method for producing a surface-modified member using the surface-modified sheet according to any one of [1] to [5],
A method for manufacturing a surface-modified member, comprising a lamination step of laminating the surface-modified layer on a resin member by thermocompression bonding.
[13]
The method for producing a surface-modified member according to [11], wherein the resin member contains a thermosetting epoxy resin.
[14]
A method for manufacturing a surface-modified member using the laminate according to [8], wherein the surface-modified layer is laminated on a resin member by thermocompression bonding using a release-treated mold and molded. A method for manufacturing a surface-modified member, comprising steps.
[15]
A method for producing a coated object using the surface-modified sheet according to any one of [1] to [5],
a step of laminating the surface-modified layer on a resin member by thermocompression bonding to manufacture a surface-modified member;
forming a coating film on the surface modification layer side of the surface modification member;
A method for producing a painted object.
[16]
The method for producing a coated object according to [15], wherein the resin member contains a thermosetting epoxy resin.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
(Surface modified sheet (1))
Polyamide copolymer resin (Amilan CM8000 manufactured by Toray Industries, Inc.) 100 parts by weight, untreated fumed silica (Cab-o-sil manufactured by CABOT, average primary particle size 12 nm) 5 parts by weight of 40 ° C. ethanol (EtOH) / It was dissolved in a mixed solvent of water=80 mass %/20 mass % to prepare a 20 mass % solid content solution (surface modification composition).

After filtering the prepared surface modification composition through a nylon mesh with an opening of 188 μm, a release sheet (Niftron 900UL: Nitto Denko Co., Ltd. fluororesin sheet film (polytetrafluoroethylene (PTFE) (thickness 0.05 mm, dimensions : width 250 mm × length 450 mm)))) and dried at 100 ° C. for 2 minutes in a constant temperature dryer to form a surface modified sheet (1) equipped with a release sheet and a surface modified layer. made.

(Surface modification member (1))
The surface-modified sheet (1) prepared above is placed on a carbon fiber reinforced thermosetting epoxy resin prepreg (Torayca, manufactured by Toray Industries, Inc.) (dimensions: width 150 mm x length 120 mm x thickness 1 mm), press processing ( 150° C. for 5 minutes) to fabricate a surface-modified member (1).

(Painted object (1))
After peeling off the release sheet of the surface-modified member (1) prepared above, apply V-top H (two-liquid curing urethane paint) manufactured by Dainippon Toryo Co., Ltd. to the surface-modified layer with an applicator, and apply at room temperature. The coating film was cured for 3 days or longer to prepare a coated article (1).

[Examples 2 to 6, 9, 10, Comparative Examples 1 to 5, 7]
The method described in Example 1 was followed except that the material used for the surface-modifying composition, the amount used, the type of resin member, and the molding temperature during molding of the surface-modifying member were changed as shown in Table 1 or 3. A surface-modified sheet, a surface-modified member, and a coated object were produced.

[Example 7]
A surface-modified sheet was produced according to the method described in Example 1, except that the materials and amounts used in the surface-modified composition were changed as shown in Table 1.

The surfaces of the two surface-modified sheets thus produced were superimposed on each other and thermally laminated at 150°C to obtain a laminate of the surface-modified sheets. The release sheet of the laminated product was peeled off, the surface modified layer sides were overlapped, and thermal lamination was performed at 150°C. This process was repeated several times to obtain a surface-modified sheet having a thickness of the surface-modified layer of 200 μm.

[Example 8, Comparative Example 6]
A surface-modified sheet, a surface-modified sheet, and a A member and a coated object were produced.

[Comparative Examples 8 and 9]
A surface-modified member was produced using the release sheet and the resin member shown in Table 3 without providing the surface-modified layer, and a coated object was produced according to the method described in Example 1.

[Example 11]
(Resin material with surface modified layer (1))
A surface-modified sheet was prepared according to the method described in Example 1, except that the amount of silica used in the surface-modified composition was changed as shown in Table 2, and the resulting surface-modified sheet was made of carbon fiber. A resin material with a surface modification layer (1 ).

(Surface modification member (11))
Mold release sheet (Niftron 900UL: manufactured by Nitto Denko Co., Ltd. Fluororesin sheet film (polytetrafluoroethylene (PTFE) (thickness 0.05 mm, dimensions: width 250 mm × After arranging the 450 mm length)), vacuum suction was performed to make the sheet conform to the mold, whereby the surface of the mold was subjected to release treatment.
The resin material with a surface modified layer (1) prepared above is placed on the side of the mold that has been subjected to mold release treatment so that the surface of the resin material with a surface modified layer on the surface modified layer side faces, and pressed. A surface-modified member (11) was produced by heating and welding by working (150° C., 5 minutes).

(Painted object (11))
Apply V top H (two-liquid curing type urethane paint) manufactured by Dainippon Toryo Co., Ltd. to the surface modified layer of the surface modified member (11) prepared above with an applicator, and cure the coating film at room temperature for 3 days or more. to produce a coated article (11).

[Examples 12 and 13]
A resin material with a surface-modified layer, a surface-modified member, And a coated product was produced.

[Example 14]
Instead of using a release sheet for the mold, we applied Chemlease HT-S (a silicone-based bake-hardening type, made by Chemtrend Japan Co., Ltd.), a hardening mold release agent, to the surface of the mold and cured it. A resin material with a surface-modified layer, a surface-modified member, and a coated object were produced according to the method described in Example 11, except that the mold surface was subjected to a release treatment.

[Example 15]
A resin material with a surface modified layer was prepared according to the method of Example 14, except that Fine Dry FB-4 (hexagonal boron nitride type, manufactured by Fine Chemicals Japan Co., Ltd.) was used as the curable release agent. A surface-modified member and a coated article were produced.

[Example 16]
In the method described in Example 11, except that a mold subjected to release treatment with PTFE (polytetrafluoroethylene) was used instead of the mold subjected to mold release treatment with a mold release sheet. Accordingly, a resin material with a surface-modified layer, a surface-modified member, and a coated object were produced.

<Average primary particle size>
The average primary particle size of each silica used as a filler in Examples and Comparative Examples was measured by optical evaluation with a transmission electron microscope (manufactured by JEOL, "JEM-2800"). For the average primary particle diameter, the average value per 100 silica particles was adopted.

<Storage modulus>
Using the surface-modified sheets produced in Examples and Comparative Examples, the storage elastic modulus was measured by the following procedure.
A laminate obtained by laminating the surface-modified layer with the release sheet peeled off to a thickness of about 500 μm was used as a measurement sample. The laminate was cut to a diameter of 8 mm to prepare a test piece. Using a jig with a diameter of 8 mm, temperature dispersion was performed at 25 to 300° C. with a viscoelasticity apparatus ARES-G2 manufactured by TA Instruments. At that time, the temperature increase rate was 5° C./min, and the frequency was 1 Hz. The elastic modulus at 160° C. at this time was taken as the storage elastic modulus (Pa).

<Cold crystallization heat amount>
DSC (differential scanning thermal analysis) measurement was performed under the following conditions, and the endothermic amount of the surface modified layer was obtained from the endothermic peak area of the heat flow curve obtained in the first cooling process, and the cold crystallization heat amount (j / g).

DSC measurement conditions Apparatus: High-sensitivity DSC Q2000 manufactured by TA Instruments
Atmospheric gas: N ₂ (50 ml/min)
Heating rate: 2°C/min
Temperature conditions: -30°C → 200°C

At this time, A was the cold crystallization heat quantity measured only for the crystalline polyamide component alone, and B was the cold crystallization heat quantity of the surface modified layer. Since the value of B includes the filler, the change in the cold crystallization heat amount of the crystalline polyamide component cannot be simply compared with A. Therefore, the cold crystallization heat amount of the crystalline polyamide component when adding X parts by mass of the filler to 100 parts by mass of the crystalline polyamide component was converted to weight according to the following formula, and the value was defined as B'. The value of cold crystallization heat quantity shown in the table is B'.
B′=B×(100+X)/100

In addition, the rate of decrease in the amount of heat for cold crystallization due to the addition of the filler to the crystalline polyamide component was calculated by the following formula and defined as the rate of decrease in the amount of heat for cold crystallization.
Cold crystallization heat quantity reduction rate = {(AB') / A} × 100

<Thickness of Surface Modified Layer>
The film thickness of the surface modified layer was measured with a dial gauge (GC-9 manufactured by Peacock). The thickness of the surface-modified sheet was measured, the thickness (μm) of the release sheet from which the surface-modified layer was removed at that location was measured, and the difference was taken as the thickness (μm) of the surface-modified layer. The film thickness (μm) of the surface modified layer is the average value obtained by measuring 10 points.

<Breaking elongation>
A tensile test was performed under the following test conditions using a tensile tester with a constant temperature bath.
Test equipment: AG-I 20kN manufactured by Shimadzu Corporation
Load cell: 50N
Sample piece: A No. 5 dumbbell piece punched out is used.
Tensile speed: 300mm/min
Gauge distance: 70mm

In the stress-strain curve measured by the above tensile test at 23° C., the breaking point was defined as the point where the surface modified layer was broken, and the elongation value at that time was defined as the breaking elongation.
At this time, C is the elongation at break of the surface-modified layer consisting of only the crystalline polyamide component alone, and D is the elongation at break of the surface-modified layer containing the crystalline polyamide component and the filler. In addition, the value of the elongation at break described in the table is D.

Also, the rate of increase in elongation at break due to the addition of the filler was calculated by the following formula and defined as the rate of increase in elongation at break.
Breaking elongation increase rate = {(D - C) / C} x 100

<Paint thickness>
The coating thickness was measured with a dial gauge (GC-9 manufactured by Peacock). The thicknesses of the coated article and the surface-modified member before coating film formation were measured, and the difference was defined as the coating film thickness (μm). The coating film thickness (μm) is the average value obtained by measuring 10 points.

<60° Glossiness>
60° glossiness at room temperature (25°C) was measured by specular glossiness measurement (JIS Z8741-1997). A gloss meter (micro-tri-gloss) manufactured by BYK was placed on the coated surface to measure the gloss of the coating film. Glossiness is an average value obtained by measuring 5 points.

Further, the 60° glossiness was measured after holding for 24 hours in a constant temperature and humidity bath set under an environment of 85°C temperature and 85% RH.
Using the 60° glossiness at room temperature (25°C) and the 60° glossiness after holding for 24 hours in an environment with a temperature of 85°C and a humidity of 85% RH, the 60° glossiness reduction rate is calculated by the following formula. bottom.
60° glossiness reduction rate (%) = [(glossiness (25°C) - glossiness (85°C / 85% RH)) / glossiness (25°C)] × 100
When the 60° glossiness decrease rate was 5% or less, it was judged that the change in appearance of the coating film could be suppressed.

<Surface Tension of Surface Modified Layer in Surface Modified Sheet>
The surface tension A (m) N/m of the surface modified layer of the surface modified sheet was measured by the wet tension test method (JIS K6768-1999). A few drops of the wet tension test mixture adjusted to have an appropriate surface tension were dropped on the surface modified layer side of the surface modified sheet, and the wet tension test mixture was spread using a cotton swab. It was judged to be wet when the applied mixture for wetting tension test did not break and the applied state was maintained for 2 seconds or longer. The liquid mixture for the wet tension test was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

<Surface Tension of Surface Modified Layer in Surface Modified Member>
The surface tension B (m) N/m of the surface modified layer of the surface modified member was measured by the wet tension test method (JIS K6768-1999). A few drops of the wet tension test mixture adjusted to have an appropriate surface tension were dropped on the surface modified layer side of the surface modified member, and the wet tension test mixture was spread using a cotton swab. It was judged to be wet when the applied mixture for wetting tension test did not break and the applied state was maintained for 2 seconds or longer. The liquid mixture for the wet tension test was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

<Paint adhesion>
The coated objects prepared in Examples and Comparative Examples were subjected to cross-cut evaluation by the cross-cut method described in JIS K5600-5-6, and the number of peeled coating films was counted. Adhesion was judged to be good when the number of peeled coating films was 0 out of 100 sheets.

Interval between cuts: 2mm
Number of cross cuts: 100 squares Release tape: (Nichiban) cellophane tape (registered trademark) 24 mm width

The results of Examples and Comparative Examples are shown in Tables 1 to 3 below. Incidentally, in Comparative Examples 8 and 9 in which no surface modification layer was provided in the surface modification member, the surface tension of the resin member was described as surface tension B.

Materials listed in Tables 1 to 3 are as follows.
CM8000: Polyamide copolymer resin (Amilan manufactured by Toray Industries, Inc.)
FR105: Methoxymethyl group-containing 6 nylon (manufactured by Namuichi Co., Ltd., fine resin)
M5: Untreated fumed silica (Cab-o-sil manufactured by CABOT, average primary particle size 12 nm)
50: Untreated fumed silica (AEROSIL manufactured by evonic, average primary particle size 30 nm)
300: Untreated fumed silica (AEROSIL manufactured by evonic, average primary particle size 7 nm)
ST-OS: Untreated colloidal silica (Snowtex manufactured by Nissan Chemical Industries, Ltd., average primary particle size 9 nm)
TS720: PDMS (polydimethylsiloxane) modified fumed silica (Cab-o-sil manufactured by CABOT, average primary particle size 12 nm, hydrophobic silica)
CF-EpTS: Carbon fiber reinforced thermosetting epoxy resin prepreg (manufactured by Toray Industries, Inc., Torayca)
CF-PPS: Carbon fiber reinforced thermoplastic polyphenylene sulfide resin (manufactured by Bond Laminates, Tepex)
No. 900UL: PTFE sheet (Nitoflon manufactured by Nitto Denko Corporation, 50 μm thick)
MRF38: Biaxially oriented polyester film (manufactured by Mitsubishi Chemical Corporation, Diafoil, 38 μm thick)
P2171: Biaxially oriented polypropylene film (Pyrene manufactured by Toyobo Co., Ltd., 30 μm thick)
Chemrease HT-S: Silicone-based baking curing type release agent (manufactured by Chemtrend Japan Co., Ltd.)
Fine Dry FB-4: Hexagonal boron nitride type release agent (manufactured by Fine Chemical Japan Co., Ltd.)

The present invention is not limited to the above-described embodiments, but can be modified in various ways within the scope of the claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. is also included in the technical scope of the present invention.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2021-160128) filed on September 29, 2021, the contents of which are incorporated herein by reference.

10 Surface Modified Layer 20 Release Sheet 30 Coating Film 100 Resin Member 200 Surface Modified Sheet 300 Painted Object 400 Resin Material

Claims

A surface-modified sheet comprising a release sheet and a surface-modified layer,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 3 to 1.0×10 8 Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The surface-modified sheet, wherein the content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component.
The surface of the filler is untreated, or the functional group on the surface of the filler is at least one selected from the group consisting of silanol groups, hydroxyl groups, amino groups, mercapto groups, carboxyl groups, isocyanate groups, and epoxy groups. The surface-modified sheet according to claim 1, which is a group of
The surface-modified sheet according to claim 1, wherein the filler is silica particles.
The surface-modified sheet according to claim 1, wherein the filler has an average primary particle size of 5 nm to 1 µm.
The surface-modified sheet according to claim 1, wherein the surface-modified layer has an average thickness of 0.1 to 2000 µm.
A laminate comprising the surface-modified sheet according to any one of claims 1 to 5 and a resin material,
A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
The laminate according to claim 6, wherein the resin material is prepreg.
A laminate comprising a surface-modified layer and a resin material,
The surface modified layer has a storage modulus at 160° C. of 5.0×10 3 to 1.0×10 8 Pa,
The surface tension of the surface modified layer is 38 mN/m or more,
The surface-modified layer has a crystalline polyamide component and a filler containing a polar group,
The content of the filler is 3 to 40 parts by mass with respect to 100 parts by mass of the crystalline polyamide component,
A laminate in which the surface-modified layer is laminated on at least part of the surface of the resin material.
A surface-modified member comprising the surface-modified sheet according to any one of claims 1 to 5 and a resin member,
A surface-modified member, wherein the surface-modified layer is laminated on at least part of the surface of the resin member.
The surface modification member according to claim 9, wherein the resin member contains a thermosetting epoxy resin.
A coated article comprising a coating film on at least a part of the surface modifying member according to claim 9,
A coated article, wherein the coating film is at least one selected from the group consisting of a coating, a printed layer, a deposited layer, and a plated layer.
A method for producing a surface-modified member using the surface-modified sheet according to any one of claims 1 to 5,
A method for manufacturing a surface-modified member, comprising a lamination step of laminating the surface-modified layer on a resin member by thermocompression bonding.
The method for manufacturing a surface-modified member according to claim 12, wherein the resin member contains a thermosetting epoxy resin.
A method for manufacturing a surface-modified member using the laminate according to claim 8, wherein the surface-modified layer is laminated on a resin member by thermocompression bonding using a release-treated mold and molded. A method for manufacturing a surface-modified member, comprising steps.
A method for producing a painted object using the surface-modified sheet according to any one of claims 1 to 5,
a step of laminating the surface-modified layer on a resin member by thermocompression bonding to manufacture a surface-modified member;
forming a coating film on the surface modification layer side of the surface modification member;
A method for producing a painted object.
The method for manufacturing a painted object according to claim 15, wherein the resin member contains a thermosetting epoxy resin.