Surface-modified member, coated article, method for manufacturing surface-modified member, and method for manufacturing coated article

Abstract

The present invention relates to a surface-modified component having a surface-modified layer laminated on at least a portion of a resin component comprising a thermosetting resin, wherein a mixed layer formed by mixing the resin component and the surface-modified layer is provided between the resin component and the surface-modified layer, the thickness of the mixed layer being 250 nm to 10 μm.

Description

Technical Field

[0001] This invention relates to surface-modified parts, coatings, methods for manufacturing surface-modified parts, and methods for manufacturing coatings. Background Technology

[0002] In recent years, lightweight and impact-resistant resins have been used in components of transportation equipment such as railway vehicles, aircraft, ships, and automobiles, as well as electronic equipment and residential equipment, to bond various materials to their surfaces. Furthermore, coatings with various functions have been formed on these resin components.

[0003] It is known that when resin components containing thermosetting resins such as epoxy resins or unsaturated polyesters are used outdoors, yellowing of the resin can occur due to sunlight. For example, in epoxy resins with bisphenol A glycidyl ether as the main component, the resin yellows because the benzene ring absorbs ultraviolet light and the free radicals generated by its energy are oxidized, forming chromophores (Patent Document 1).

[0004] As methods to suppress resin yellowing, methods have been studied including adding ultraviolet absorbers and shielding agents to resin molded articles (Patent Document 2); coating the surface of resin molded articles with weather-resistant materials (Patent Document 3); making the resin composition of the resin molded article itself a material with high weather resistance (Patent Document 4); and so on.

[0005] Furthermore, when bonding resin components to metals, other resins, or other substrates, sufficient adhesive strength is required. Additionally, when applying coatings to resin components, various resins are used as base polymers in the coating; therefore, strengthened adhesion between the resin component and the coating is required to prevent coating peeling.

[0006] However, depending on the type of resin component and the substrate, compatibility with the adhesive can sometimes be difficult, and even with existing adhesives, sufficient bond strength cannot be achieved. Furthermore, if coating is applied directly to the resin component, compatibility can be poor depending on the type of resin component and coating, resulting in insufficient bond strength between the resin component and the coating, leading to unevenness, coating peeling, and other problems.

[0007] As a resin component with sufficient adhesive strength, for example, Patent Document 5 describes a surface-modified thermoplastic resin component, which has an easy-to-adhere layer stacked on a resin component formed of thermoplastic resin, and a mixed layer formed by mixing the thermoplastic resin and the easy-to-adhere layer is provided between the thermoplastic resin and the easy-to-adhere layer.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2005-213337

[0011] Patent Document 2: Japanese Patent Application Publication No. 2020-7408

[0012] Patent Document 3: Japanese Patent Publication No. 2009-505871

[0013] Patent Document 4: Japanese Patent Application Publication No. 2008-250106

[0014] Patent Document 5: Japanese Patent Application Publication No. 2017-128722 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] However, in the prior art, the yellowing caused by outdoor use of coatings with resin components is not sufficiently suppressed, and the weather resistance and the adhesion between the resin components and the coating film are not taken into account.

[0017] The object of this invention is to provide surface-modified parts and coatings with excellent weather resistance and excellent adhesive strength. Furthermore, another object of this invention is to provide a method for manufacturing the aforementioned surface-modified parts and coatings.

[0018] Methods for solving problems

[0019] The inventors of this application conducted in-depth research to solve the aforementioned problems. As a result, they discovered that by fabricating a surface-modified part on which a surface-modified layer is laminated on at least a portion of a resin part containing a thermosetting resin, and by having a mixed layer of the resin part and the surface-modified layer of a specific thickness between the resin part and the surface-modified layer, both improved weather resistance and improved adhesive strength can be achieved, thus completing the present invention.

[0020] The methods used to solve the above problems are as follows.

[0021] [1]

[0022] A surface-modified component having a surface-modified layer laminated on at least a portion of a resin component comprising a thermosetting resin, wherein the surface-modified component has a mixed layer formed by mixing the resin component and the surface-modified layer between the resin component and the surface-modified layer, the thickness of the mixed layer being 250 nm to 10 μm.

[0023] [2]

[0024] The surface-modified component as described in [1], wherein the surface-modified layer comprises a thermoplastic resin.

[0025] [3]

[0026] The surface-modified component as described in [2], wherein the weight-average molecular weight of the thermoplastic resin is 10,000 to 100,000.

[0027] [4]

[0028] The surface-modified component as described in [2] or [3], wherein the HSP distance between the thermoplastic resin and the thermosetting resin is 8 or less.

[0029] [5]

[0030] The surface-modified component as described in any one of [2] to [4], wherein the thermoplastic resin is a polymer having polar and non-polar units.

[0031] [6]

[0032] The surface-modified component as described in any one of [1] to [5], wherein the thermosetting resin has aromatic groups.

[0033] [7]

[0034] The surface-modified component as described in any one of [1] to [6], wherein the thermosetting resin has a group comprising a benzene ring.

[0035] [8]

[0036] The surface-modified component as described in any one of [1] to [7], wherein the thermosetting resin is an epoxy resin.

[0037] [9]

[0038] The surface-modified component as described in [8], wherein the epoxy resin has a structure derived from bisphenol A type glycidyl ether.

[0039]

[10]

[0040] The surface-modified component as described in any one of [1] to [9], wherein the resin component comprises fiber-reinforced resin.

[0041]

[11]

[0042] The surface-modified component as described in any one of [1] to

[10] , wherein,

[0043] The Δb of the above-mentioned surface-modified component is defined by the following equation (1). * Values ​​below 5

[0044] Δb * Value = b * 1-b * 0···Equation (1)

[0045] In equation (1), b* 0 refers to an irradiation intensity of 0.35 W / m on the surface-modified component. 2 The surface b of the surface modified layer side of the surface modified component was measured using a spectrophotometer with a reflection angle of 45° and an incident angle of 45° in front of ultraviolet light / h. * Value, b * 1. The surface-modified component is irradiated with an intensity of 0.35 W / m. 2 The surface b of the surface modified layer side of the surface modified component was determined by measuring the light incident at an incident angle of 45° against a reflection angle of 45° after 250 hours of ultraviolet light exposure per hour using a spectrophotometer. * value

[0046]

[12]

[0047] A coated object, wherein at least a portion of the surface-modified component described in any one of [1] to

[11] has a coating film.

[0048]

[13]

[0049] The coating as described in

[12] , wherein the coating film is selected from at least one of the following: paint layer, printing layer, vapor deposition layer and plating layer.

[0050]

[14]

[0051] The coating as described in

[12] , wherein the coating film is a transparent resin layer.

[0052]

[15]

[0053] A method for manufacturing a surface-modified component, wherein at least a portion of a resin component comprising a thermosetting resin is laminated with a surface-modified layer comprising a thermoplastic resin, the method comprising a lamination step of laminating the surface-modified layer onto the resin component by means of heat pressing, wherein the degree of curing of the thermosetting resin at the start of the heat pressing is 0 to 93%.

[0054]

[16]

[0055] A method for manufacturing a coated object according to any one of

[12] to

[14] , the method comprising: a lamination step of laminating the surface modification layer onto the resin component by means of heat pressing to manufacture the surface modification component; and a step of forming the coating film on the surface modification layer side of the surface modification component, wherein the degree of curing of the thermosetting resin at the start of the heat pressing is 0 to 93%.

[0056] Invention Effects

[0057] According to the present invention, surface-modified parts and coatings with excellent weather resistance and excellent adhesive strength can be provided. Furthermore, methods for manufacturing the aforementioned surface-modified parts and coatings with excellent productivity can be provided. Attached Figure Description

[0058] [ Figure 1 [This is a schematic cross-sectional view showing an example of a surface-modified component.]

[0059] [ Figure 2 [Illustration] is a schematic cross-sectional view showing an example of a resin material with a surface-modified layer.

[0060] [ Figure 3 [ ] is a schematic cross-sectional view showing an example of a coated object. Detailed Implementation

[0061] The embodiments of the present invention will now be described in detail.

[0062] (Surface-modified components)

[0063] The surface-modified component of the present invention is a surface-modified component in which a surface-modified layer is laminated on at least a portion of a resin component comprising a thermosetting resin, and a mixed layer formed by mixing the resin component and the surface-modified layer is provided between the resin component and the surface-modified layer, wherein the thickness of the mixed layer is 250 nm to 10 μm.

[0064] The surface-modified component of the present invention requires a mixed layer formed by mixing the resin component and the surface-modified layer with a specific thickness or greater between the resin component and the surface-modified layer. In this mixed layer, the concentration of free radicals generated by irradiating the thermosetting resin with sunlight is reduced. Therefore, it is presumed that the reaction between free radicals is suppressed, and the yellowing of the thermosetting resin is suppressed.

[0065] In addition, it is speculated that the formation of the hybrid layer improves the adhesion strength between the resin component and the surface modification layer, which in turn can also impart good adhesion to the coating.

[0066] The surface modification component of the embodiments of the present invention is preferably defined by Δb as shown in the following formula (1). * The value is below 5.

[0067] Δb ＊ Value = b ＊ 1-b ＊ 0···Equation (1)

[0068] (In equation (1), b) * 0 refers to an irradiation intensity of 0.35 W / m on the surface-modified component. 2The surface b of the surface modified layer side of the surface modified component was measured using a spectrophotometer with a reflection angle of 45° and an incident angle of 45° in front of ultraviolet light / h. * Value, b * 1. The surface-modified component is irradiated with an intensity of 0.35 W / m. 2 The surface b of the surface modified layer side of the surface modified component was determined by measuring the light incident at an incident angle of 45° against a reflection angle of 45° after 250 hours of ultraviolet light exposure per hour using a spectrophotometer. * value.)

[0069] Δb * The value is preferably 5.15 or less, more preferably 5 or less, and even more preferably 4.5 or less.

[0070] For b * 0 and b * Specifically, the determination method for 1 can be performed using the method described in the examples.

[0071] <Surface Modification Layer>

[0072] The surface modification layer preferably comprises a thermoplastic resin.

[0073] From the viewpoint that thermosetting resins do not volatilize at molding temperatures, the weight-average molecular weight (Mw) of the thermoplastic resin is preferably 500 or more, more preferably 10,000 or more. Furthermore, from the viewpoint of enabling interlayering, it is preferably 1,000,000 or less, more preferably 100,000 or less.

[0074] From the viewpoint of improving compatibility with thermosetting resins, the weight-average molecular weight of the thermoplastic resin is preferably 10,000 to 100,000. By improving the compatibility between the thermosetting resin in the resin component and the thermoplastic resin in the surface modification layer, it becomes easier to form a mixed layer in the manufacturing process of the surface modified component, which will be described later, and it is easier to obtain a mixed layer of the desired thickness.

[0075] In this invention, the weight-average molecular weight (Mw) of the thermoplastic resin is a polymethyl methacrylate (PMMA) conversion value obtained using gel permeation chromatography (GPC) from a calibration curve prepared from standard polystyrene. Details of the determination are described later in the examples.

[0076] It should be noted that the surface-modified layer may contain only one type of thermoplastic resin or two or more types. When containing two or more types of thermoplastic resin, it is preferable that the weight-average molecular weight of the thermoplastic resin as the main component is within the above-mentioned range. The thermoplastic resin as the main component means that it contains 50% by mass or more of the total amount of thermoplastic resin contained in the surface-modified layer.

[0077] Furthermore, from the viewpoint of improving compatibility with thermosetting resins, the HSP distance between the thermoplastic resin and the thermosetting resin is preferably 8 or less. By making the HSP distance 8 or less, the compatibility between the thermosetting resin in the resin component and the thermoplastic resin in the surface modification layer is improved, thereby making it easier to form a mixed layer in the manufacturing process of the surface modification component described later, and making it easier to obtain a mixed layer of the desired thickness.

[0078] The HSP distance between the thermoplastic resin and the thermosetting resin is more preferably 8 or less, and even more preferably 5 or less.

[0079] The following explains the Hansen solubility parameter (hereinafter referred to as HSP value) and the HSP distance.

[0080] Hansen solubility parameters are decomposed into dispersive forces (δ) by Hildebrand solubility parameters. D ), permanent dipole intermolecular forces (δ P ), hydrogen bond force (δ H These three components are represented by vectors obtained by plotting them in 3D space. Substances with similar vectors can be judged to have high solubility. That is, the similarity of solubility can be judged based on the distance between their HSP values ​​(HSP distance). The definition and calculation of the Hansen solubility parameter are described in Charles M. Hansen's *Hansen Solubility Parameters: A Users Handbook* (CRC Publishing, 2007).

[0081] HSP values ​​are known values ​​for various resins and solvents and can be used directly, or calculated using HSPiP (Hansen Solubility Parameters in Practice), a computer software program. It should be noted that HSPiP also includes a database of resins and solvents.

[0082] In this specification, the HSP value of the resin is calculated using the Hansen sphere method and the following steps with HSPiP. A calculation method utilizing a neural network called Y-MB installed in HSPiP is employed. At this point, for the molecular structure, the linear representation of the molecule, the Smiles formula, is input, and δ is calculated. D δ P δ H A 3D drawing was performed, and the Hansen sphere was determined from these coordinates. The center coordinates of the Hansen sphere are the HSP value of the resin being evaluated.

[0083] Thermosetting resin (HSP value: δ) D1 δP1 δ H1 ) and thermoplastic resins (HSP value: δ D2 δ P2 δ H2 The HSP distance Ra of ) can be calculated using equation (3).

[0084] Ra={4×(δ D1 -δ D2 ) 2 + (δ P1 -δ P2 ) 2 + (δ H1 -δ H2 ) 2} 1 / 2 (3)

[0085] (In equation (3), δ D1 δ represents the dispersing force of thermosetting resins. P1 δ represents the permanent dipole intermolecular force of thermosetting resins. H1 δ represents the hydrogen bonding force of thermosetting resins. D2 δ represents the dispersing force of thermoplastic resins. P2 δ represents the permanent dipole intermolecular force of thermoplastic resins. H2 (This represents the hydrogen bonding force of thermoplastic resins)

[0086] It should be noted that when the surface modification layer contains two or more thermoplastic resins, the HSP distance between the thermoplastic resin and the thermosetting resin, which are the main components, is preferably within the range described above.

[0087] Thermoplastic resins are preferably polymers having polar and nonpolar units.

[0088] That is, the thermoplastic resin contained in the surface-modified layer (or the material of the surface-modified layer) more preferably has non-polar units and polar units with polar groups. The content of thermoplastic resin in the surface-modified layer is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, further preferably 90% to 100% by mass, particularly preferably 92% to 100% by mass, and most preferably 95% to 100% by mass.

[0089] As

[0090] Examples of non-polar units in thermoplastic resins include polyethylene units, polypropylene units, and polystyrene units. There can be only one type of non-polar unit, or there can be two or more types.

[0091] Examples of polar units possessing polar groups in thermoplastic resins include epoxy, carboxyl, nitrile, amide, ester, hydroxyl, acid anhydride, and silanol groups. Examples of polar units possessing such polar groups include glycidyl methacrylate, vinyl acetate, acrylonitrile, amide, (meth)acrylate, (meth)hydroxyethyl methacrylate, and maleic anhydride. There may be only one type of polar unit or two or more types.

[0092] The surface-modified layer (which may be the material of the surface-modified layer) may contain a thermoplastic resin that is selected from at least one of polymers containing methoxymethyl groups, polymers containing hydroxyl groups, polymers containing carboxyl groups, polymers containing amino groups, and polymers containing amide groups.

[0093] As a methoxymethyl-containing polymer, any suitable polymer can be used without impairing the effects of the present invention, as long as it contains methoxymethyl (-CH2-OCH3). Examples of such methoxymethyl-containing polymers include polyamide resins.

[0094] As a polymer containing methoxymethyl groups, commercially available products can be used. Examples of such commercially available products include the "Fine Resin" (registered trademark) series (manufactured by Lead Co., Ltd.).

[0095] The polymer containing methoxymethyl can be one type or two or more types.

[0096] As a hydroxyl-containing polymer, any polymer containing a hydroxyl group (-OH) is acceptable, and any suitable polymer can be used without impairing the effects of the present invention. Examples of such hydroxyl-containing polymers include, for instance, hydroxyl-containing acrylic polymers.

[0097] As a hydroxyl-containing polymer, commercially available products can also be used. Examples of such commercially available products include "ARUFON (registered trademark) UH-2000 series" (manufactured by Toa Synthetic Co., Ltd.).

[0098] The polymer containing hydroxyl groups can be one type or two or more types.

[0099] As a carboxyl-containing polymer, any suitable polymer can be used as long as it contains a carboxyl group (-COOH) without impairing the effects of the present invention. Examples of such carboxyl-containing polymers include acrylic polymers.

[0100] As a carboxyl-containing polymer, commercially available products can be used. Examples of such commercially available products include "ARUFON (registered trademark) UC-3000 series" and "ARUFON (registered trademark) UC-3510 series" (manufactured by Toa Synthetic Co., Ltd.).

[0101] The polymer containing carboxyl groups can be one type or two or more types.

[0102] As an amino-containing polymer, any suitable polymer can be used as long as it contains an amino group (-NH2) without impairing the effects of the present invention.

[0103] As an amino-containing polymer, commercially available products can be used.

[0104] The amino-containing polymer can be one type or two or more types.

[0105] The surface-modified layer (or the material of the surface-modified layer) may contain at least one of the following: a compound containing a tertiary amine or a strong acid.

[0106] As the tertiary amine-containing compound, any suitable compound can be used without impairing the effects of the present invention. Examples of such tertiary amine-containing compounds include imidazole derivatives and polyethyleneimine.

[0107] As compounds containing tertiary amines, commercially available products can be used. Examples of such commercially available products include, for instance, imidazole derivatives such as the "Curezol" series (imidazole-based epoxy resin curing agents, manufactured by Shikoku Chemical Industry Co., Ltd.), and polyethyleneimine such as the "Epomin" (registered trademark) series (manufactured by Nippon Shokubai Co., Ltd.).

[0108] The compound containing tertiary amines can be one type or two or more types.

[0109] As a strong acid, any suitable strong acid may be used without impairing the effects of the present invention. Examples of such strong acids include trifluoroborane, ionic liquids, and Nafion.

[0110] Examples of ionic liquids include BF3-C2H5NH2 and HMI-PF6.

[0111] Commercially available products can also be used as strong acids.

[0112] There can be one strong acid or two or more strong acids.

[0113] As the amide-containing polymer, any polymer containing an amide group (-CO-NH2) is acceptable, and any suitable polymer can be used without impairing the effects of the present invention. Examples of such amide-containing polymers include polyamide copolymer resins.

[0114] Commercially available products can also be used as polymers containing amide groups. Examples of such commercially available products include "Amilan CM8000" (manufactured by Toray Industries, Inc.).

[0115] The polymer containing amide groups can be one type or two or more types.

[0116] The surface modification layer (or the material of the surface modification layer) may contain other polymer components to the extent that it does not impair the effect of the invention.

[0117] The surface-modified layer (or the material of the surface-modified layer) may further contain crosslinking agents, microparticles, organic components, etc. as additives.

[0118] The thickness of the surface modification layer is not particularly limited, but is 0.01 μm to 2000 μm, more preferably 0.1 to 1000 μm, even more preferably 0.5 to 500 μm, and particularly preferably 1 μm to 200 μm.

[0119] <Resin Components>

[0120] The surface-modified component in this embodiment has a resin component comprising a thermosetting resin.

[0121] Resin components are obtained by molding a resin material containing a thermosetting resin.

[0122] Examples of thermosetting resins contained in resin components (or resin materials) include unsaturated polyester resins, vinyl ester resins, epoxy resins, melamine resins, phenolic resins, polyurethane resins, polyisocyanate resins, polyisocyanurate resins, and polyimide resins.

[0123] Thermosetting resins are preferred because they readily exhibit the yellowing-inhibiting effect of the present invention, and more preferably contain aromatic groups, and even more preferably contain groups containing benzene rings.

[0124] Furthermore, from the same point of view, epoxy resins are preferred, and epoxy resins having a structure derived from bisphenol A type glycidyl ether are even more preferred.

[0125] The resin component may also contain fiber-reinforced resin, and the thermosetting resin may also be a fiber-reinforced thermosetting resin.

[0126] Examples of fiber-reinforced thermosetting resins include carbon fiber-reinforced curing resins and glass fiber-reinforced thermosetting resins.

[0127] Alternatively, the resin material can also be a prepreg blank. That is, the resin part can also be a part formed by curing a prepreg blank.

[0128] Here, prepreg refers to a material in a semi-cured state, in which resin mixed with additives such as curing agents is impregnated with reinforcing materials such as carbon fibers and glass fibers, and then heated or dried.

[0129] Examples of shapes for resin materials and resin components include planar plates, curved plates, sheets, and films.

[0130] From the viewpoint of rigidity of the molded article, the thickness of the resin material and resin parts is preferably 0.001 mm or more, more preferably 0.1 mm or more, and even more preferably 1 mm or more. Furthermore, from the viewpoint of lightweighting and material cost, it is preferably 50 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less.

[0131] The surface-modified component of the present invention has the aforementioned surface-modified layer laminated on at least a portion of a resin component comprising a thermosetting resin. Here, "at least a portion of the resin component" refers to at least a portion of all surfaces of the resin component. For example, when the resin component is in the form of a plate, sheet, or film, it refers to a portion of at least one of its surfaces, or all of at least one of its surfaces, etc.

[0132] <Hybrid Layer>

[0133] A hybrid layer is a layer formed by mixing a resin component with a surface-modified layer. For example, it is formed by applying a surface-modified layer to at least a portion of the surface of a resin material and then heating and molding it, thereby causing the surface-modified layer and the resin material to melt and fuse at their interface, resulting in a hybrid layer. By forming a hybrid layer of a specified thickness or greater, yellowing inhibition of the thermosetting resin can be achieved, and the adhesive strength between the resin component and the surface-modified layer can be improved. By mixing at the interface, the interface between the resin component and the surface-modified layer disappears, and the resin component and the surface-modified layer become integrated, resulting in excellent adhesive strength.

[0134] The thickness of the hybrid layer is 250 nm to 10 μm. By setting the thickness of the hybrid layer to 250 nm or more, the concentration of free radicals generated by the thermosetting resin under sunlight is reduced in the hybrid layer, and the reaction between free radicals is suppressed, thus inhibiting the yellowing of the thermosetting resin. Furthermore, by improving the adhesion strength between the resin component and the surface-modified layer, coating adhesion is improved. Additionally, by making the thickness of the hybrid layer 10 μm or less, the reduction in coating adhesion caused by cohesive failure of the surface-modified layer can be suppressed.

[0135] From the viewpoint of suppressing yellowing, the thickness of the mixed layer is preferably 250 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more. Furthermore, from the viewpoint of preventing a decrease in coating adhesion, it is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less.

[0136] In this invention, the thickness of the hybrid layer is determined by imaging a cross-section of the surface-modified component using micro-Raman spectrophotometry. The layer in which peaks from both the thermosetting resin in the resin component and the thermoplastic resin in the surface-modified layer are detected is taken as the hybrid layer and measured. Details of the measurement will be described later in the embodiments.

[0137] The thickness of the mixed layer can be appropriately determined based on the heat forming conditions, the resin component, and the type of surface modification layer. In particular, it can be adjusted by changing the degree of curing of the thermosetting resin in the resin material before the start of the heat pressing step in the manufacturing method of the surface modified component described later.

[0138] [Manufacturing method of surface-modified parts]

[0139] The surface-modified component of the present invention is obtained by heat molding a laminate (hereinafter referred to as a resin material with a surface-modified layer) having a surface-modified layer laminated on at least a portion of the surface of a resin material.

[0140] By heating and molding a resin material with a surface-modified layer, the thermoplastic resin contained in the surface-modified layer and the thermosetting resin contained in the resin material are melted and mixed, so that the interface between the surface-modified layer and the resin material is melted and fused together to form a mixed layer, which can form a surface-modified part.

[0141] Thermoforming can be performed simultaneously with the placement of the surface-modified sheet, or it can be performed after the placement of the surface-modified sheet.

[0142] <Method for manufacturing resin materials with surface modification layers>

[0143] Methods for producing resin materials with surface-modified layers include, for example, coating at least a portion of the surface of a resin material with a solution containing a surface-modified layer and a solvent; melt-extruding a surface-modified layer onto at least a portion of the surface of a resin material; and forming a laminated surface-modified layer onto at least a portion of the surface of a resin material, etc.

[0144] "At least a portion of the surface of the resin material" means at least a portion of all the surfaces of the resin material. For example, in the case of a resin material in the form of a plate, sheet, or film, it means a portion of at least one of its surfaces, or all of at least one of its surfaces, etc.

[0145] The above description can be directly applied as a resin material and surface modification layer.

[0146] As an embodiment of the present invention, a coating method for a solution containing a surface-modified layer and a solvent includes, for example, impregnating a resin material in a solution containing a surface-modified layer and a solvent; brush-coating at least a portion of the surface of the resin material with a solution containing a surface-modified layer and a solvent; coating at least a portion of the surface of the resin material with a solution containing a surface-modified layer and a solvent using various coating machines; spray-coating at least a portion of the surface of the resin material with a solution containing a surface-modified layer and a solvent, etc.

[0147] As a solution comprising the material of the surface-modified layer and the solvent, examples include surface-modified compositions obtained by dissolving the material of the surface-modified layer in any suitable solvent without impairing the effects of the present invention.

[0148] Examples of solvents 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; sulfoxides such as dimethyl sulfoxide; ethers such as dimethyl ether and tetrahydrofuran; etc. To suppress the formation of gels, ethanol or a mixture of ethanol, isopropanol, and water is preferred. There may be only one solvent or two or more solvents.

[0149] The concentration of solid components in the surface-modified composition can be appropriately set according to the purpose. From the viewpoint of the thickness accuracy of the surface-modified layer, the preferred mass ratio is 1% to 40% by mass, more preferably 10% to 35% by mass, and even more preferably 15% to 30% by mass.

[0150] The surface-modified composition may contain various additives as needed, such as pH adjusters, crosslinking agents, viscosity modifiers (thickeners, etc.), leveling agents, peeling modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), surfactants, antistatic agents, preservatives, anti-aging agents, ultraviolet absorbers, antioxidants, and light stabilizers.

[0151] For example, by adding colorants to make the surface modification layer visible, it is easy to identify whether the surface of the resin part has been modified, which has advantages in process management.

[0152] Examples of colorants include dyes or pigments. Additionally, fluorescent materials that are visually recognizable by black light can also be used as colorants.

[0153] When a solution comprising a surface-modified layer and a solvent is applied to at least a portion of the surface of a resin material, at least a portion of the solvent is subsequently removed by drying. In such drying, removing at least a portion of the solvent is sufficient; preferably, removing 50% by mass or more of the solvent, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably removing all of the solvent.

[0154] As for the drying method, any method capable of removing the solvent, such as oven heating, infrared heating, or high-frequency heating, can be used. Any suitable method can be employed without compromising the effectiveness of the present invention. Furthermore, as for the drying temperature, any appropriate temperature can be set according to the boiling point of the solvent used.

[0155] As a method for melt extrusion of surface-modified layers, examples include methods such as using a melt extruder to melt extrude the material of the surface-modified layer onto at least a portion of the surface of a resin material.

[0156] Methods for surface modification layers in the form of laminated sheets include, for example, placing a surface modification layer side of a laminate of a release sheet and a surface modification layer on at least a portion of the surface of a resin material, and so on.

[0157] The following describes the surface-modified sheet. The surface-modified sheet is a laminate of a release sheet and a surface-modified layer. There are no particular limitations on the release sheet, but a heat resistance of 100°C or higher is preferred. Furthermore, it can be a non-silicone resin sheet or a silicone resin sheet, but a non-silicone resin sheet is preferred. Examples include fluorine-based resin sheets (manufactured by Nitto Denko Corporation, NITOFLON), polyester-based resin sheets, polymethylpentene-based resin sheets (manufactured by Mitsui Chemicals East CELLO, Opulan (registered trademark)), polystyrene-based resin sheets (manufactured by KURABO Corporation, Oidys (registered trademark)), polyamide-based resin sheets, and polyolefin-based resin sheets.

[0158] As a release sheet material that can be used for surface modification sheets, more specifically, examples include unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide 66, biaxially stretched polypropylene, biaxially stretched polyethylene terephthalate, biaxially stretched polybutylene terephthalate, easily formed polyethylene terephthalate, cast polytetrafluoroethylene, unstretched extruded tetrafluoroethylene-ethylene copolymer (ETFE), unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), unstretched extruded tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and laminates in which these are used as the main layer.

[0159] From the viewpoint of shape following, the thickness of the release sheet is preferably 1μm to 1000μm, more preferably 10μm to 500μm, even more preferably 20μm to 300μm, and particularly preferably 30μm to 100μm.

[0160] In addition, as needed, the surface modification layer of the release sheet can be treated with a suitable release agent such as silicone on one or both sides.

[0161] Surface-modified sheets can be manufactured using any suitable method. For example, methods include impregnating the release sheet in a solution (surface-modified composition) containing a surface-modified layer material and a solvent, followed by drying as needed; brush-coating the surface of the release sheet with a solution containing a surface-modified layer material and a solvent, followed by drying as needed; coating the surface of the release sheet with a solution containing a surface-modified layer material and a solvent using various coating machines, followed by drying as needed; and spray-coating the surface of the release sheet with a solution containing a surface-modified layer material and a solvent, followed by drying as needed.

[0162] The above description can be directly applied as a surface modification layer and surface modification composition.

[0163] In the method for manufacturing a surface-modified component according to an embodiment of the present invention, it is preferable to use a surface-modified sheet to manufacture a resin material with a surface-modified layer.

[0164] Because the surface modification layer of the surface-modified sheet is sheet-like, it can be integrally formed by placing it on the resin material and heat treatment, without coating it on the surface of the resin part. Therefore, unevenness caused by repulsion can be prevented, and a surface modification layer of uniform thickness can be formed on the surface of the resin part. In addition, as a pretreatment, various surface treatments and drying processes such as sandblasting, corona treatment, and plasma treatment are not required.

[0165] By heating and molding the resin material with the surface-modified layer obtained by this method and then performing surface treatment on the resin part to form a hybrid layer, not only can the resin part be given yellowing inhibition and sufficient adhesive strength, but the surface-modified part can also be manufactured with high productivity and low cost. The method for manufacturing surface-modified parts can also be a method for treating the surface of the resin part (resin part surface treatment method).

[0166] <Heat forming of resin materials with surface modification layer>

[0167] The manufacturing method of the surface-modified component according to the embodiments of the present invention may include a step of heating and molding the resin material with the surface-modified layer described above.

[0168] In the manufacture of surface-modified parts, when the curing temperature of the thermosetting resin contained in the resin part is set to T2°C, it is preferable to provide a surface-modified layer on at least a portion of the surface of the resin material containing the thermosetting resin, and to heat-form it at a temperature of T1°C or higher. It should be noted that the curing temperature is the temperature within the heating temperature range of the heat flow curve obtained by measuring the uncured thermosetting resin using DSC.

[0169] The preferred heating and forming temperature is T1℃~T3℃, more preferably (T1+10)℃~(T3-10)℃, and even more preferably (T1+20)℃~(T3-20)℃.

[0170] Here, T1 is the temperature at which exothermic reaction begins (°C) when measured by DSC on uncured thermosetting resin, and T3 is the temperature at which exothermic reaction ends (°C).

[0171] By setting the heating molding temperature within the above range and performing surface treatment of the resin component using the method described above, the surface modification layer and the resin component melt into contact and fuse together to form a mixed layer, thereby imparting yellowing inhibition effect and sufficient adhesive strength to the resin component.

[0172] Alternatively, after at least a portion of the surface of the resin component is in a molten or softened state, a surface modification layer can be applied to the surface of the resin component in the molten or softened state. By applying a surface modification layer to the surface of the resin component in the molten or softened state, and by using the heat of the resin component surface to fuse and mix the surface modification layer, sufficient adhesive strength can be imparted to the resin component.

[0173] "Melted state" is a state in which at least a portion of the surface of the resin component is molten, preferably formed by heating the resin component to a temperature above its melting point.

[0174] "Softened state" refers to a state in which at least a portion of the surface of the resin component is softened, preferably formed by heating the resin component to a temperature above its softening temperature.

[0175] Methods of thermoforming include, for example, oven heating, infrared heating, high-frequency heating, and thermoforming pressing. Preferred methods include resin molding, and more preferably thermoforming pressing (press molding).

[0176] The heating and forming time is preferably 1 second or more, and may also be 1 minute or more. In addition, the heating and forming time is preferably 120 minutes or less, more preferably 60 minutes or less, further preferably 30 minutes or less, and even more preferably 15 minutes or less.

[0177] As a form of heated pressing, for example, a molding process in which a resin material with a surface-modified layer is placed in a molding machine (e.g., a press) and heated is performed (e.g., integral molding using heated pressing).

[0178] Preferably, the surface-modified layer of a surface-modified sheet is placed on at least a portion of the surface of the resin material within a molding machine, and integrally formed by heating and pressing. According to this method, the surface treatment and molding of the resin part can be performed simultaneously, thus providing high productivity and low cost.

[0179] From the viewpoint of deforming the molded article using a mold, the molding pressure during compression molding is preferably 1 MPa or more, more preferably 2 MPa or more, and even more preferably 3 MPa or more. Furthermore, from the viewpoint of maintaining the resin content of the molded article, it is preferably 30 MPa or less, more preferably 20 MPa or less, and even more preferably 10 MPa or less.

[0180] One embodiment of the present invention relates to a method for manufacturing a surface-modified component, which is a method for manufacturing a surface-modified component comprising a thermoplastic resin surface-modified layer laminated on at least a portion of a resin component comprising a thermosetting resin, comprising a lamination step of laminating the surface-modified layer onto the resin component by heating and pressing, wherein the degree of curing of the thermosetting resin in the resin material at the start of the heating and pressing is 0 to 93%.

[0181] By setting the degree of curing of the thermosetting resin to 0–93% at the start of heat pressing (or before pressurization based on heat pressing), the increase in the molecular weight of the thermosetting resin can be suppressed, thereby improving its compatibility with the thermoplastic resin in the surface-modified layer. With improved compatibility with the thermoplastic resin, a hybrid layer can be easily formed by heat pressing, making it easier to obtain a hybrid layer of the desired thickness.

[0182] It should be noted that, in this specification, the degree of curing of thermosetting resin is determined by differential scanning calorimetry (DSC) of uncured thermosetting resin and thermosetting resin at the beginning of heating and pressing. The heat generation (A) of uncured thermosetting resin and the heat generation (B) of thermosetting resin at the beginning of heating and pressing are obtained from the heat flow curves obtained during the heating process, and are calculated by the following formula (2).

[0183] Curing degree (%) = (1 - B / A) × 100 (2)

[0184] Details of the measurement are described later in the examples.

[0185] The degree of curing is preferably 0% or more. Furthermore, from the viewpoint of suppressing the increase in molecular weight of the thermosetting resin, it is preferably 93% or less, and more preferably 75% or less.

[0186] When using heat pressing to process resin, a preheating process is usually set up before heat pressing, and the resin material is fully heated before heat pressing.

[0187] However, in the manufacturing method of the surface-modified component according to the embodiments of the present invention, in order to make the degree of curing of the thermosetting resin at the start of heating and pressing 0 to 93%, it is preferable not to set a preheating step, shorten the preheating time in the preheating step, or reduce the preheating temperature.

[0188] In the manufacturing method of the surface-modified part according to the embodiments of the present invention, if a preheating process is provided before the pressing process using heat pressing, the preheating temperature can be set to the above-mentioned heating forming temperature, and the preferred temperature range is also the same.

[0189] The method for manufacturing a surface-modified component according to the embodiments of the present invention is a method for manufacturing a surface-modified component using a surface-modified sheet, which includes a lamination process of placing a surface-modified layer of the surface-modified sheet on at least a portion of the surface of a resin material, and laminating the surface-modified layer onto the resin component by heating and pressing. Preferably, the degree of curing of the thermosetting resin at the start of heating and pressing is 0 to 93%.

[0190] Heating and pressing can be performed simultaneously with the placement of the surface-modified sheet, or after the placement of the surface-modified sheet.

[0191] The surface-modified sheet, which serves as a release sheet and a surface-modified layer, is placed on at least a portion of the surface of the resin component. After heating and pressing, the release sheet is preferably removed. By removing the release sheet in this way, the surface-modified layer is transferred onto the surface of the resin component, resulting in a surface-modified component.

[0192] Furthermore, by peeling the release sheet from the surface-modified part, a surface-modified part with a surface-modified layer on its surface can be obtained. There are no particular limitations on whether the release sheet is peeled by hand or using a dedicated peeling device.

[0193] Through the above manufacturing method, such as Figure 1 As shown, a surface modification layer 10 is provided on the surface of the resin component 30, and a surface modification component 100 is provided between the resin component 30 and the surface modification layer 10, which is a mixture layer 20 formed by mixing the resin component and the surface modification layer.

[0194] As a preferred embodiment of the manufacturing method of the surface-modified component according to the present invention, a method using a surface-modified sheet can be cited. For the method of placing the surface-modified sheet 200, which is a laminate of a release sheet 40 and a surface-modified layer 10, on at least a portion of the surface of the resin material, such as... Figure 2 As shown, the surface-modified sheet 200 is placed on the surface of the resin material 50 in such a way that the surface-modified layer 10 side of the surface-modified sheet 200 becomes the surface side of the resin material 50.

[0195] [Coated objects and methods for manufacturing coated objects]

[0196] In embodiments of the present invention, the coated material has a coating film on at least a portion of the surface-modified component. The coating film is preferably disposed on at least a portion of the surface of the surface-modified component on the surface-modified layer side. The coating film can be at least one selected from paint layers, printed layers, vapor-deposited layers, and plating layers.

[0197] As an example of a coated object according to an embodiment of the present invention, Figure 3 The coating 400 is shown to have a surface modification layer 10 provided on the surface of the resin component 30, and a mixed layer 20 formed by mixing the resin component and the surface modification layer is provided between the resin component 30 and the surface modification layer 10. The coating 400 has a coating film 60 on the surface of the surface modification layer side.

[0198] When a surface-modified sheet is used instead of a surface-modified layer on the surface of the component, unevenness caused by repulsion can be prevented. Therefore, a surface-modified layer with a uniform thickness can be formed on the surface of the resin component, and a coating film with a uniform film thickness can be applied.

[0199] Furthermore, by applying a surface modification layer to the surface of a resin component in a molten or softened state, the surface modification layer is fused and mixed using the heat of the resin component surface. This forms a hybrid layer between the resin component and the surface modification layer, increasing the adhesive strength between the surface modification layer and the resin component, thus resulting in a coating film with excellent adhesion. Moreover, since the surface modification layer and the resin component can be integrally formed during coating formation, there is no need for cleaning or grinding processes using organic solvents to remove release agents before coating film formation, resulting in excellent safety and reduced environmental and operational burdens.

[0200] As a coating, there are no particular limitations; for example, various coatings such as epoxy, polyester-melamine, alkyd resin-melamine, acrylic-melamine, acrylic-polyurethane, and acrylic-polyacid curing agent coatings can be cited.

[0201] The coating can be a transparent resin layer, such as a resin layer formed by transparent coatings, hard coatings, or other transparent resins.

[0202] The thickness of the coating is not particularly limited, and is 0.01 to 2000 μm, more preferably 0.1 to 1000 μm, even more preferably 0.5 to 500 μm, and particularly preferably 1 to 200 μm.

[0203] The method for manufacturing a coated object according to the embodiments of the present invention includes: a lamination step of manufacturing a surface-modified component by laminating a surface-modified layer onto a resin component by heating and pressing; and a step of forming a coating film on the surface-modified layer side of the surface-modified component, wherein the degree of curing of the thermosetting resin at the start of the heating and pressing is 0 to 93%.

[0204] There are no particular restrictions on the coating method; common methods such as brush coating, roller coating, spray coating, and various coaters can be used, and there are no specific limitations on the coating amount. In addition, the heating time and temperature of the coating can be appropriately determined according to the paint used and the coating amount.

[0205] The above description can be directly applied as a surface modification layer, resin component, resin material, and surface modification component.

[0206] [Process Management Methods]

[0207] In the manufacture of surface-modified parts and coated products according to embodiments of the present invention, for example, by including additives such as dyes, pigments or crystalline substances in the surface-modified composition or surface-modified layer, the surface-modified layer is made visible, making it easier to manage the manufacturing process.

[0208] The above description can be directly applied as a surface-modifying composition, coating, and additive.

[0209] As a process management method, examples include visually confirming the colored parts after surface treatment, or identifying them by recognizing images taken with a camera.

[0210] Example

[0211] The present invention will be specifically described below through embodiments, but the present invention is not limited to these embodiments.

[0212] <Measurement of Mixed Layer Thickness>

[0213] The cross-sections of the surface-modified components obtained in each embodiment and comparative example were adjusted using the FIB microsampling method, and the images of these cross-sections were measured by micro Raman spectrophotometry under the following conditions. A peak (822 cm⁻¹) originating from the thermosetting resin, i.e., epoxy resin, in the resin component was observed. -1 3064cm -1The peak (1441 cm⁻¹) originates from the thermoplastic resin, i.e., polyamide resin, in the surface-modified layer. -1 2921cm -1 ) or the peak originating from acrylic resin (1730 cm⁻¹) -1 The two layers are used as a hybrid layer. The thickness of the hybrid layer is measured using the accompanying software (Project Five).

[0214] Device: WITec Alpha 300RSA

[0215] Excitation wavelength: 532nm

[0216] Wavenumber range for measurement: approximately 200–3600 cm⁻¹ -1

[0217] Grating: 600gr / mm

[0218] Objective lens: ×100

[0219] Detector: EMCCD

[0220] <Film thickness of surface modification layer>

[0221] The thickness of the surface-modified layer was measured using a dial gauge (PEACOCK GC-9). The thickness of the surface-modified sheet was measured, and the thickness (μm) of the release sheet after removing the surface-modified layer from that area was also measured. The difference between these measurements was taken as the thickness (μm) of the surface-modified layer. The average thickness (μm) was the average of 10 measurements taken.

[0222] <Weight-average molecular weight of thermoplastic resins>

[0223] The weight-average molecular weight (Mw) of thermoplastic resins is a polymethyl methacrylate (PMMA) conversion value obtained using gel permeation chromatography (GPC) from a calibration curve prepared using standard polystyrene.

[0224] (Determination conditions of weight-average molecular weight (Mw))

[0225] Device name: Made by Tosoh Co., Ltd., HLC-8420GPC

[0226] Test tablet concentration: 1 mg / mL

[0227] Test piece injection volume: 20 μl

[0228] Elution buffer: HFIP + 10mM-CF3COONa

[0229] Flow rate: 0.300 ml / min

[0230] Measurement (column) temperature: 40℃

[0231] Columns: Test column; TSKgel SuperAWM-H (2 columns), reference column; TSKgel SuperH-RC (1 column), manufactured by Tosoh Corporation.

[0232] Detector: Differential refractometer (RI)

[0233] <HSP distance between thermoplastic and thermosetting resins>

[0234] The calculation method, known as the Y-MB neural network method, was used in the HSP value calculation software (HSPiP Ver. 4.1.0.7 (Hansen SolubilityParameters in Practice)). Here, for the molecular structure, the linear Smiles expression of the molecule is input, and the HSP value (δ) of the thermosetting resin is calculated. D1 δ P1 δ H1 ) and the HSP value (δ) of thermoplastic resins D2 δ P2 δ H2 ).

[0235] The HSP distance Ra is calculated using equation (3).

[0236] Ra={4×(δ D1 -δ D2 ) 2 +(δ P1 -δ P2 ) 2 +(δ H1 -δ H2 ) 2} 1 / 2 (3)

[0237] (In equation (3), δ D1 For the dispersing force of thermosetting resins, δ P1 For permanent dipole intermolecular forces in thermosetting resins, δ H1 For the hydrogen bonding force of thermosetting resins, δ D2 For the dispersing force of thermoplastic resins, δ P2 For permanent dipole intermolecular forces in thermoplastic resins, δ H2 (This represents the hydrogen bonding force of thermoplastic resins)

[0238] <Degree of Curing of Thermosetting Resins>

[0239] For the degree of curing of thermosetting resin, DSC (differential scanning thermal analysis) of uncured thermosetting resin and thermosetting resin at the beginning of heating and pressing is performed under the following conditions. The heat release (A) of uncured thermosetting resin and the heat release (B) of thermosetting resin at the beginning of heating and pressing are obtained from the heat release peak area of ​​the heat flow curve obtained during the heating process, and are calculated by the following formula (2).

[0240] Curing degree (%) = (1 - B / A) × 100 (2)

[0241] As test samples, 5 mg of unheated material cut from the thermosetting resin used in the fabrication of the surface-modified parts was used, as well as heated material heated under preheating conditions (preheating temperature, preheating time) equivalent to the start of heating and pressing in each example and comparative example.

[0242] Device: TA Instruments High Sensitivity DSC Q2000

[0243] Atmospheric gas: N2 (50 ml / min)

[0244] Heating rate: 10℃ / min

[0245] Temperature conditions: -30℃→300℃

[0246] 〔evaluate〕

[0247] <Weathering Resistance Test>

[0248] The release sheet of the surface-modified component obtained in the examples and comparative examples was peeled off and irradiated with ultraviolet light under the following conditions.

[0249] It should be noted that in Comparative Examples 2 and 3, for the press-molded laminates, in Comparative Example 2, SANTOMO Ti used a primer as the primer, and in Comparative Example 3, CM8000 / UC3510 (100 / 2) was dissolved in a mixed solvent of ethanol (EtOH) / water / isopropanol (IPA) = 68% / 12% / 20% by mass, and a solution with 20% by mass of solids was applied, and the resulting surface-modified part was used.

[0250] (Ultraviolet radiation conditions)

[0251] Apparatus: DJK xenon lamp weathering tester ATLAS Ci4000

[0252] Panel temperature: 85℃

[0253] Irradiation intensity: 0.35W / m 2 / hr (340nm wavelength conversion)

[0254] Humidity: 5% RH

[0255] Evaluation time: 250 hours

[0256] For surface-modified parts before and after UV irradiation, b was measured using a multi-angle spectrophotometer (X-rite product name: Multi-angle Spectrophotometer MA98). * 1 and b * 0, calculate Δb using the following formula (1) * value.

[0257] Δb * Value = b * 1-b * 0···Equation (1)

[0258] (In formula (1),)

[0259] b * 0 refers to an irradiation intensity of 0.35 W / m on the surface-modified component. 2 The surface b of the surface modified layer side of the surface modified component was measured using a spectrophotometer with a reflection angle of 45° and an incident angle of 45° in front of ultraviolet light / h. * value,

[0260] b * 1. The surface-modified component is irradiated with an intensity of 0.35 W / m. 2 The surface b of the surface modified layer side of the surface modified component was determined by measuring the light incident at an incident angle of 45° against a reflection angle of 45° after 250 hours of ultraviolet light exposure per hour using a spectrophotometer. * value.)

[0261] will be b * The change in value Δb * Values ​​below 5 are considered to indicate a yellowing inhibition effect (○), and Δb is used to evaluate this. * Values ​​exceeding 5 indicate no yellowing inhibition effect (×).

[0262] <Evaluation of Coating Adhesion>

[0263] After coating the surface-modified parts prepared in the examples and comparative examples, the coatings were allowed to dry at room temperature for 24 hours. Then, each coated part was cut into strips approximately 40 mm wide and 50 mm long. Cross-cut evaluation was performed using the cross-cut method described in JIS K5600-5-6, and the number of peels was counted. If the number of peels was 0 out of 100, the adhesion was considered good (○); if it was 1 or more, the adhesion was considered poor (×).

[0264] • Coating: "V TOP H Topcoat" polyurethane coating manufactured by Dai Nippon Paint Co., Ltd.

[0265] • Cutting interval: 2mm

[0266] • Number of squares: 100

[0267] • Release tape: (Nichiban) Cellophane tape (registered trademark) 24mm wide

[0268] [Example 1]

[0269] (Surface-modified sheet (1))

[0270] 100 parts by weight of polyamide copolymer resin (Amilan CM8000 manufactured by Toray Industries, Inc.) were dissolved in a mixed solvent of ethanol (EtOH) / water / isopropanol (IPA) at 40°C, which was 68% by weight / 12% by weight / 20% by weight, to prepare a 20% by weight solution of solid components (surface modified composition).

[0271] The prepared surface-modified composition was filtered through a nylon mesh with an opening of 188 μm and then coated onto a release sheet (NITOFLON 900UL: fluoropolymer sheet film (polytetrafluoroethylene (PTFE) manufactured by Nitto Denko Corporation (thickness 0.05 mm, dimensions: width 250 mm × length 450 mm)) using a coater. The film was then dried at 100°C for 2 minutes using a constant temperature dryer to prepare a surface-modified sheet (1) as a release sheet with a surface-modified layer.

[0272] (Surface modified component (1))

[0273] The surface-modified sheet (1) prepared above is laminated on the surface-modified layer side onto a carbon fiber reinforced thermosetting epoxy resin prepreg blank (manufactured by Toray Industries, Inc., FK6244C-84K) (dimensions: 120mm wide × 150mm long × 1mm thick). The mold formed by the upper and lower parts of the pressing machine is heated to 150°C, and the laminate is placed on the lower part with the demolded sheet side facing up. The laminate is preheated at 150°C for 15 seconds. After preheating, the laminate is clamped by the upper and lower parts of the mold, and heated and fused by pressure forming (forming pressure 3MPa, 150°C, 5 minutes) to produce the surface-modified part (1).

[0274] (Painted material (1))

[0275] After peeling off the release sheet of the surface-modified part (1) prepared above, apply "V TOP H topcoat" polyurethane coating manufactured by Dai Nippon Paint Co., Ltd. to the surface-modified layer using a coater to produce a coated object (1) with a film thickness of 50 μm.

[0276] [Examples 2-14]

[0277] The materials and amounts used in the surface modification composition were changed as shown in Table 1 or Table 2. The preheating temperature, preheating time, molding temperature and molding time were changed as shown in Table 1 or Table 2. Otherwise, the same operation as in Example 1 was performed to produce surface modified parts (2) to (14) and coatings (2) to (14).

[0278] [Comparative Example 1]

[0279] Instead of applying the surface-modifying composition to the release sheet, the release sheet was overlapped on a carbon fiber reinforced thermosetting epoxy resin prepreg blank (manufactured by Toray Industries, Inc., FK6244C-84K). Otherwise, the same procedure as in Example 1 was followed to produce the surface-modified part (r1) and the coating (r1).

[0280] [Comparative Example 2]

[0281] (Surface modified component (r2))

[0282] A release sheet (NITOFLON 900UL: Nitto Denko Corporation fluoropolymer sheet film (PTFE) (thickness 0.05mm, dimensions: 250mm wide × 450mm long)) is overlapped onto a carbon fiber reinforced thermosetting epoxy resin prepreg blank (Toray Industries, Inc., FK6244C-84K) (dimensions: 120mm wide × 150mm long × 1mm thick). The mold formed by the upper and lower parts of a pressing machine is heated to 150°C. The laminate is placed on the lower part with the release sheet side facing up, and preheated at 150°C for 15 seconds. After preheating, the laminate is clamped by the upper and lower parts of the mold and pressed (forming pressure 3MPa, 150°C for 5 minutes). After forming, the release sheet is peeled off, and SANTOMO is applied to the peeled surface using a coater to achieve a dried film thickness of 20μm. Ti is coated with a primer (Dafeng Coatings, primer) and dried in a constant temperature dryer at 150°C for 30 minutes to obtain a surface-modified part (r2).

[0283] (Painting material (r2))

[0284] On the surface modification layer (primer layer) of the surface modified part (r2) prepared above, a polyurethane coating of "V TOP H topcoat" manufactured by Dai Nippon Paint Co., Ltd. is applied with a coater to create a coated object (r2) with a film thickness of 50 μm.

[0285] [Comparative Example 3]

[0286] (Layered body (r3))

[0287] A release sheet (NITOFLON 900UL: Nitto Denko Corporation fluoropolymer sheet film (polytetrafluoroethylene (PTFE) (thickness 0.05mm, dimensions: 250mm wide × 450mm long))) is overlapped onto a carbon fiber reinforced thermosetting epoxy resin prepreg blank (Toray Industries, Inc., FK6244C-84K) (dimensions: 120mm wide × 150mm long × 1mm thick). The mold formed by the upper and lower parts of the pressing machine is heated to 150°C, and the release sheet side is placed on the lower part. The laminate was prepared by preheating it at 150°C for 15 seconds. After preheating, the laminate was clamped by the upper and lower parts of a mold and pressed into shape (forming pressure 3 MPa, 150°C for 5 minutes). After forming, the release sheet was peeled off, and the surface-modified composition filtered through a nylon mesh with an opening of 188 μm was applied to the peeled surface using a coater to achieve a dried film thickness of 40 μm. The surface was then dried in a constant temperature dryer at 100°C for 2 minutes to produce the surface-modified part (r3).

[0288] (Surface-modified composition)

[0289] 100 parts by weight of polyamide copolymer resin (Amilan CM8000 manufactured by Toray Industries, Inc.) and 2 parts by weight of carboxyl-containing acrylic oligomer (ARUFON UC3510 manufactured by Toa Synthetic) were dissolved in a mixed solvent at 40°C with ethanol (EtOH) / water / isopropanol (IPA) = 68% by weight / 12% by weight / 20% by weight to prepare a 20% by weight solution of solid components (surface modified composition).

[0290] (Paintwork (r3))

[0291] On the surface-modified layer of the surface-modified component (r3) prepared above, a polyurethane coating of "V TOP H Topcoat" manufactured by Dai Nippon Paint Co., Ltd. is applied using a coater to produce a coated object (r3) with a film thickness of 50 μm.

[0292] [Comparative Examples 4-6]

[0293] Except for changing the materials and amounts used in the surface modification composition as shown in Table 2, and changing the preheating conditions (preheating temperature, preheating time) and molding conditions (molding pressure, molding temperature, molding time) as shown in Table 2, the surface modified parts (r4) to (r6) and the coatings (r4) to (r6) were made in the same manner as in Example 1.

[0294] Examples and comparative examples are shown in Tables 1 and 2 below. It should be noted that the temperatures listed in Tables 1 and 2 regarding molding conditions are both preheating and molding temperatures. Furthermore, the values ​​listed in the thermoplastic resin composition indicate the proportions (parts by mass) of each component.

[0295] [Table 1]

[0296]

[0297] [Table 2]

[0298]

[0299] The materials recorded in Tables 1 and 2 are as follows.

[0300] Polyamide resin

[0301] CM8000: Polyamide copolymer resin (Amilan manufactured by Toray Industries, Inc.)

[0302] FR-105: Methoxymethylated polyamide (Fine Resin Co., Ltd., Lead Industry Co., Ltd.)

[0303] PA-100: Polyamide copolymer resin (solvent-soluble grade PA-100 manufactured by T&K TOKA Co., Ltd.)

[0304] Oligomers

[0305] UC3510: A carboxyl-containing acrylic oligomer (manufactured by Toa Synthetic Co., Ltd., ARUFON)

[0306] UC3000: A carboxyl-containing acrylic oligomer (manufactured by Toa Synthetic Co., Ltd., ARUFON)

[0307] UP1000: Non-functional acrylic oligomer (manufactured by Toa Synthetic Co., Ltd., ARUFON)

[0308] Hardener

[0309] C11Z-CN: Imidazole-based curing agent (Curezol manufactured by Shikoku Chemical Industry Co., Ltd.)

[0310] Commercially available primer

[0311] SANTOMO Ti primer: (SANTOMO manufactured by Daifeng Coatings Co., Ltd.)

[0312] • Demolding sheet

[0313] NITOFLON No. 900UL: Fluoropolymer sheet film (polytetrafluoroethylene (PTFE), manufactured by Nitto Denko Corporation, NITOFLON 900UL)

[0314] Thermosetting resins

[0315] FK6244C-84K: Carbon fiber reinforced thermosetting epoxy resin prepreg blank (Toray Industries, Inc. FK6244C-84K)

[0316] Industrial availability

[0317] According to the present invention, surface-modified parts and coatings with excellent weather resistance and excellent adhesive strength can be provided. Furthermore, methods for manufacturing the aforementioned surface-modified parts and coatings with excellent productivity can be provided.

[0318] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0319] This application is based on Japanese patent application filed on February 26, 2021 (Japanese Patent Application No. 2021-30600), the contents of which are incorporated herein by reference.

[0320] Explanation of reference numerals in the attached figures

[0321] 10 Surface Modification Layer

[0322] 20 hybrid layers

[0323] 30 Resin Parts

[0324] 40 release sheet

[0325] 50 resin material

[0326] 60 coating

[0327] 100 Surface Modified Components

[0328] 200 Surface Modified Sheets

[0329] 300 resin parts with surface-modified layers

[0330] 400 paint

Claims

1. A surface-modified member in which a surface-modified layer is laminated to at least a part of a resin member comprising a thermosetting resin, wherein, The surface-modified member has a mixed layer of the resin member and the surface-modifying layer mixed together between the resin member and the surface-modifying layer, and the thickness of the mixed layer is 250 nm to 10 μm.

2. The surface-modified component of claim 1, wherein, The surface-modifying layer contains a thermoplastic resin.

3. The surface-modified component of claim 2, wherein, The thermoplastic resin has a weight average molecular weight of 10,000 to 100,000.

4. The surface-modified component of claim 2 or 3, wherein, The thermoplastic resin and the thermosetting resin have a Hansen solubility parameter HSP distance of 8 or less.

5. The surface-modified member according to claim 2 or 3, wherein, The thermoplastic resin is a polymer having a polar unit and a nonpolar unit.

6. The surface-modified component of claim 1 or 2, wherein, The thermosetting resin has an aromatic group.

7. The surface-modified component of claim 1 or 2, wherein, The thermosetting resin has a group containing a benzene ring.

8. The surface-modified component of claim 1 or 2, wherein, The thermosetting resin is an epoxy resin.

9. The surface-modified component of claim 8, wherein, The epoxy resin has a structure from a bisphenol A type glycidyl ether.

10. The surface-modified component of claim 1 or 2, wherein, The resin member contains a fiber-reinforced resin.

11. The surface-modified component of claim 1 or 2, wherein, The surface-modified member has a value of 5 or less values of 5 or less, values formula (1) In equation (1), The surface-modified component was irradiated with an intensity of 0.35 W / m. 2 The surface modification layer of the surface-modified component was measured using a spectrophotometer with a reflection angle of 45° and an incident angle of 45° in front of ultraviolet light at a time of / h. value The surface-modified component was irradiated with an intensity of 0.35 W / m. 2 The surface of the surface-modified component was determined by measuring the surface of the surface-modified layer after 250 hours of exposure to ultraviolet light at a reflection angle of 45° and an incident angle of 45° using a spectrophotometer. value.

12. A coated article having a coating film on at least a portion of the surface-modified member according to any one of claims 1 to 11.

13. The coated article of claim 12, wherein, The coating film is at least one selected from a paint layer, a printed layer, an evaporation-deposited layer, and a plated layer.

14. The coated article of claim 12, wherein, The coating film is a transparent resin layer.

15. A method for producing the surface-modified member according to any one of claims 1 to 11, the surface-modified member having a surface-modifying layer containing a thermoplastic resin laminated on at least a portion of a resin member containing a thermosetting resin, the method comprising a lamination step of laminating the surface-modifying layer to the resin member using heat press, the thermosetting resin having a degree of cure of 0 to 93% at the start of the heat press.

16. A method for producing the coated article according to any one of claims 12 to 14, the method comprising: a lamination step of laminating the surface-modifying layer to the resin member using heat press to produce the surface-modified member; and a step of forming the coating film on the surface-modifying layer side of the surface-modified member, wherein the thermosetting resin has a degree of cure of 0 to 93% at the start of the heat press. ​

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