TW202330268A - Surface modification sheet, multilayer body, surface-modified member, coated article, method for producing surface-modified member, and method for producing coated article - Google Patents

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 DEG 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 article, manufacturing method of surface-modified member, and painted article’s manufacturing method

The present invention relates to a surface-modified sheet, a laminate, a surface-modified member, a coated object, a method for manufacturing a surface-modified member, and a method for manufacturing a coated object.

In recent years, rail vehicles, aircraft, ships, automobiles and other transportation equipment, electronic equipment, housing equipment, etc., use resins that are lightweight and have excellent impact resistance, and adherends of various materials are bonded to their surfaces. Also, a coating film having various functions is formed on the resin member.

When bonding a resin member to metal or other resins, sufficient adhesion is required. Conventionally, rubber epoxy-based curable resin compositions have been known as such adhesives.

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

Therefore, it is necessary to apply a primer solution when bonding the resin member, or to perform various surface treatments such as sandblasting, corona treatment, and plasma treatment as pretreatment before applying the primer solution.

For example, as a method to obtain sufficient bonding strength, there is a technique of coating an appropriate primer solution to modify the surface of a thermoplastic resin member. For resins with high solvent resistance (such as PPS, PA, PP, etc.) In some cases, there is a problem that sufficient bonding strength cannot be exhibited. Furthermore, in such a surface treatment method, it is necessary to provide a surface treatment step and a drying step, which increases the number of steps and lowers productivity, so there is also a problem in terms of cost.

Also, as one of the methods for easily bonding a resin member to impart sufficient bonding strength, there is a technique of using a surface-modified sheet. For example, Patent Document 1 describes a surface-modified sheet capable of imparting sufficient adhesive strength to a thermoplastic resin.

Furthermore, the technique of producing a surface-modified member with a smooth surface using a surface-modified sheet (Patent Document 2), or the technique of suppressing wrinkles of a surface-modified member using a release sheet with low linear expansion (Patent Document 2) Document 3) has been studied. prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2017-128722 Patent Document 2: Japanese Patent Laid-Open No. 2019-194016 Patent Document 3: Japanese Patent Laid-Open No. 2020-163831

[Problem to be solved by the invention]

However, in the technologies described in Patent Documents 1 to 3, when the resin member constituting the surface modified member contains a reinforcing material such as carbon fiber or glass fiber, for example, by using a surface modified sheet, the resin member and the The adhesion of the coating film is improved, but the appearance may change over time under high temperature and high humidity environment. Also, in Patent Documents 1 to 3, no study has been made on the elongation at break of the surface modification layer used for the surface modification sheet.

The present invention has been made in view of the above-mentioned prior circumstances, and as a problem to be solved, it provides a surface-modified sheet having a surface-modified layer with improved elongation at break, which suppresses changes in appearance even in high-temperature and high-humidity environments material.

Furthermore, in the present invention, the surface modified layer having an improved elongation at break means a surface modified layer whose elongation until fracture due to stress is increased. [Technical means to solve the problem]

The inventors of the present invention have intensively studied to achieve the above objects, and as a result, found that the above problems can be solved by the following surface-modified sheet, and completed the present invention.

That is, the present invention relates to the following <1> to <16>. <1> A modified surface sheet, which has a release sheet and a modified surface layer, and the storage modulus of the modified surface layer at 160°C is 5.0×10 ³ ~1.0×10 ⁸ Pa, The surface tension of the above-mentioned surface modification layer is 38 mN/m or more, the above-mentioned surface modification layer has a crystalline polyamide component and a filler containing a polar group, and the content of the above-mentioned filler is relative to 100 parts by mass of the above-mentioned crystalline polyamide component It is 3-40 mass parts. <2> The surface-modified sheet as described in <1>, wherein the surface of the above-mentioned filler is not treated, or the functional group on the surface of the above-mentioned filler is selected from the group consisting of silanol group, hydroxyl group, amino group, mercapto group, carboxyl group, and isocyanate At least one group selected from the group consisting of an acid group and an epoxy group. <3> The surface-modified sheet as described in <1>, wherein the above-mentioned filler is silica particles. <4> The surface-modified sheet as described in <1>, wherein the average primary particle diameter of the filler is 5 nm to 1 μm. <5> The surface-modified sheet according to <1>, wherein the average thickness of the above-mentioned surface-modified layer is 0.1-2000 μm. <6> A laminate comprising the surface-modified sheet according to any one of <1> to <5> and a resin material, wherein the surface-modified laminate is layered on at least a 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, wherein the storage modulus of the surface modified layer at 160°C is 5.0×10 ³ to 1.0×10 ⁸ Pa, and the surface of the surface modified layer The tension is 38 mN/m or more, the surface modification layer has a crystalline polyamide component and a polar group-containing filler, and the content of the filler is 3 to 40 parts by mass relative to 100 parts by mass of the crystalline polyamide component, The above-mentioned surface modification layer is laminated on at least a part of the surface of the above-mentioned resin material. <9> A surface-modified member comprising the surface-modified sheet and a resin member according to any one of <1> to <5>, wherein the surface-modified layer is layered on at least a part of the surface of the resin member . <10> The surface modification member according to <8>, wherein the resin member includes a thermosetting epoxy resin. <11> A coated article having a coating film on at least a part of the surface modification member as described in <9>, and the coating film is selected from the group consisting of coating, printing layer, vapor deposition layer, and plating layer. At least one of the group formed. <12> A method for producing a surface-modified member, which is a method for producing a surface-modified member using the surface-modified sheet according to any one of <1> to <5>, comprising modifying the above-mentioned surface The layer is laminated on the resin member by thermocompression bonding. <13> The method for producing a surface-modified member according to <12>, wherein the resin member includes a thermosetting epoxy resin. <14> A method for producing a surface-modified member, which is a method for producing a surface-modified member using the laminate described in <8>, and includes using a release-treated mold to apply the above-mentioned surface-modified layer by The step of laminating and molding the resin member by heat and pressure bonding. <15> A method for producing a coated article using the surface-modified sheet described in any one of <1> to <5>, comprising: adding the above-mentioned surface-modified layer a step of manufacturing a surface-modified member by laminating on 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. <16> The method for producing a coated article according to <15>, wherein the resin member includes a thermosetting epoxy resin. [Effect of Invention]

The surface-modified sheet of the present invention has excellent adhesive strength, can suppress changes in appearance even in high-temperature and high-humidity environments, and has a surface-modified layer with improved elongation at break. In addition, by using the surface modified sheet of the present invention, unevenness can be prevented, and a surface modified layer with a uniform thickness and smoothness can be formed. When forming a surface modified member, the integrated molding of the surface modified layer and the resin member can be realized. .

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

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

The surface-modified sheet according to the embodiment of the present invention can be integrally formed by placing and laminating on a resin material and performing heat treatment because the surface-modified layer is in the form of a sheet, instead of being coated on the surface of a resin member. Therefore, unevenness due to shrinkage or the like can be prevented, and the surface modification layer can be formed 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, a decrease in yield due to exposure or the like can be suppressed. Furthermore, by setting the storage modulus of the surface modification layer at 160°C to 5.0×10 ³ to 1.0×10 ⁸ Pa, deformation in high humidity and heat environments can be suppressed, and by setting the surface tension of the surface modification layer to Setting it above 38 mN/m can increase the activity of the surface modification layer and impart adhesion to the coating film. Therefore, when forming a surface-modified member, even in a high-temperature, high-humidity environment, changes in appearance can be suppressed, and adhesion to a coating film can also be imparted.

When the resin member constituting the surface modifying member contains, for example, a reinforcing material such as carbon fiber or glass fiber, the appearance may change over time under a high-temperature and high-humidity environment. It is presumed that the reinforcing material migrated to the surface modified layer because the surface modified layer became less elastic due to the high-temperature, high-humidity environment.

In the surface modified sheet according to the embodiment of the present invention, the surface tension of the surface modified layer is adjusted by setting the storage modulus of the surface modified layer at 160°C to 5.0×10 ³ to 1.0×10 ⁸ Pa. If it is set 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 reinforcement material in the resin member is prevented from migrating to the surface modified layer, so it can be suppressed. Appearance changes.

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

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

Also, by setting the storage modulus at 160°C of the surface modification layer to 1.0×10 ⁸ Pa or less, there is an advantage of being able to follow a curved surface.

The storage modulus of the surface modification layer at 160°C is preferably at most 1.0×10 ⁶ Pa, more preferably at most 5.0×10 ⁵ Pa, and still more preferably at most 1.0×10 ⁵ Pa. Also, it is preferably at least 1.0×10 ⁴ Pa, more preferably at least 3.0×10 ⁴ Pa, and still more preferably at least 5.0×10 ⁴ Pa.

If the storage modulus of the surface modification layer exceeds 1×10 ⁸ Pa at 160°C, the storage modulus will become higher than that of the release sheet, resulting in poor curve followability. In addition, if the storage modulus at 160°C is less than 5.0×10 ³ Pa, the uniformity of the thickness of the surface modified layer will be damaged, or the fluidity of the surface modified layer under high temperature and high humidity will be improved, resulting in poor appearance. Aesthetically reduced.

The storage modulus refers to the storage modulus measured by the following method using a laminate obtained by laminating the surface-modified layer constituting the part to be measured to a thickness of 500 μm as a measurement sample. Specifically, the above-mentioned laminate was cut into a diameter of 8 mm to prepare a test piece. Using a jig with a diameter of 8 mm, the viscoelastic device ARES-G2 manufactured by TA Instruments was used to implement temperature dispersion at 25-200°C. At this time, the heating rate was set at 5° C./min, and the frequency was set at 1 Hz. At this time, the modulus of elasticity at 160° C. was defined as the storage modulus.

In the surface modified sheet according to the embodiment of the present invention, the surface tension of the surface modified layer needs to be 38 mN/m or more. Adhesion to the coating film can be obtained by setting the surface tension to 38 mN/m or more. The surface tension of the surface modification layer is preferably at least 41 mN/m, more preferably at least 44 mN/m, and still more preferably at least 48 mN/m. The upper limit of the surface tension of the surface modification layer is not particularly limited, and may be set to be 73 mN/m or less.

The surface tension of the surface modification layer can be measured, for example, by the wetting tension test method (JIS K6768). Specifically, the surface tension of the surface modification layer can be measured by the method described in the examples.

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

The average thickness of the surface modified layer is to measure the thickness of the surface modified sheet with a dial thickness gauge (such as PeacockGC-9), measure the thickness of the release sheet with the surface modified layer removed from this part, and measure its The difference is taken as the thickness of the surface modification layer. The average thickness of the surface modification layer is the average value obtained by measuring 10 places.

The surface modification layer (may also be a material of the surface modification layer) has a crystalline polyamide component. The content ratio of the crystalline polyamide component in the surface modification layer is preferably from 50% by mass to 98% by mass, more preferably from 70% by mass to 98% by mass, still more preferably from 80% by mass to 98% by mass, especially Preferably, it is 85 mass % - 98 mass %, Most preferably, it is 90 mass % - 98 mass %.

Examples of the crystalline polyamide-based resin constituting the crystalline polyamide component include polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide Aliphatic polyamide resins such as amide 12; for example, hexamethylene terephthalamide, hexamethylene isophthalimide, adipyl m-xylylenediamine, etc. contain terephthalic acid Aromatic polyamide resins with aromatic components such as isophthalic acid and m-xylylenediamine, and copolymerized polyamides and mixed polyamides mainly composed of them.

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.

As the crystalline polyamide resin, any appropriate crystalline polyamide resin can be selected within the range that does not impair the effect 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, fatty acid modified permanent polyamide resin, etc.

Among them, as the crystalline polyamide-based resin suitable for the present invention, for example, a methoxymethyl group-containing polyamide resin, a polyamide copolymer resin, and the like may, for example, be mentioned.

As the methoxymethyl group-containing polyamide resin, commercially available items can also be used. As such a commercial item, "Fine Resin" (trademark) series (manufactured by Suenshi Co., Ltd.) etc. are mentioned, for example. The methoxymethyl group-containing polyamide resin may be used alone or in combination of two or more.

The polyamide resin containing methoxymethyl group can further exhibit the effect of the present invention, its weight average molecular weight (Mw) is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and even more preferably 5000~100000.

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

Commercially available items can also be used as the polyamide copolymer resin. As such a commercial item, "Amilan CM8000" (made by Toray Co., Ltd.) etc. are mentioned, for example. As the polyamide copolymer resin, only one type may be used, or two or more types may be used.

As far as the polyamide copolymer resin can further exhibit the effects of the present invention, its weight average molecular weight (Mw) is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, further preferably 5,000 to 200,000, especially 10,000 to 100,000, preferably 20,000 to 70,000.

The surface modification layer (may also be the material of the surface modification layer) has fillers containing polar groups. If the surface modification layer has fillers containing polar groups, the heat of cold crystallization of the polyamide resin will decrease, the polyamide resin will not be easily crystallized, and the amount of crystallization can be reduced. Therefore, it is believed that the elongation at break of the surface modification layer is increased. In addition, the fillers containing polar groups interact with the polyamide resin at the interface, making damage less likely to occur, and it is believed that the elongation at break of the surface modification layer is increased.

The content of the polar group-containing filler is 3 to 40 parts by mass relative to 100 parts by mass of the crystalline polyamide component, preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass. If the content is less than 3 parts by mass, the elongation at break of the surface modified layer is difficult to increase. If the content exceeds 40 parts by mass, the ratio of the resin as a binder will decrease, and the surface modified layer will become brittle.

Fillers containing polar groups can also be fibrous, plate-like, needle-like, amorphous and other non-particulate, fine particles, and secondary particles (agglomerates) of fine particles.

In addition, the surface of the filler containing polar groups can be untreated or surface-treated, preferably the surface of the filler containing polar groups is not treated, or the functional group on the surface of the filler containing polar groups is selected At least one group selected from the group consisting of a silanol group, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, an isocyanato group, and an epoxy group.

As fillers containing polar groups, for example: fumed silica, colloidal silica, precipitated silica and other silica particles; silica gel, silica aerosol, quartz glass, glass fiber and other silica-based fillers. Among them, from the viewpoint of improving the elongation at break, the polar group-containing filler is preferably silica particles, particularly fumed silica and 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, and even 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 (may also be the material of the surface modification layer) may further contain a crosslinking agent as an additive. The cross-linking agent may be contained in the surface modifying layer in the form after the cross-linking reaction, the form before the cross-linking reaction, the form in which the cross-linking reaction has partially occurred, or an intermediate or composite form thereof.

[Release sheet] The release sheet is not particularly limited, but the heat resistance is preferably 100°C or higher, and the tensile modulus at 100°C is preferably 1 GPa or lower. Also, it may be a non-polysiloxane resin sheet, or a polysiloxane resin sheet, but preferably a non-polysiloxane resin sheet, for example: a fluorine resin sheet film (Nitto Denko Co., Ltd., NITOFLON), polyester-based resin sheet, polymethylpentene-based resin sheet (manufactured by Mitsui Chemicals Tohcello, Opulent (registered trademark)), polystyrene-based resin sheet (manufactured by Kurabo Textiles, Oidys (registered trademark)), polyamide-based resin sheets, polyolefin-based resin sheets, and the like.

As the release sheet that can be used for the surface modification sheet, more specifically, for example, unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide Amide 66, Biaxially Extended Polypropylene, Biaxially Extended Polyethylene Terephthalate, Biaxially Extended Polybutylene Terephthalate, Easy Formable Polyethylene Terephthalate, Cast Polyethylene Terephthalate Fluoroethylene, unextruded tetrafluoroethylene-ethylene copolymer (ETFE), unextruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), unextruded tetrafluoroethylene-hexa Fluoropropylene copolymer (FEP), and laminates using it as the main layer, etc.

Regarding the thickness of the release sheet, from the viewpoint of shape followability, it is preferably 1 μm to 1000 μm, more preferably 10 μm to 200 μm, further preferably 15 μm to 100 μm, and most preferably 20 μm ~50 μm. Also, if necessary, release treatment may be performed on the side or both surfaces of the surface modification layer of the release sheet using an appropriate release treatment agent such as polysiloxane.

Furthermore, the surface was produced using a laminate (the following second laminate) having a structure obtained by peeling off the release sheet from a laminate (the following first laminate) provided with the surface modifying sheet and the resin material. In the case of the modified member (that is, the case where the release sheet is peeled off before forming the surface modified member), the release sheet provided as the surface modified sheet is not particularly limited, and the heat resistance is preferably 100 °C or higher, and the tensile modulus at 100 °C is preferably not less than 1 MPa and not more than 1 GPa. In addition, a non-silicone-based resin sheet may be used, or a silicone-based resin sheet may be used. In the case of a non-polysiloxane resin sheet, for example, a fluorine resin sheet film (manufactured by Nitto Denko Co., Ltd., NITOFLON), polyester resin sheet, polymethylpentene resin Sheets (manufactured by Mitsui Chemicals Tohcello, Opulent (registered trademark)), polystyrene-based resin sheets (manufactured by Kurabo Industries, Oidys (registered trademark)), polyamide-based resin sheets, polyolefin-based resin sheets, and the like.

When peeling off the release sheet before forming the surface modifying member, as the release sheet that can be used for the surface modifying sheet, more specifically, for example, unstretched polyamide 6, unstretched polyamide Amide 66, Biaxially Extended Polyamide 6, Biaxially Extended Polyamide 66, Biaxially Extended Polypropylene, Biaxially Extended Polyethylene Terephthalate, Biaxially Extended Polybutylene Terephthalate, Easy-to-form polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, cast polytetrafluoroethylene, unextruded tetrafluoroethylene-ethylene copolymer ( ETFE), non-extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), non-extruded tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and the like as the main layer Laminates, etc.

When the release sheet is peeled off before forming the surface modified member, the thickness of the release sheet is preferably 1 μm to 1000 μm, more preferably 10 μm to 200 μm from the viewpoint of shape followability, and further Preferably it is 15 μm to 100 μm, especially preferably 20 μm to 75 μm. Also, if necessary, release treatment may be performed on the side or both surfaces of the surface modification layer of the release sheet using an appropriate release treatment agent such as polysiloxane.

[Manufacture of surface modified sheet] The surface modified sheet can be produced by any appropriate method. For example, a method of immersing a release sheet in a solution (surface modifying composition) of a material containing a surface modifying layer and a solvent, followed by drying if necessary; After the solution is brushed on the surface of the release sheet, the method of drying if necessary; after using various coating machines to coat the solution of the material and solvent containing the surface modification layer on the surface of the release sheet, if necessary A method of drying; a method of drying, if necessary, after spraying a solution of the material including the surface modifying layer and a solvent on the surface of the release sheet.

As a surface modification composition, the solution which melt|dissolved the material of a surface modification layer in a solvent is mentioned. Examples of the solvent include: water; alcohols such as methanol, ethanol, and isopropanol (IPA); ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic, and aromatic hydrocarbons; halogenated hydrocarbons; Amides such as dimethylformamide; sulfides such as dimethylsulfide; ethers such as dimethyl ether and tetrahydrofuran; etc., in order to suppress the formation of gels, ethanol or ethanol or isopropanol is preferred. Mixed solvent with water. Only 1 type may be sufficient as a solvent, and 2 or more types may be sufficient as it.

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

In the surface modifying composition, pH adjusters, crosslinking agents, viscosity adjusters (tackifiers, etc.), leveling agents, peeling adjusters, plasticizers, softeners, fillers, and colorants may also be contained as needed (pigments, dyes, etc.), surfactants, antistatic agents, preservatives, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers and other additives.

For example, by adding a colorant to visualize the surface modification layer, it becomes easy to determine whether the surface of the resin member has been modified, which is advantageous in terms of process management. As a coloring agent, a dye or a pigment is mentioned, for example. Moreover, as a coloring agent, the fluorescent material which can be recognized with a black light may be used.

[Laminates and surface modified prepregs] (first embodiment) The laminate system according to the first embodiment of the present invention includes a surface modified sheet and a resin material, and is a laminate in which the surface modified layer of the surface modified sheet is laminated on at least a part of the surface of the resin material (hereinafter , also known as the first laminate). The resin material can also be a prepreg.

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

The resin contained in the resin material may be a thermoplastic resin or a thermosetting resin. As a thermoplastic resin, for example, PP (polypropylene, polypropylene), PA (polyamide, polyamide), PPE (polyphenylene ether, polyphenylene ether), PPS (polyphenylene sulfide, polyphenylene sulfide), PET (polyethylene terephthalate, polyethylene terephthalate), PBT (polybutylene terephthalate, polybutylene terephthalate), POM (polyoxymethylene, polyoxymethylene) (polyacetal), PEEK (Polyether ether ketone, polyether ether ketone ), PC (polycarbonate, polycarbonate), PES (polyether sulfide, polyether sulfide), EP (epoxy, epoxy resin), etc. Among these resins, examples of thermoplastic resins that can advantageously exhibit the effects of the present invention include PPS (polyphenylene sulfide), PA (polyamide), PES (polyether sulfide), EP (cyclic oxygen resin).

As the thermoplastic resin, fiber-reinforced thermoplastic resin (FRTP) can be used. As fiber reinforced thermoplastic resin (FRTP), carbon fiber reinforced thermoplastic resin (CFRTP), glass fiber reinforced thermoplastic resin (GFRTP), etc. are mentioned, for example.

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

Examples of the glass fiber reinforced thermoplastic resin (GFRTP) include PPS-based glass fiber-reinforced thermoplastic resins, PA-based glass fiber-reinforced thermoplastic resins, PP-based glass fiber-reinforced thermoplastic resins, and the like.

Examples of thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy resins, melamine resins, phenol resins, urethane resins, polyisocyanate resins, polyisocyanurate resins, polyamide imide resin, etc. Among them, epoxy resin is preferable.

As the shape of the resin material, 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 may, for example, be mentioned. The thickness of the resin material is, for example, 0.001 mm˜10 mm.

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

Regarding the surface-modified sheet and the surface-modified layer, the above description can be directly referred to.

Here, the prepreg is a resin mixed with additives such as a curing agent, impregnated with a reinforcing material such as carbon fiber or glass fiber, and heated or dried to become a semi-cured state.

(Second Embodiment) The laminate system according to the second embodiment of the present invention has a surface modification layer and a resin material, and the storage modulus of the above surface modification layer at 160°C is 5.0×10 ³ to 1.0×10 ⁸ Pa, the surface tension of the above-mentioned surface modification layer is 38 mN/m or more, the above-mentioned surface modification layer has a crystalline polyamide component and a filler containing a polar group, and the content of the above-mentioned filler is 100% relative to the above-mentioned crystalline polyamide component. The mass part is 3-40 mass parts, and the said surface modification layer is laminated|stacked on at least a part of the surface of the said resin material. The resin material can also be a prepreg.

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

As the surface modification layer, resin material, and prepreg, the description in the above-mentioned first aspect can be directly applied.

[Surface modification member] The surface modified member according to the embodiment of the present invention is formed by laminating the surface modified layer on at least a part of the surface of the resin member. The surface modified member according to the first embodiment of the present invention is provided with a surface modified sheet and a resin member, and is formed by laminating the surface modified layer of the surface modified sheet on at least a part of the surface of the resin member (hereinafter, Also referred to as the first surface modifying member). The surface-modified member according to the first embodiment of the present invention can be obtained by molding a resin material with a surface-modified sheet (that is, the above-mentioned first laminate), and a resin material is provided between the resin member and the surface-modified layer. A mixed layer formed by mixing a component and a surface modification layer.

As the surface-modified sheet, surface-modified layer, and resin material, the above description can be directly applied. The resin member can be obtained by shaping a resin material. The resin contained in the resin component can be thermosetting resin or thermoplastic resin, preferably thermosetting resin, especially thermosetting epoxy resin.

Mixed layer is a layer formed by mixing a resin member and a surface modified layer, for example, by providing a surface modified layer on at least a part of the surface of a resin material and performing thermoforming, so that the interface between the surface modified layer and the resin member is in melt contact Whereas welding is mixed or chemically bonded, whereby layers of mixed parts are obtained. By forming the mixed layer, the adhesion strength between the resin member and the surface modification layer is improved. In the mixed layer, it is preferable that the resin contained in the resin member and the crystalline polyamide component constituting the surface modifying layer are bonded by a chemical reaction such as covalent bonding. The interface between the resin component and the surface modification layer disappears through chemical reactions such as covalent bonding, so that the resin component and the surface modification layer are integrated, and better bonding strength can be obtained.

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

Thermoforming can be performed simultaneously with the lamination of the resin material and the surface-modified sheet, or after laminating the surface-modified sheet on the resin material. By performing the surface treatment of the resin member by such a method, sufficient adhesive strength can be imparted to the resin member, and a surface modified member can be manufactured with high productivity and at low cost. The method of manufacturing the surface modified member may also be a method of treating the surface of the resin member (resin surface treatment method).

The surface modified member according to the second embodiment of the present invention is provided with a surface modified layer and a resin member, and the surface modified layer is laminated on at least a part of the surface of the resin member (hereinafter also referred to as the second surface modified member). . In the second surface modification member, its composition does not include a release sheet. The surface modified member according to the second embodiment of the present invention is, for example, for the resin material with the surface modified layer (that is, the second laminate) using a release-treated mold, and the above surface modified layer It is obtained by heat-compression lamination on a resin member and molding, and a mixed layer in which the resin member and the surface modification layer are mixed is provided between the resin member and the surface modification layer. Furthermore, the surface modification member of the second embodiment of the present invention can also be obtained by peeling the release sheet from the above-mentioned first surface modification member.

As the surface modification layer, the resin material, the resin member, and the mixed layer, the above description can be directly applied. The mixed layer is formed, for example, by thermoforming a resin material with a 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 needs to be 38 mN/m or more. Adhesion to the coating film can be obtained by setting the surface tension to 38 mN/m or more. The surface tension of the surface modification layer is preferably at least 41 mN/m, more preferably at least 44 mN/m, and still more preferably at least 48 mN/m. The upper limit of the surface tension of the surface modification layer is not particularly limited, and may be set to 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 above-mentioned surface-modified sheet.

<Manufacturing method of surface modified member> The method of manufacturing the surface modified member according to the embodiment of the present invention is not particularly limited. For example, a surface modified sheet that is a laminate of a release sheet and a surface modified layer can be placed on at least a part of the surface of the resin material. The surface modified layer side is subjected to thermoforming to manufacture a surface modified member.

By thermoforming, the crystalline polyamide component contained in the surface modification layer and the resin contained in the resin material are melt-mixed or reacted to chemically bond, whereby the interface between the surface modification layer and the resin material is melted and contacted. Fusion mixing or chemical bonding to form surface-modified components.

Thermoforming can be carried out simultaneously with placing the surface-modified sheet, or after placing the surface-modified sheet.

By performing the surface treatment of the resin member by such a method, sufficient adhesive strength can be imparted to the resin member, and a surface modified member can be manufactured with high productivity and at low cost. The method of manufacturing the surface modified member may also be a method of treating the surface of the resin member (surface treatment method of the resin member).

As the resin member, surface-modified sheet, release sheet, and surface-modified layer, the above description can be directly applied.

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

In the manufacture 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, it is preferable to provide the surface modified on at least a part of the surface of the thermoplastic resin. The material layer is heated and welded at a temperature above (T ₁ -50)°C. The temperature of the heat welding is preferably (T ₁ -50) °C ~ (T ₁ +150) °C, more preferably (T ₁ -25) °C ~ (T ₁ +100) °C, and more preferably (T ₁ -10) °C )°C to (T ₁ +75)°C, especially preferably (T ₁ )°C to (T ₁ +50)°C. Set the thermoforming temperature, that is, the molding temperature, within the above range, and use the above-mentioned method to carry out the surface treatment of the resin member, so that the interface between the surface modification layer and the thermoplastic resin member is melt-contacted and welded and mixed, and the thermoplastic resin can be treated. The member imparts sufficient bonding strength. Such imparting 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 a part of the surface of the thermoplastic resin member is melted, a surface modification layer may be provided on the surface of the thermoplastic resin member in a molten state. By providing the surface modifying layer on the molten surface of the plastic resin member, and utilizing the heat of the surface of the thermoplastic resin member to fuse and mix the surface modifying layer, sufficient adhesive strength can be imparted to the thermoplastic resin member.

In the manufacture 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, it is preferable to provide a surface on at least a part of the surface of the thermosetting resin. Modified layer, and heat forming at a temperature above (T ₂ -50)°C. In addition, the curing temperature was set as the peak temperature of the heat generation 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, and more preferably (T ₂ -30)°C ~(T ₂ +30)°C, especially preferably (T ₂ -20)°C to (T ₂ +20)°C.

The thermoforming temperature is set within the above range, and the surface treatment of the resin member is carried out by the above-mentioned method, so that the interface between the surface modification layer and the resin member is melted and contacted, and fusion mixing or chemical bonding can be performed, and the resin member can be given Adequate bonding strength. Moreover, such imparting can be performed with high productivity and low cost.

After making at least a part of the surface of the resin member into a molten state or a softened state, a surface modification layer may be provided on the surface of the resin member in a molten state or a softened state. By providing the surface modified layer on the surface of the resin member in the molten state or softened state, the surface modified 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.

The "molten state" is a state in which at least a part of the surface of the resin member is molten, and can be preferably achieved by heating the resin member to a temperature above its melting point.

The "softened state" is a state in which at least a part of the surface of the resin member is softened, and can be preferably achieved by heating the resin member to a temperature above its softening temperature.

"Chemical bonding" can be realized by chemically forming a covalent bond between the resin component and the material of the surface modification layer.

Examples of thermoforming methods include oven heating, infrared heating, high-frequency heating, thermocompression bonding, etc., preferably by resin molding, more preferably thermocompression bonding (press molding). The time for thermoforming is preferably 1 second to 2 hours.

The method of manufacturing a surface-modified member according to the embodiment of the present invention is a method of manufacturing a surface-modified member using a surface-modified sheet, and may include a lamination step of laminating the above-mentioned surface-modified layer on a resin member by thermocompression bonding . Here, the resin contained in the resin component may be thermosetting resin or thermoplastic resin, preferably thermosetting resin, especially thermosetting epoxy resin.

As thermocompression bonding, for example, in a molding processing machine (such as a press machine, etc.), the surface modification layer side of the surface modification sheet is placed on at least a part of the surface of the resin member, and molding is performed with heating. Processing (such as integral forming by thermocompression bonding). According to this aspect, since the molding process of the resin member can be performed simultaneously with the surface treatment of the resin member, high productivity and low cost can be provided. As the molding process of resin components, injection molding, SMC (Sheet Molding Compound) molding, BMC (Bulk Molding Compound) molding, internal pressure molding, and autoclave molding can also be used.

Furthermore, "shaping" means processing a material into a predetermined shape regardless of whether a mold is used, and "forming" means processing a material into a predetermined shape using a mold.

For injection molding, for example, an injection molding machine equipped with a movable side mold and a fixed side mold can be used. For example, the surface modification sheet is accommodated in the concave part of the mold cavity of the movable side mold in such a way that the release sheet faces, and the movable side mold and the fixed side mold are clamped. Then, the molten resin in the cavity is injected.

Then, after the resin is cooled and solidified in the mold, the movable side mold is separated from the fixed side mold. In this way, a surface modified member in which the surface modified sheet and the resin member are integrated can be obtained.

In addition, a surface modified member having a surface modified layer on the surface can be obtained by peeling the release sheet from the surface modified member. The peeling of the release sheet is not particularly limited, for example, peeling by hand or using a dedicated peeling device.

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 thermoforming, it is preferable to remove the release sheet . That is, the second surface modified member can be obtained by removing the release sheet after manufacturing the first surface modified member.

By removing the release sheet in this way and transferring the surface modification layer to the surface of the resin member, a surface modification member (also sometimes referred to as a laminated member of a resin member and a surface modification layer) can be obtained.

Furthermore, as described above, it is preferable to provide a mixing layer in which the resin and the surface modification layer are mixed between the resin member and the surface modification 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 a surface modified member. Furthermore, in FIG. 1, the surface modified layer 10 is layered on the surface of the resin member 100, but it is preferable to have the resin member mixed with the surface modified layer between the resin member 100 and the surface modified layer 10. into a mixed layer (not shown).

As shown in FIG. 2 , the surface-modified sheet that is a laminate of a release sheet and a surface-modified layer is a surface-modified sheet 200 that is a laminate of a release sheet 20 and a surface-modified layer 10 .

In the method for producing a surface modified member according to an embodiment of the present invention, the surface modified sheet, which is a laminate of a release sheet and a surface modified layer, is placed on the resin member on the surface modified layer side. The form of at least a part of the surface is as follows: As shown in FIG. 3 , the surface modified sheet 200 is placed on the the surface of the resin material 400 .

(second embodiment) The method of manufacturing a surface modified member according to the second embodiment of the present invention is a method of manufacturing a surface modified member using the above-mentioned second laminate as a resin material with a surface modified layer, which includes: using a release-treated The mold is a step of forming the above-mentioned surface modification layer on the resin member by heat-compression lamination. Here, the resin contained in the resin component may be thermosetting resin or thermoplastic resin, preferably thermosetting resin, especially thermosetting epoxy resin.

As the release treatment of the mold, for example, setting a release sheet for the mold on the surface of the mold, coating a solidified release agent on the surface of the mold, peeling the surface of the mold, etc.

・Setting of mold release sheet The release sheet for the mold that can be used when the release sheet for the mold is provided on the surface of the mold is not particularly limited. For example, the release sheet that can be used for the above-mentioned surface modification sheet can be non-polymer The silicone resin sheet may also be a silicone resin sheet.

As a method of installing the release sheet for the mold on the surface of the mold, for example, the following method can be mentioned: the release sheet for the mold is placed in the mold, and the release sheet for the mold is vacuum-suctioned from the suction port provided in the mold. , so that the release sheet for the mold follows the mold and is shaped.

・Coating of curing release agent The curing type release agent used for mold surface treatment is not particularly limited, and examples include: polysiloxane-based curing type, fluorine-based curing type, boron nitride type, and the like. Specifically, Chemlease HT-S: Polysiloxane-based heat curing type (manufactured by Chem-Trend Japan Co., Ltd.), Fine Dry FB-4: hexagonal boron nitride type (Fine Chemical Japan Co., Ltd. Co., Ltd.), Fluoro Surf FG-5905: fluororesin reaction coating type (manufactured by Fluoro Technology Co., Ltd.), etc.

The coating method of the curable release agent is not particularly limited, 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, etc. can be appropriately determined according to the release agent used, the coating amount, and the like. For example, when using Chemlease HT-S, the mold can be spray-coated and heated at 100°C for 5 minutes to cure the coating film.

・Peel processing of mold surface The peeling treatment on the surface of the mold is not particularly limited, and examples include fluorine-based processing, ceramic-based processing, and inorganic-based processing. For example, a commercially available mold that has been subjected to such peeling processing can be used. .

The release treatment of the mold is preferably at least one of the following treatments: setting a release sheet for the mold on the surface of the mold; coating a solidified release agent on the surface of the mold; ceramic processing on the surface of the mold; Inorganic processing. Furthermore, the above-mentioned release treatment may be performed on the mold surface on the side opposite to the surface-modified layer when the resin material with the surface-modified layer is placed on the mold, but it may also be performed on both mold surfaces.

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

In the method of manufacturing a surface-modified member according to the second embodiment, for the above-mentioned second laminate as a resin material with a surface-modified layer, the above-mentioned surface-modified layer is heated and pressed using a mold that has undergone a mold release process. The build-up layer is formed on the resin member. The above-mentioned molding is a mode in which a resin material with a surface-modified layer is placed on a mold subjected to mold release treatment so that the surface-modified layer side faces each other, and molding processing with heating (by thermocompression bonding) is performed. integrally formed).

By thermoforming, the crystalline polyamide component contained in the surface modification layer and the resin contained in the resin material are melted and mixed or reacted to chemically bond, and the interface between the surface modification layer and the resin material is melted and contacted to be welded and mixed or Chemically bonded to form surface modifying components.

By performing the surface treatment of the resin member by such a method, sufficient adhesive strength can be imparted to the resin member, and a surface modified member can be manufactured with high productivity and low cost.

What is necessary is just to set it as the range similar to the thermoforming temperature in 1st Embodiment as a molding temperature. By performing the surface treatment of the resin member by the above-mentioned method, the interface between the surface modified layer and the resin member is melted and contacted, welded and mixed, and sufficient adhesive strength can be imparted to the resin member. In this way, a surface modified member in which the surface modified layer and the resin member are integrated can be obtained. The surface modified member obtained in this embodiment is the above-mentioned second surface modified member including a surface modified layer and a resin member.

Furthermore, as described above, it is preferable to provide a mixing layer in which the resin and the surface modification layer are mixed between the resin member and the surface modification 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 a surface modified member. Furthermore, in FIG. 1, the surface modified layer 10 is layered on the surface of the resin member 100, but it is preferable to have the resin member mixed with the surface modified layer between the resin member 100 and the surface modified layer 10. into a mixed layer (not shown).

[painting] The coated product according to the embodiment of the present invention is a coated product having a coating film on at least a part of the surface modified member, and preferably has a coating film on at least a part of the surface of the surface modified member on the surface modification layer side. The coating film is at least one selected from the group consisting of painting, printing layer, vapor deposition layer, and plating layer.

As an example of a coated object according to an embodiment of the present invention, FIG. 4 shows a coated object 300 on the surface modified layer side of a surface modified member formed by providing a surface modified layer 10 on the surface of a resin member 100. The surface is provided with a coating film 30 .

The surface modifying layer is formed using a sheet-shaped surface modifying sheet instead of being applied to the surface of the member, so unevenness due to shrinkage and the like can be prevented. Therefore, the surface modifying layer can be formed with a uniform thickness on the surface of the resin member, and a coating film can be applied with a uniform film thickness. Also, by providing the surface modified layer on the surface of the resin member in the molten state or softened state, the surface modified layer is welded and mixed or chemically bonded due to the heat of the surface of the resin member, so that the adhesive strength between the surface modified layer and the resin member is relatively low. High, so it can form a coating film with excellent adhesion. Furthermore, when the coating is formed, the surface modification layer and the resin member can be integrally molded, so there is no need for a cleaning treatment step or a grinding treatment step using an organic solvent to remove the release agent before forming the coating film, and it is safe. Excellent performance, can reduce environmental load and work load.

The coating film is not particularly limited, and examples include: epoxy-based, polyester-melamine-based, alkyd-melamine-based, acrylic-melamine-based, acrylic-urethane-based, acrylic-polyacid curing agents Department of various coatings.

The thickness of the coating film is not particularly limited, for example, it is 1-1000 μm, more preferably 3-300 μm, further preferably 5-100 μm, especially preferably 10-50 μm.

The coating method of the coating film is not particularly limited, 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, temperature, and the like for heating the coating film can also be appropriately determined according to the paint used, the amount of coating, and the like.

[Manufacturing method of the painted article of the first embodiment] The method of manufacturing a painted article according to the first embodiment of the present invention is a method of manufacturing a painted article using the surface-modified sheet according to the embodiment of the present invention, and includes: laminating the surface-modified layer by thermocompression bonding A step of forming a surface-modified member on the resin member; and a step of forming a coating film on the surface-modified layer side of the above-mentioned surface-modified member.

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

The resin contained in the resin component can be thermosetting resin or thermoplastic resin, preferably thermosetting resin, especially 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, and polyisocyanurate resins. , Polyimide resin.

Moreover, the surface modification member can be formed by resin molding, and as resin molding, injection molding, press molding, etc. are mentioned, for example.

As the resin member, thermoplastic resin, thermosetting resin, surface-modified sheet, surface-modified layer, and surface-modified member, the above description can be directly applied.

The coating film is not particularly limited, and examples include: acrylic, urethane, epoxy, fluorine, silicone, polyester/melamine, alkyd/melamine, acrylic, Various coating films such as melamine-based, acrylic-urethane-based, acrylic-polyacid curing agent-based, etc.

The coating method of the coating film is not particularly limited, 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, temperature, and the like for heating the coating film can also be appropriately determined according to the paint used, the amount of coating, and the like.

The step of forming the surface modified member by laminating the above-mentioned surface modified layer on the resin member by heat and pressure bonding can be adopted as follows: Laminate the surface modified layer in the surface modified sheet on the resin member by heat and pressure bonding Then, the surface modified member is formed (that is, the method for manufacturing the surface modified member of the first embodiment described above). Alternatively, it is also possible to adopt the following aspect: the release sheet is peeled off from the above-mentioned first laminate which is a resin material with a surface-modified sheet to obtain the second laminate, and the second laminate is obtained using a mold that has undergone release treatment. The two laminates are thermoformed (that is, the method of manufacturing the surface-modified member of the second embodiment described above).

[Manufacturing method of the painted article of the second embodiment] The manufacturing method of the painted article according to the second embodiment of the present invention is a method of manufacturing a painted article in which the painted article of the present invention is laminated on a resin member. In the case where at least one part of the surface modified member made of the surface modified layer of the embodiment has a coating film, the resin contained in the resin member is a thermoplastic resin with a melting point of T ₁ °C, and the method for manufacturing the above coating includes: A step of providing a surface-modified layer on at least a part of the surface of the resin member, and heating and welding at a temperature above (T ₁ -50)°C to form a surface-modified member; and on the surface-modified layer side of the above-mentioned surface-modified member The step of forming a coating film.

In the method of manufacturing a painted object according to the second embodiment of the present invention, stronger adhesive strength can be obtained, and the surface treatment steps as previously performed can be preferably reduced. Also, in one embodiment of the method of manufacturing a coated article according to the second embodiment of the present invention, by performing surface treatment simultaneously with the forming process, there is no need to use a release agent, and the step of removing the release agent (sand blasting treatment) can be reduced. , degreasing treatment, etc.).

In the method of manufacturing a coated article according to the second embodiment of the present invention, when the melting point of the thermoplastic resin included in the resin member is set to T ₁ °C, on the surface of the resin member (thermoplastic resin member) containing the thermoplastic resin At least one part is provided with a surface modification layer, which is heated and welded at a temperature above (T ₁ -50)°C. By performing the surface treatment of the thermoplastic resin member by such a method, sufficient adhesive strength can be imparted to the thermoplastic resin member, and it is preferable that such imparting can be performed with high productivity and at low cost.

The temperature of the heat welding is preferably (T ₁ -50) °C ~ (T ₁ +150) °C, more preferably (T ₁ -25) °C ~ (T ₁ +100) °C, and more preferably (T ₁ -10) °C )°C to (T ₁ +75)°C, especially preferably (T ₁ )°C to (T ₁ +50)°C. By setting the heating and welding temperature within the above range, and performing the surface treatment of the thermoplastic resin member by the above-mentioned method, the interface between the surface modification layer and the thermoplastic resin member is melt-contacted and welded and mixed, and the thermoplastic resin member can be imparted It is preferable that sufficient adhesive strength can be imparted at high and low cost.

As the thermoplastic resin contained in the resin member according to the embodiment of the present invention, for example, PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET ( Polyethylene terephthalate), PBT (polybutylene terephthalate), POM (polyacetal), PEEK (polyether ether ketone), PC (polycarbonate), etc. Among these resins, examples of thermoplastic resins that can advantageously exhibit the effects of the present invention include PPS (polyphenylene sulfide), PA (polyamide), and PP (polypropylene).

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

As fiber reinforced thermoplastic resin (FRTP), carbon fiber reinforced thermoplastic resin (CFRTP), glass fiber reinforced thermoplastic resin (GFRTP), etc. are mentioned, for example.

The carbon fiber reinforced thermoplastic resin (CFRTP) may, for example, be a PPS-based carbon fiber-reinforced thermoplastic resin, a PA-based carbon fiber-reinforced thermoplastic resin, or a PP-based carbon fiber-reinforced thermoplastic resin.

Examples of the glass fiber reinforced thermoplastic resin (GFRTP) include PPS-based glass fiber-reinforced thermoplastic resins, PA-based glass fiber-reinforced thermoplastic resins, PP-based glass fiber-reinforced thermoplastic resins, and the like.

As the surface modifying layer, the above description can be directly applied. As the coating film and the coating method of the coating film, the description in the section of [Manufacturing method of the coated object of the first embodiment] can be directly used.

[Manufacturing method of the painted article of the third embodiment] The manufacturing method of the painted article according to the third embodiment of the present invention is a method of manufacturing a painted article in which the painted article of the present invention is laminated on a resin member. In the case where at least a part of the surface-modified member made of the surface-modified layer of the embodiment has a coating film, the resin contained in the resin member is a thermosetting resin with a curing temperature of T ₂ °C, and the method for manufacturing the above-mentioned coating includes: A step of providing a surface modification layer on at least a part of the surface, and forming a surface modification member by heating and forming at a temperature above T ₂ °C; and a step of forming a coating film on the surface modification layer side of the surface modification member.

In the manufacturing method of the painted object according to the third embodiment of the present invention, stronger adhesive strength can be obtained, and the surface treatment steps as previously performed can be preferably reduced. Also, in one embodiment of the method of manufacturing a coated article according to the third embodiment of the present invention, by performing surface treatment simultaneously with the forming process, the use of a release agent can be eliminated, and the step of removing the release agent (sand blasting treatment) can be reduced. , degreasing treatment, etc.).

In the method of manufacturing a painted article according to the third embodiment of the present invention, when the curing temperature of the thermosetting resin contained in the resin member is set to T ₂ °C, the thermosetting resin member is provided on at least a part of the surface of the resin member (thermosetting resin member). The surface modification layer is heat-formed at a temperature above T ₂ ℃. By performing the surface treatment of the thermosetting resin member by such a method, sufficient adhesive strength can be imparted to the thermosetting resin member, and it is preferable that such imparting can be performed with high productivity and at low cost.

The thermoforming temperature is preferably (T ₂ -50) °C ~ (T ₂ +50) °C, more preferably (T ₂ -40) °C ~ (T ₂ +40) °C, and more preferably (T ₂ -30) °C )°C to (T ₂ +30)°C, especially preferably (T ₂ -20)°C to (T ₂ +20)°C. By setting the thermoforming temperature within the above-mentioned range, and performing the surface treatment of the thermosetting resin member by the above-mentioned method, the interface between the surface modification layer and the thermosetting resin member is softened by heating to mix or chemically bond the thermosetting resin. It is preferable to impart sufficient adhesive strength to the members, and it is preferable that such imparting can be performed with high productivity and at low cost.

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

As the thermosetting resin, a fiber-reinforced thermosetting resin may be used.

As a fiber-reinforced thermosetting resin, a carbon fiber-reinforced cured plastic resin, a glass fiber-reinforced thermosetting resin, etc. are mentioned, for example.

"At least a part of the surface of the thermoplastic resin member" and "at least a part of the surface of the thermosetting resin member" mean at least a part of all the surfaces of the thermoplastic resin member or the thermosetting resin member. For example, when a thermoplastic resin member or a thermosetting resin member is in the form of a plate, a sheet, or a film, it means a part of at least one surface thereof, or the entirety of at least one surface thereof.

As the shape of the thermoplastic resin member and the thermosetting resin member, 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 may, for example, be mentioned.

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

In the method of manufacturing a painted article according to the second embodiment of the present invention or the method of manufacturing a painted article according to the third embodiment of the present invention, as a method of providing a surface modification layer on at least a part of the surface of a thermoplastic resin member or a thermosetting resin member , for example: a method of coating a solution of a material containing a surface modifying layer and a solvent on at least a part of the surface of a thermoplastic resin member or a thermosetting resin member; melt-extruding a surface modifying layer onto a thermoplastic resin member or a thermosetting resin A method of at least a part of the surface of a member; a method of laminating a sheet-shaped surface modification layer on at least a part of the surface of a thermoplastic resin member or a thermosetting resin member, etc.

As a method of applying a solution of a material and a solvent for the surface modifying layer according to an embodiment of the present invention, for example, immersing a thermoplastic resin member or a thermosetting resin member in a solution containing the material for the surface modifying layer and a solvent ; At least a part of the surface of a thermoplastic resin member or a thermosetting resin member is brushed with a solution of a material and a solvent including a surface modification layer; using various coating machines, the solution of a material and a solvent including a surface modification layer is coated on the thermoplastic At least a part of the surface of a resin member or a thermosetting resin member; spraying a solution of a material including a surface modifying layer and a solvent on at least a part of the surface of a thermoplastic resin member or a thermosetting resin member, etc.

As a solution containing the material of the surface modification layer and a solvent, there may be mentioned a surface modification composition obtained by dissolving the material of the surface modification layer in any appropriate solvent within the range that does not impair the effects of the present invention.

As the surface modifying layer and the surface modifying composition, the above description can be directly applied.

In the case where a solution including a material for the surface modifying layer and a solvent is applied to at least a part of the surface of the thermoplastic resin member or the thermosetting resin member, at least a part of the solvent is removed by drying thereafter. In such drying, it is sufficient to remove at least a part of the solvent, preferably at least 50% by mass of the solvent, more preferably at least 80% by mass of the solvent, further preferably at least 90% by mass of the solvent, especially More than 95% by mass of the solvent is preferably removed, and most preferably all of the solvent is removed.

As the drying method, any suitable method can be adopted as long as the solvent can be removed such as oven heating, infrared heating, high-frequency heating, etc. within the range not impairing the effects of the present invention. Moreover, as drying temperature, arbitrary appropriate temperature can be set suitably according to the boiling point of the solvent used.

As a method of melt-extruding the surface modification layer, for example, the method of melt-extruding the material of the surface modification layer onto at least a part of the surface of the thermoplastic resin member or the thermosetting resin member with a melt extruder etc. method etc.

As a method for the surface modification layer in the form of a laminated sheet, for example, lamination on at least a part of the surface of a thermoplastic resin member or a thermosetting resin member as described in the item of the production method of a surface modification member according to an embodiment of the present invention A method on the surface modification layer side of the above-mentioned surface modification sheet (a laminate of a release sheet and a surface modification layer), etc.

As a method of thermoforming, for example, oven heating, infrared heating, high-frequency heating, thermocompression bonding, etc. may be mentioned, and thermocompression bonding is preferable.

The time for thermoforming is preferably 1 second to 2 hours.

Surface modification can be obtained by providing a surface modifying layer on the surface of a thermoplastic resin member or a thermosetting resin member by the method of manufacturing a painted article according to the second embodiment or the method of manufacturing a painted article according to the third embodiment of the present invention. A component (also sometimes referred to as a laminated component of a thermoplastic resin component or a thermosetting resin component and a surface-modified layer), and a coating film is formed on the surface-modified layer side of the surface-modified component to obtain a coated object. Preferably, a mixing layer in which the thermoplastic resin member or thermosetting resin member and the surface modification layer are mixed is provided between the thermoplastic resin member or thermosetting resin member and the surface modification layer. The thickness of the mixed layer is preferably at least 1.5 nm, more preferably at least 2.0 nm.

The average thickness of the surface modification layer is preferably from 0.1 to 2000 μm, more preferably from 1 to 1000 μm, still more preferably from 3 to 200 μm, especially preferably from 5 to 30 μm.

As the coating film and the coating method of the coating film, the description in the section of [Method for Manufacturing Coated Object of the First Embodiment] can be directly used.

[Manufacturing Method of Coated Article of Fourth Embodiment] The method of manufacturing a painted article according to the fourth embodiment of the present invention is a method of manufacturing a painted article in which a coating film is formed on the surface modified layer side of a surface modified member formed by laminating a surface modified layer on a resin member. . In the method for producing a coated article according to the fourth embodiment of the present invention, after making at least a part of the surface of the resin member into a molten state or a softened state, a surface modification layer is provided on the surface of the resin member in the molten state or softened state . By performing the surface treatment of the resin member by such a method, sufficient adhesive strength can be imparted to the resin member, and it is preferable that such imparting can be performed with high productivity and at low cost.

In the method of manufacturing a coated article according to the fourth embodiment of the present invention, at least a part of the surface of the resin member is made into a molten state or a softened state, and a surface modification layer is provided on the surface.

As "at least a part of the surface of the resin member", the description in the section of [Method for Manufacturing Coated Article of First Embodiment] can be directly used.

As the resin member, the description in the section of "Manufacturing Method of Coated Article of First Embodiment" can be directly used.

The "molten state" is a state in which at least a part of the surface of the resin member is melted, and is preferably achieved by bringing the resin member to a temperature above its melting point.

The "softened state" is a state in which at least a part of the surface of the resin member is softened, and can be preferably achieved by heating the resin member to a temperature above its softening temperature.

In the method for producing a coated article according to the fourth embodiment of the present invention, after making at least a part of the surface of the resin member into a molten state or a softened state, a surface modification layer is provided on the surface of the resin member in the molten state or softened state . By providing the surface modified layer on the surface of the resin member in the molten state or softened state, the surface modified layer can be welded and mixed by the heat of the surface of the resin member, so that sufficient adhesive strength can be given to the resin member, and it is preferable to allow high production Such endowment can be performed efficiently and at low cost.

As the surface modifying layer, the coating film, and the coating method of the coating film, the description in the section of [Manufacturing method of the coated object according to the first embodiment] can be directly used.

In the method of manufacturing a coated article according to the fourth embodiment of the present invention, as a method of providing a surface modification layer on the surface of a resin member in a molten state or a softened state, for example, a release sheet and a surface A method in which the surface modified layer side of the surface modified sheet of the modified layer laminate is placed on the molten or softened surface of the resin member. By the method described above, more sufficient adhesive strength can be imparted to the resin member, and it is preferable that such imparting can be performed with high productivity and low cost.

[Step management method] In the manufacture of the surface modified sheet, the manufacture of the surface modified member, and the manufacture of the coated article according to the embodiment of the present invention, for example, by making the surface modifying composition or the surface modifying layer contain dyes, pigments, or additives such as crystalline substances, the surface modification layer can be visualized, making it easy to manage the manufacturing steps.

As the surface modifying composition, surface modifying sheet, coating material, and additives, the above description can be directly applied.

As a process management method, for example, the method of performing surface treatment and visually confirming the colored part, or recognizing and discriminating an image captured by a camera can be mentioned.

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

[1] A surface-modified sheet comprising a release sheet and a surface-modified layer, and the storage modulus of the above-mentioned surface-modified layer at 160°C is 5.0×10 ³ to 1.0×10 ⁸ Pa, The surface tension of the above-mentioned surface modification layer is 38 mN/m or more, the above-mentioned surface modification layer has a crystalline polyamide component and a filler containing a polar group, and the content of the above-mentioned filler is relative to 100 parts by mass of the above-mentioned crystalline polyamide component It is 3-40 mass parts. [2] The surface modified sheet as described in [1], wherein the surface of the above-mentioned filler is not treated, or the functional group on the surface of the above-mentioned filler is selected from the group consisting of silanol group, hydroxyl group, amino group, mercapto group, carboxyl group, and isocyanate At least one group selected from the group consisting of an acid group and an epoxy group. [3] The surface-modified sheet according to [1] or [2], wherein the above-mentioned 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 diameter 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, wherein the surface-modified laminate is layered on at least a part of the surface of the resin material . [7] The laminate described in [6], wherein the resin material is a prepreg. [8] A laminate comprising a surface-modified layer and a resin material, wherein the storage modulus of the surface-modified layer at 160°C is 5.0×10 ³ to 1.0×10 ⁸ Pa, and the above-mentioned surface-modified layer The surface tension is 38 mN/m or more, the above-mentioned surface modification layer has a crystalline polyamide component and a filler containing a polar group, and the content of the above-mentioned filler is 3 to 40 mass parts relative to 100 mass parts of the above-mentioned crystalline polyamide component The above-mentioned surface modification layer is laminated on at least a part of the surface of the above-mentioned resin material. [9] A surface modified member comprising the surface modified sheet according to any one of [1] to [5] and a resin member, wherein the surface modified layer is laminated on the surface of the resin member at least partly. [10] The surface modifying member according to [9], wherein the resin member includes a thermosetting epoxy resin. [11] A coated article having a coating film on at least a part of the surface modifying member described in [9] or [10], wherein the coating film is selected from the group consisting of coating, printing layer, vapor deposition layer, and At least one of the group consisting of plating layers. [12] A method for producing a surface-modified member, which is a method for producing a surface-modified member using the surface-modified sheet described in any one of [1] to [5], and comprising modifying the above-mentioned surface The layer is laminated on the resin member by thermocompression bonding. [13] The method for producing a surface modified member according to [11], wherein the resin member includes a thermosetting epoxy resin. [14] A method of manufacturing a surface-modified member, which is a method of manufacturing a surface-modified member using the laminate described in [8], and includes: using a mold that has undergone release treatment, applying the above-mentioned surface-modified layer to A step of laminating and molding a resin member by thermocompression bonding. [15] A method of manufacturing a coated object, which is a method of manufacturing a coated object using the surface modified sheet described in any one of [1] to [5], comprising: adding the above-mentioned surface modified layer a step of manufacturing a surface-modified member by laminating on 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. [16] The method for producing a coated article according to [15], wherein the resin member includes a thermosetting epoxy resin. [Example]

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples.

[Example 1] (Surface modified sheet(1)) Dissolve 100 parts by mass of polyamide copolymer resin (Amilan CM8000 manufactured by Toray Co., Ltd.) and 5 parts by mass of untreated fumed silica (Cab-o-sil manufactured by CABOT, average primary particle size: 12 nm) In a mixed solvent of ethanol (EtOH)/water=80% by mass/20% by mass at 40° C., a solution with a solid content of 20% by mass (surface modifying composition) was produced.

After the prepared surface modifying composition was filtered through a nylon mesh with a mesh size of 188 μm, it was applied to a release sheet (NITOFLON 900UL: fluororesin sheet film (polyester) manufactured by Nitto Denko Co., Ltd. with an applicator. Tetrafluoroethylene (PTFE) (thickness 0.05 mm, size: width 250 mm x length 450 mm)) was dried with a constant temperature dryer at 100 ° C x 2 minutes to produce a surface with a release sheet and a surface modification layer Modified sheet (1).

(Surface modified member (1)) Lay the surface-modified sheet (1) prepared above on a carbon fiber-reinforced thermosetting epoxy resin prepreg (manufactured by Toray Co., Ltd., Torayca) (dimensions: width 150 mm x length 120 mm x thickness 1 mm) Above, heat welding was performed by press working (150° C., 5 minutes) to produce a surface modifying member ( 1 ).

(Painting (1)) After peeling off the release sheet of the surface modification member (1) prepared above, apply V-top H (two-component curing urethane paint) manufactured by Dainippon Paint Co., Ltd. with an applicator Apply it on the surface modification layer, and cure the coating film at room temperature for more than 3 days to prepare a coated object (1).

[Examples 2-6, 9, 10, Comparative Examples 1-5, 7] In addition to changing the material used in the surface modification composition, the amount used, the type of resin member, and the molding temperature when the surface modification member is formed, as shown in Table 1 or 3, according to the method described in Example 1, Fabrication of surface-modified sheets, surface-modified members, and painted objects.

[Example 7] The surface modification sheet was produced according to the method described in Example 1, except that the materials and usage amounts of the surface modification composition were changed as shown in Table 1.

The surface-modified layer sides of the produced two surface-modified sheets 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 laminate was peeled off, and the surface-modified layer sides were superimposed on each other, and heat lamination was performed at 150°C. This step was repeated several times until the thickness of the surface modification layer reached 200 μm to form a surface modification sheet.

[Example 8, Comparative Example 6] In addition to changing the materials used in the surface modification composition, the usage amount, and the thickness of the surface modification layer as shown in Table 1 or 3, according to the method described in Example 7, the surface modification sheet and the surface modification layer were prepared. Modified components, and coatings.

[Comparative Examples 8 and 9] The surface modification layer was not provided, and the surface modification member was produced using the release sheet and the resin member described in Table 3, and the coated object was produced according to the method described in Example 1.

[Example 11] (Resin material with surface modification layer (1)) Except that the amount of silicon dioxide used in the surface modification composition was changed as shown in Table 2, the surface modification sheet was prepared according to the method described in Example 1, and the obtained surface modification sheets were stacked On top of carbon fiber reinforced thermosetting epoxy resin prepreg (manufactured by Toray Co., Ltd., Torayca) (dimensions: width 150 mm x length 120 mm x thickness 1 mm), the release sheet was peeled off to obtain an attached surface The resin material (1) of the modification layer.

(surface modification member (11)) A release sheet for the mold (NITOFLON 900UL: fluororesin sheet film (PTFE) manufactured by Nitto Denko Co., Ltd. (thickness 0.05 mm, size: width 250 mm ×Length 450 mm)) After that, perform vacuum suction to make the sheet follow the mold, thereby performing release treatment on the surface of the mold. The surface-modified resin material (1) prepared above is placed on the side of the mold that has been subjected to release treatment in such a manner that the surface-modified layer side of the resin material with a surface-modified layer is facing. Press processing (150° C., 5 minutes) was performed to perform heat welding to produce a surface-modified member ( 11 ).

(Paint (11)) Using an applicator, apply V-top H (two-component curing urethane paint) manufactured by Dainippon Paint Co., Ltd. on the surface modification layer of the surface modification member (11) prepared above, The coating film was cured at room temperature for more than 3 days to prepare a coated object (11).

[Example 12, 13] Except that the mold release sheet used in the mold release treatment was changed as shown in Table 2, according to the method described in Example 11, a resin material with a surface modification layer, a surface modification member, and a coating were produced. loading.

[Example 14] In addition to performing release treatment on the surface of the mold by applying Chemlease HT-S (polysiloxane-based baking-curable type Chem-Trend Japan Co., Ltd.) as a curing type release agent to the surface of the mold and curing it , instead of the release treatment using the mold release sheet, according to the method described in Example 11, a resin material with a surface modification layer, a surface modification member, and a coated object were produced.

[Example 15] In addition to using Fine Dry FB-4 (manufactured by hexagonal boron nitride type Fine chemical Japan Co., Ltd.) as a curing type release agent, according to the method of Example 14, a resin material with a surface modification layer and a surface modification layer were produced. Quality components, and coatings.

[Example 16] In addition to using a mold that has been subjected to a peeling process using PTFE (polytetrafluoroethylene) instead of a mold that has been released with a mold release sheet, according to the method described in Example 11, a surface modification Resin materials for the textured layer, surface modified components, and coatings.

＜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"). In addition, the average primary particle diameter adopts the average value per 100 silica particles.

＜Storage modulus＞ Using the surface-modified sheets produced in Examples and Comparative Examples, the storage modulus was measured by the following operation. The surface modified layer from which the release sheet was peeled was laminated, and the laminated product laminated to about 500 μm was used as a measurement sample. The said laminated product was cut into diameter 8mm, and the test piece was produced. Using a jig with a diameter of 8 mm, the viscoelastic device ARES-G2 manufactured by TA Instruments was used to implement temperature dispersion at 25-300°C. At this time, the heating rate was set at 5° C./min, and the frequency was set at 1 Hz. The modulus of elasticity at 160° C. at this time was defined as the storage modulus (Pa).

＜Heat of cold crystallization＞ Carry out DSC (differential operation type thermal analysis) measurement under the following conditions, calculate the heat absorption of the surface modification layer according to the heat absorption peak area of the heat flow curve obtained in the first cooling process, and set it as the heat of cold crystallization (j /g).

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

At this time, the heat of cold crystallization obtained by measuring only the crystalline polyamide component alone was defined as A, and the heat of cold crystallization of the surface modified layer was defined as B. The value of B includes the value of the filler, so the change in the heat of cold crystallization of the crystalline polyamide component cannot be simply compared with A. Therefore, when X parts by mass of filler are added to 100 parts by mass of the crystalline polyamide component, the heat of cold crystallization of the crystalline polyamide component is converted by weight according to the following formula, and the value is set to B' . Furthermore, the value of the heat of cold crystallization recorded in the table is B'. B'=B×(100+X)/100

Moreover, by adding a filler to the crystalline polyamide component, the reduction rate of the heat of cold crystallization was calculated by the following formula, and it was set as the reduction rate of the heat of cold crystallization. Heat reduction rate of cold crystallization = {(AB')/A}×100

<Film thickness of surface modification layer> The film thickness of the surface modification layer was measured with a dial gauge (GC9 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 was measured, and the difference was taken as the thickness (μm) of the surface-modified layer. The film thickness (μm) of the surface modification layer is an average value obtained by measuring 10 places.

＜Elongation at break＞ Using a tensile testing machine with a constant temperature bath, perform a tensile test under the following test conditions. Test device: AG-I 20 kN manufactured by Shimadzu Corporation Load cell: 50 N Sample piece: Use the one punched into No. 5 dumbbell piece. Tensile speed: 300mm/min Distance between marking lines: 70 mm

In the stress-strain curve measured by the above tensile test at 23°C, the point at which the surface modification layer was cut was taken as the breaking point, and the elongation value at this time was taken as the elongation at break. In this case, C is the elongation at break of the surface modified layer containing only the crystalline polyamide component alone, and D is the elongation at break of the surface modified layer containing the crystalline polyamide component and filler. In addition, the value of elongation at break described in the table|surface is D.

Moreover, the increase rate of the elongation at break by adding a filler was calculated by the following formula, and it was set as the increase rate of elongation at break. Increase rate of elongation at break = {(D－C)/C}×100

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

＜60° glossiness＞ The 60° gloss at room temperature (25° C.) was measured by Specular Gloss Measurement (JIS Z8741-1997). Install a BYK gloss meter (micro-tri-gloss) on the surface of the coating to measure the gloss of the coating film. The glossiness is the average value obtained by measuring 5 places.

Moreover, the 60 degree glossiness after holding|maintaining for 24 hours in the constant temperature and humidity chamber set to the environment of temperature 85 degreeC, and humidity 85%RH was measured. Using the above-mentioned 60° gloss at room temperature (25°C) and the 60° gloss after being kept for 24 hours in an environment with a temperature of 85°C and a humidity of 85%RH, the 60° gloss reduction rate was calculated by the following formula. 60° Gloss Reduction Rate (%) = [(Gloss (25°C) - Gloss (85°C/85%RH))/Gloss (25°C)]×100 When the 60° gloss reduction rate was 5% or less, it was judged that the change in appearance of the coating film was 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 is measured by the wetting tension test method (JIS K6768-1999). Add a few drops of the mixed solution for wetting tension test adjusted to an appropriate surface tension on the surface modified layer side of the surface modified sheet, and spread the mixed solution for wetting tension test with a cotton swab. When the applied mixed solution for the wetting tension test does not break and remains in the applied state for more than 2 seconds, it is judged as wet. The mixed solution for the wetting 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 modification layer of the surface modification member is measured by the wetting tension test method (JIS K6768-1999). Add a few drops of the mixed solution for wetting tension test adjusted to an appropriate surface tension on the surface modified layer side of the surface modified member, and spread the mixed solution for wetting tension test with a cotton swab. When the applied mixed solution for the wetting tension test does not break and remains in the applied state for more than 2 seconds, it is judged as wet. The mixed solution for the wetting tension test was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

＜Paint Adhesion＞ The coated objects produced in Examples and Comparative Examples were evaluated by cross-cutting by the cross-cut method described in JIS K5600-5-6, and the number of peeled pieces of the coating film was counted. Adhesiveness was judged to be good when the number of peeled sheets of a coating film was 0 sheet|seat in 100 sheets.

Interval between cuts: 2 mm Number of cross cuts: 100 pieces Peeling tape: (Miqibang) scotch tape (registered trademark) 24 mm wide

The results of Examples and Comparative Examples are shown in Tables 1 to 3 below. In addition, regarding 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.

[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 surface modification layer polymer CM8000 (Copolyamide) 100 100 100 100 100 100 100 100 - 100 FR105 (polyamide containing methoxymethyl group) - - - - - - - - 100 - silicon dioxide M5 (untreated fumed silica) 5 10 20 - - - 12.5 12.5 10 20 50 (untreated fumed silica) - - - 10 - - - - - - 300 (untreated fumed silica) - - - - 10 - - - - - ST-OS (untreated colloidal silicon dioxide) - - - - - 30 - - - - TS720 (PDMS Modified Fumed Silica) - - - - - - - - - - Average primary particle size nm 12 12 12 30 7 9 12 12 12 12 160℃ storage modulus Pa 28000 90680 793622 15806 69878 71942 120000 120000 222518 793622 cold crystallization heat J/g 23.6 22.2 15.3 23.2 20.8 12.3 21.2 21.2 9.6 15.3 Cold crystallization heat reduction rate % 1.8 7.8 36.3 3.5 13.3 48.8 11.8 11.8 12.9 36.3 surface tension A mN/m >56 >56 >56 >56 >56 >56 >56 >56 >56 >56 Release sheet No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL Manufacturing method Manufacturing method apply apply apply apply apply apply Lamination of coatings Lamination of coatings apply apply Solid content quality% 20% 20% 20% 20% 20% 20% 20% 20% 20% 20% solvent EtOH/water 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 thickness μm 10 10 10 10 10 10 200 1000 10 10 Forming method resin component CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-PPS Forming method Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Molding temperature (T°C) 150°C 150°C 150°C 150°C 150°C 150°C 150°C 150°C 150°C 300℃ Release treatment With or without release sheet during molding have have have have have have have have have have Release sheet for mold - - - - - - - - - - Release agent - - - - - - - - - - Mold surface processing - - - - - - - - - - Elongation elongation at break % 316.2 338.6 356.9 322.3 351.6 376.0 359.0 359.0 379.9 356.9 Elongation at break increase rate % 2.0 9.2 15.1 4.9 14.4 22.4 15.8 15.8 7.4 15.1 Coating Appearance Coating thickness μm 50 50 50 50 50 50 50 50 50 50 60° Gloss (25°C) 85.6 86.0 86.4 88.2 87.5 87.6 87.9 88.6 87.5 88.6 60° Gloss (after 85℃/85% input) 84.0 86.3 86.3 88.3 87.6 87.9 86.5 87.1 87.3 87.9 60° Gloss Reduction Rate % 1.9 -0.3 0.1 -0.1 -0.1 -0.3 1.6 1.7 0.2 0.8 Closeness surface tension B mN/m >56 >56 >56 >56 >56 >56 >56 >56 >56 >56 Coating adhesion Number of peeled parts (in 100 pieces) 0 0 0 0 0 0 0 0 0 0

[Table 2] Table 2 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 surface modification layer polymer CM8000 (Copolyamide) 100 100 100 100 100 100 FR105 (polyamide containing methoxymethyl group) - - - - - - silicon dioxide M5 (untreated fumed silica) 20 20 20 20 20 20 50 (untreated fumed silica) - - - - - - 300 (untreated fumed silica) - - - - - - ST-OS (untreated colloidal silicon dioxide) - - - - - - TS720 (PDMS Modified Fumed Silica) - - - - - - Average primary particle size nm 12 12 12 12 12 12 160℃ storage modulus Pa 793622 793622 793622 793622 793622 793622 cold crystallization heat J/g 15.3 15.3 15.3 15.3 15.3 15.3 Cold crystallization heat reduction rate % 36.3 36.3 36.3 36.3 36.3 36.3 surface tension A mN/m >56 >56 >56 >56 >56 >56 Release sheet No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL Manufacturing method Manufacturing method apply apply apply apply apply apply Solid content quality% 20% 20% 20% 20% 20% 20% solvent EtOH/water 80/20 80/20 80/20 80/20 80/20 80/20 thickness μm 10 10 10 10 10 10 Forming method resin component CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS Forming method Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Molding temperature (Tt) 150°C 150°C 150°C 150°C 150°C 150°C Release treatment With or without release sheet during molding none none none none none none Release sheet for mold No.900UL MRF38 P2171 - - - Release agent - - - Chemlease HT-S Fine Dry FB-4 - Mold surface processing - - - - - Fluorine processing Elongation elongation at break % 356.9 356.9 356.9 356.9 356.9 356.9 Elongation at break increase rate % 15.1 15.1 15.1 15.1 15.1 15.1 Coating Appearance Coating thickness μm 50 50 50 50 50 50 60° Gloss (25°C) 86.4 86.4 86.4 86.4 86.4 86.4 60° Gloss (after 85℃/85% input) 86.3 86.3 86.3 86.3 86.3 86.3 60° Gloss Reduction Rate % 0.1 0.1 0.1 0.1 0.1 0.1 Closeness surface tension B mN/m >56 38.0 38.0 38.0 38.0 >56 Coating adhesion Number of peeling parts (in 100 pieces) 0 0 0 0 0 0

[table 3] table 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 surface modification layer polymer CM8000 (Copolyamide) 100 - 100 100 100 100 100 - - FR105 (polyamide containing methoxymethyl group) - 100 - - - - - - - silicon dioxide M5 (untreated fumed silica) - - 1 - - - - - - 50 (untreated fumed silica) - - - - - - - - - 300 (untreated fumed silica) - - - - - - - - - ST-OS (untreated colloidal silicon dioxide) - - - 50 - - - - - TS720 (PDMS Modified Fumed Silica) - - - - 10 - - - - Average primary particle size nm - - 12 twenty two 12 - - - - 160℃ storage modulus Pa 4478 4600 2952 51000 41867 4478 4478 - - cold crystallization heat J/g 24.0 11.0 24.5 9.2 23.5 24.0 23.6 - - Cold crystallization heat reduction rate % - - -2.0 61.7 2.1 - 1.8 - - surface tension A mN/m >56 >56 >56 >56 >56 >56 >56 Release sheet No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL No.900UL Manufacturing method Manufacturing method apply apply apply apply apply Lamination of coatings apply - - Solid content quality% 20% 20% 20% 20% 20% 20% 20% - - solvent EtOH/water 80/20 80/20 80/20 80/20 80/20 80/20 80/20 - - thickness μm 10 10 10 10 10 200 10 - - Forming method resin component CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-EpTS CF-PPS CF-EpTS CF-PPS Forming method Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Compression molding Molding temperature (Tt) 150°C 150°C 150°C 150°C 150°C 150°C 300℃ 150°C 300℃ Release treatment With or without release sheet during molding have have have have have have have have have Release sheet for mold - - - - - - - - - Release agent - - - - - - - - - Mold surface processing - - - - - - - - - Elongation elongation at break % 310.1 353.8 316.2 266.9 151.9 310.1 316.2 - - Elongation at break increase rate % - - 2.0 -13.9 -51.0 - 2.0 - - Coating Appearance Coating thickness μm 50 50 50 50 50 50 50 50 50 60° Gloss (25°C) 85.8 86.3 86.5 87.2 86.5 83.4 86.7 88.3 88.4 60° Gloss (after 85℃/85% input) 48.5 54.2 82.0 87.1 86.5 70.3 67.6 88.1 87.7 60° Gloss Reduction Rate % 43.4 37.2 5.2 0.1 0.0 15.7 22.0 0.3 0.8 Closeness surface tension B mN/m >56 >56 >56 >56 >56 >56 >56 35.0 30.0 Coating adhesion Number of peeling parts (in 100 pieces) 0 0 0 0 0 0 0 95 100

The materials described in Tables 1 to 3 are as follows. CM8000: Polyamide copolymer resin (Amilan manufactured by Toray Co., Ltd.) FR105: Nylon 6 with methoxymethyl group (FineResin manufactured by Lead City Co., Ltd.) 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 Co., 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 Co., Ltd., Torayca) CF-PPS: Carbon fiber reinforced thermoplastic polyphenylene sulfide resin (manufactured by Bond Laminates, Tepex) No.900UL: PTFE sheet (NITOFLON manufactured by Nitto Denko Co., Ltd., 50 μm thick) MRF38: Biaxially stretched polyester film (DIAFOIL manufactured by Mitsubishi Chemical Co., Ltd., 38 μm thick) P2171: Biaxially stretched polypropylene film (PYLEN manufactured by Toyobo Co., Ltd., 30 μm thick) Chemlease HT-S: Silicone-based bake-curable release agent (manufactured by Chem-Trend 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-mentioned embodiments, and various changes can be made within the range indicated in the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. . [Industrial availability]

The surface-modified sheet of the present invention has excellent adhesive strength, can suppress changes in appearance even in high-temperature and high-humidity environments, and has a surface-modified layer with improved elongation at break. In addition, by using the surface modified sheet of the present invention, unevenness can be prevented, and a smooth surface modified layer can be formed with a uniform thickness, and the surface modified layer and the resin member can be formed when the surface modified member is formed. Formed in one piece.

Although the present invention has been described in detail with reference to specific embodiments, it is clear to those skilled in the art that various changes and corrections can be made without departing from the spirit and scope of the present invention. This application is based on the Japanese patent application (Japanese Patent Application No. 2021-160128) for which it applied on September 29, 2021, The content is taken in here as a reference.

10: Surface modification layer 20: Release sheet 30: Coating film 100: Resin components 200: surface modified sheet 300: coating 400: resin material

Fig. 1 is a schematic sectional view showing an example of a surface modifying member. Fig. 2 is a schematic cross-sectional view showing an example of a surface-modified sheet. 3 is a schematic sectional view showing a state in which the surface modification layer side of the surface modification sheet, which is a laminate of a release sheet and a surface modification layer, is placed on at least a part of the surface of a resin material. Fig. 4 is a schematic sectional view showing an example of a coated object.

Claims (16)

A surface-modified sheet, which is provided with a release sheet and a surface-modified layer, and the storage modulus of the above-mentioned surface-modified layer at 160°C is 5.0×10 ³ to 1.0×10 ⁸ Pa, and the above-mentioned surface-modified The surface tension of the textured layer is 38 mN/m or more, the above-mentioned surface modified layer has a crystalline polyamide component and a filler containing a polar group, and the content of the above-mentioned filler is 3 to 100 parts by mass relative to 100 parts by mass of the above-mentioned crystalline polyamide component. 40 parts by mass. Such as the surface modified sheet of claim 1, wherein the surface of the above-mentioned filler is untreated, or the functional group on the surface of the above-mentioned filler is selected from the group consisting of silanol group, hydroxyl group, amino group, mercapto group, carboxyl group, isocyanate group, and At least one group of epoxy groups. The surface modified sheet according to claim 1, wherein the above-mentioned filler is silica particles. The surface modified sheet according to claim 1, wherein the average primary particle size of the filler is 5 nm to 1 μm. The surface-modified sheet according to claim 1, wherein the average thickness of the above-mentioned surface-modified layer is 0.1-2000 μm. A laminate comprising the surface-modified sheet and resin material according to any one of Claims 1 to 5, and The above-mentioned surface modification layer is laminated on at least a part of the surface of the above-mentioned resin material. The laminate according to claim 6, wherein the resin material is a prepreg. A laminate comprising a surface-modified layer and a resin material, and the storage modulus of the above-mentioned surface-modified layer at 160°C is 5.0×10 ³ to 1.0×10 ⁸ Pa, and the surface tension of the above-mentioned surface-modified layer 38 mN/m or more, the above-mentioned surface modification layer has a crystalline polyamide component and a filler containing a polar group, the content of the above-mentioned filler is 3 to 40 parts by mass relative to 100 parts by mass of the above-mentioned crystalline polyamide component, and the above-mentioned The surface modification layer is laminated on at least a part of the surface of the resin material. A surface modified member comprising the surface modified sheet and a resin member according to any one of claims 1 to 5, and The above-mentioned surface modification laminate is layered on at least a part of the surface of the above-mentioned resin member. The surface modification member according to claim 9, wherein the resin member comprises a thermosetting epoxy resin. A coated article having a coating film on at least a part of the surface modification member according to claim 9, and The coating film is at least one selected from the group consisting of coating, printing layer, vapor deposition layer, and plating layer. A method of manufacturing a surface modified member, which is a method of manufacturing a surface modified member using the surface modified sheet according to any one of claims 1 to 5, and It includes a lamination step of laminating the above-mentioned surface modification layer on the resin member by thermocompression bonding. The method of manufacturing a surface modified member according to claim 12, wherein the resin member includes a thermosetting epoxy resin. A method for manufacturing a surface-modified member, which is a method for manufacturing a surface-modified member using the laminate according to claim 8, and includes using a mold that has undergone release treatment, and bonding the above-mentioned surface-modified layer by heating and pressing The step of laminating and forming on the resin member. A method of manufacturing a coated object, which is a method of manufacturing a coated object using the surface modified sheet according to any one of claims 1 to 5, and includes: A step of laminating the above-mentioned surface modification layer on the resin member by thermocompression bonding to manufacture a surface modification member; and A step of forming a coating film on the surface modification layer side of the surface modification member. The method of manufacturing a painted article according to claim 15, wherein the resin member includes a thermosetting epoxy resin.