WO2022202455A1 - 表面改質シート、積層体、表面改質部材、塗装物、表面改質部材の製造方法、及び塗装物の製造方法 - Google Patents

表面改質シート、積層体、表面改質部材、塗装物、表面改質部材の製造方法、及び塗装物の製造方法 Download PDF

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Publication number
WO2022202455A1
WO2022202455A1 PCT/JP2022/011435 JP2022011435W WO2022202455A1 WO 2022202455 A1 WO2022202455 A1 WO 2022202455A1 JP 2022011435 W JP2022011435 W JP 2022011435W WO 2022202455 A1 WO2022202455 A1 WO 2022202455A1
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Prior art keywords
modified
layer
resin
sheet
modified layer
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English (en)
French (fr)
Japanese (ja)
Inventor
涼平 大幡
佳世 下川
明日香 遠藤
繁樹 石黒
絵里子 中尾
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to CN202280024009.9A priority Critical patent/CN117042965A/zh
Priority to JP2023509034A priority patent/JPWO2022202455A1/ja
Priority to EP22775246.6A priority patent/EP4316809A4/en
Priority to KR1020237032370A priority patent/KR20230161446A/ko
Priority to US18/283,899 priority patent/US20240217219A1/en
Publication of WO2022202455A1 publication Critical patent/WO2022202455A1/ja
Anticipated expiration legal-status Critical
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
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    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to a surface-modified sheet, a laminate, a surface-modified member, a coated article, a method for producing the surface-modified member, and a method for producing a coated article.
  • resins which are lightweight and have excellent impact resistance, are used for parts such as transportation equipment such as railway vehicles, aircraft, ships, and automobiles, electronic equipment, and housing equipment. is joined. Coating films having various functions are formed on the resin member.
  • a suitable primer solution to modify the surface of a thermoplastic resin member, but resins with high solvent resistance (such as PPS, PA, PP, etc.), there is a problem that sufficient adhesive strength cannot be exhibited.
  • a surface treatment step and a drying step must be provided, which increases the number of steps and lowers productivity, which also poses a problem in terms of cost.
  • Patent Literature 1 describes a surface-modified sheet capable of imparting sufficient adhesive strength to a thermoplastic resin.
  • Patent Document 2 a technology for manufacturing a surface-modified member having a smooth surface using a surface-modified sheet
  • Patent Document 3 a technology for suppressing wrinkles in the surface-modified member using a low linear expansion release sheet.
  • the surface-modified sheet is used to improve the adhesion between the resin member and the coating film.
  • the adhesiveness is improved, a new problem was found that the appearance may change over time in a high-temperature and high-humidity environment.
  • the present invention has excellent adhesive strength, prevents the occurrence of unevenness, can form a smooth surface modified layer with a uniform thickness, and does not change the appearance even in a high-temperature and high-humidity environment. It is an object of the present invention to provide a surface-modified sheet capable of suppressing the surface-modified member and integrally molding the surface-modified layer and the resin member when forming the surface-modified member. Another object of the present invention is to provide a laminate, a surface-modified member, a coated article, a method for producing a surface-modified member, and a method for producing a coated article using this surface-modified sheet.
  • the inventor of the present invention has made intensive studies to solve the above problems.
  • the surface modified layer is made into a sheet, and by adding an oligomer component having low compatibility with the resin contained in the resin member and having a molecular weight within a specific range to the surface modified layer, the adhesive strength is excellent and the unevenness is reduced. It is possible to form a smooth surface modified layer with a uniform thickness, suppressing changes in appearance even in a high temperature and high humidity environment, and when forming a surface modified member, the surface modified layer and resin The inventors have found that integral molding with members is possible, and have completed the present invention.
  • the surface modification layer comprises a polymer component and an oligomer component;
  • the oligomer component has a weight average molecular weight (Mw) of 100 to 7000,
  • the HSP distance (Ra) between the oligomer component and bisphenol A type glycidyl ether is 7.5 or more, and the oligomer component is contained in 0.1 to 30 parts by mass based on 100 parts by mass of the polymer component. quality sheet.
  • Mw weight average molecular weight
  • Ra HSP distance between the oligomer component and bisphenol A type glycidyl ether
  • a coated article comprising a coating film on at least a part of the surface modifying member according to [6].
  • a method for producing a coated object comprising: laminating to produce a surface-modified member; and forming a coating film on the surface-modified layer side of the surface-modified member.
  • the surface-modified sheet according to the embodiment of the present invention has excellent adhesive strength, prevents the occurrence of unevenness, can form a smooth surface-modified layer with a uniform thickness, and does not change in appearance even in a high-temperature and high-humidity environment. This makes it possible to integrally mold the surface-modified layer and the resin member when forming the surface-modified member.
  • FIG. 1 is a schematic cross-sectional view showing an example of a surface-modified sheet according to an embodiment of the invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of the surface modifying member according to the embodiment of the invention.
  • FIG. 3 is a schematic cross-sectional view showing how the surface-modified sheet according to the embodiment of the present invention is placed on a resin material.
  • FIG. 4 is a schematic cross-sectional view showing an example of a coated object according to an embodiment of the invention.
  • a surface-modified sheet comprises a release sheet and a surface-modified layer, the surface modification layer comprises a polymer component and an oligomer component;
  • the oligomer component has a weight average molecular weight (Mw) of 100 to 7000,
  • the HSP distance (Ra) between the oligomer component and bisphenol A-type glycidyl ether is 7.5 or more,
  • the surface-modified sheet contains 0.1 to 30 parts by mass of the oligomer component with respect to 100 parts by mass of the polymer component.
  • the surface modified sheet 200 includes a release sheet 20 and a surface modified layer 10.
  • the surface-modified sheet according to the embodiment of the present invention has a sheet-like surface-modified layer, it is not coated on the surface of the resin member, but is placed on the resin material and heat-treated, so that integral molding can be performed. can. Therefore, it is possible to prevent unevenness due to repelling or the like, and to form a surface modified layer with a uniform thickness on the surface of the resin member.
  • the surface modification layer is provided on a part of the surface of the resin member, it is possible to suppress a decrease in yield due to protrusion or the like.
  • the appearance may change over time in a high-temperature, high-humidity environment.
  • the inventors presume the reason for this as follows.
  • the unreacted resin uncured resin in the thermosetting resin contained in the resin material Move to the surface modification layer.
  • the unreacted resin acts as a plasticizer in the surface-modified layer, and the elasticity of the surface-modified layer is reduced.
  • the reinforcing material migrates to the surface-modified layer, causing a change in appearance.
  • the surface-modified layer contains an oligomer component having a specific range of molecular weight. Since the oligomer component has a low molecular weight and high mobility, it is thought that at least a part of it segregates (bleeds out) on the surface of the surface-modified sheet on the surface-modified layer side during or after the formation of the surface-modified layer.
  • the oligomer component has low compatibility with the resin in the resin material. It can suppress the transition to the layer.
  • the surface modified layer is less likely to become low in elasticity even when exposed to a high temperature and high humidity environment, and the reinforcing material in the resin member is prevented from moving to the surface modified layer. It is possible to prevent deformation of the surface modified layer. As a result, it is presumed that the good appearance can be maintained and the coating film adhesion is improved.
  • the term "block layer" is used for convenience. At least a part of the surface of the surface-modified sheet on the surface-modified layer side may be segregated, and a layer may not necessarily be formed.
  • the weight-average molecular weight (Mw) of the oligomer component contained in the surface-modified sheet according to the embodiment of the invention is 100-7,000. If the weight-average molecular weight is less than 100, the mobility of the oligomer component becomes too high. suppression function) becomes insufficient, and changes in appearance tend to occur. On the other hand, when it exceeds 7000, the oligomer component is difficult to segregate on the surface of the surface-modified layer during or after the surface-modified layer is formed.
  • the weight-average molecular weight of the oligomer component is preferably 200 or more, more preferably 300 or more, even more preferably 500 or more, from the viewpoint of suppressing appearance change. In addition, from the viewpoint of facilitating segregation of the oligomer component on the surface of the surface-modified layer, it is preferably 6,500 or less, more preferably 6,000 or less, and even more preferably 5,500 or less.
  • the weight average molecular weight (Mw) of the oligomer component is a polymethyl methacrylate conversion value obtained from a calibration curve prepared with standard polystyrene using the gel permeation chromatography (GPC) method. Details of the measurement will be described later in Examples.
  • the HSP distance (Ra) between the oligomer component and bisphenol A-type glycidyl ether is 7.5 or more.
  • the surface-modified sheet according to the embodiment of the present invention can be suitably used for manufacturing a surface-modified member using a resin member containing a thermosetting epoxy resin.
  • the HSP distance (Ra) is an indicator of the compatibility between the oligomer component and the thermosetting epoxy resin contained in the resin member (which may be a resin material), and the larger the value, the lower the compatibility. show.
  • the oligomer component functions as a block layer and the surface modified member It is possible to suppress migration of unreacted epoxy resin in the resin material to the surface modified layer during production.
  • the HSP distance (Ra) is preferably 7.8 or more, more preferably 8.0 or more, and even more preferably 8.5 or more, from the viewpoint of suppressing appearance change. Further, the larger the HSP distance (Ra), the lower the compatibility between the oligomer component and the thermosetting epoxy resin contained in the resin member. is preferred.
  • the HSP distance (Ra) between the oligomer component and bisphenol A-type glycidyl ether is used as an index of compatibility between the oligomer component and the thermosetting epoxy resin contained in the resin member.
  • the A-type glycidyl ether is merely a compound used as an indicator, and the bisphenol A-type glycidyl ether may or may not be contained in the resin member. That is, the thermosetting epoxy resin contained in the resin member may be bisphenol A-type glycidyl ether, but may be other thermosetting epoxy resins.
  • the Hansen solubility parameter (hereinafter referred to as HSP value) and HSP distance are described below.
  • the Hansen solubility parameter divides the Hildebrand solubility parameter into three components: dispersion force ( ⁇ D ), permanent dipole intermolecular force ( ⁇ P ), and hydrogen bonding force ( ⁇ H ). represented by a vector plotted on Those with similar vectors can be judged to have high solubility. That is, the similarity of solubility can be determined from the distance between HSP values (HSP distance).
  • HSP distance The definition and calculation of the Hansen Solubility Parameter is provided by Charles M. et al. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007).
  • HSPiP Hanesen Solubility Parameters in Practice
  • This HSPiP also has a database of resins and solvents.
  • the HSP values of the oligomer component and bisphenol A type glycidyl ether are calculated using HSPiP according to the following procedure using the Hansen sphere method.
  • An estimation method using a neural network method called Y-MB implemented in HSPiP was used.
  • Smiles formula a molecular linear notation
  • ⁇ D , ⁇ P , and ⁇ H are calculated and three-dimensionally plotted
  • a Hansen sphere is obtained from these coordinates.
  • the center coordinates of this Hansen sphere are the HSP value of the resin to be evaluated.
  • the HSP distance (Ra) between the oligomer components (HSP values: ⁇ D1 , ⁇ P1 , ⁇ H1 ) and the bisphenol A-type glycidyl ethers (HSP values: ⁇ D2 , ⁇ P2 , ⁇ H2 ) is calculated by the formula (1). be able to.
  • Ra ⁇ 4 ⁇ ( ⁇ D1 ⁇ D2 ) 2 +( ⁇ P1 ⁇ P2 ) 2 +( ⁇ H1 ⁇ H2 ) 2 ⁇ 1/2 (1)
  • ⁇ D1 is the dispersion force of the oligomer component
  • ⁇ P1 is the permanent dipole intermolecular force of the oligomer component
  • ⁇ H1 is the hydrogen bonding force of the oligomer component
  • ⁇ D2 is the dispersion force of the bisphenol A-type glycidyl ether.
  • ⁇ P2 represents the permanent dipole intermolecular force of bisphenol A-type glycidyl ether
  • ⁇ H2 represents the hydrogen bonding force of bisphenol A-type glycidyl ether.
  • the oligomer component that can be used is not particularly limited as long as the weight average molecular weight and the HSP distance (Ra) to bisphenol A type glycidyl ether are within the above ranges.
  • examples include acrylic oligomers, styrene oligomers, xylene oligomers, and rosin esters. system oligomers, rosin-based oligomers, terpene-based oligomers, terpene-phenol-based oligomers, petroleum-based oligomers, amine-based oligomers, amide-based oligomers, epoxy-based oligomers, and the like.
  • the acrylic oligomer is preferably a non-functional type oligomer having no functional group.
  • a commercial product may be employed as the oligomer component.
  • acrylic oligomers include “UP-1000” and “UP-1080” (manufactured by Toagosei Co., Ltd., ARUFON (registered trademark)).
  • styrene oligomers include “UP-1150” (manufactured by Toagosei Co., Ltd., ARUFON (registered trademark)).
  • xylene-based oligomers include "Nikanol H-80” (Nikanol (registered trademark) manufactured by Fudo Co., Ltd.).
  • rosin ester-based oligomers include "Pencel D-125" (manufactured by Arakawa Chemical Industries, Ltd., (registered trademark)).
  • the surface modification layer contains 0.1 to 30 parts by weight of the oligomer component per 100 parts by weight of the polymer component described later. If the amount is less than 0.1 part by mass, it is difficult to obtain the effect of suppressing appearance change due to the addition of the oligomer component. On the other hand, when the amount exceeds 30 parts by mass, the fluidity of the surface-modified layer is increased and deformation is likely to occur, resulting in a change in appearance. From the viewpoint of suppressing appearance change, the oligomer component is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and 0.5 parts by mass or more with respect to 100 parts by mass of the polymer component. is more preferable.
  • the amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and 20 parts by mass. Part or less is more preferable.
  • the number of oligomer components contained in the surface-modified layer may be one, or two or more.
  • the weight average molecular weight of the main component oligomer, the HSP distance (Ra) to bisphenol A-type glycidyl ether, and the addition amount should be within the above ranges.
  • the oligomer, which is the main component represents a component that is contained in an amount of 50% by mass or more with respect to the total amount of the oligomer component contained in the surface modified layer.
  • the surface-modifying layer (which may be the material of the surface-modifying layer) preferably comprises a polymer component, the polymer component having non-polar units and polar units.
  • a polar unit comprises a polar group.
  • the content of the polymer component in the polar unit surface-modified layer is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 99.9% by mass, and still more preferably 90% by mass. % to 99.9% by mass, particularly preferably 92% to 99.9% by mass, most preferably 95% to 99.9% by mass.
  • the polymer component represents a component having a weight average molecular weight of more than 7000.
  • the weight average molecular weight (Mw) of the polymer can be measured using the GPC method in the same manner as the weight average molecular weight measurement of the oligomer.
  • non-polar units in polymer components include polyethylene units, polypropylene units, and polystyrene units. Only one type of non-polar unit may be used, or two or more types may be used.
  • the polar groups of the polar units in the polymer component include, for example, epoxy groups, carboxyl groups, nitrile groups, amide groups, ester groups, hydroxyl groups, acid anhydride groups, and silanol groups.
  • Examples of polar units having such polar groups include glycidyl methacrylate units, vinyl acetate units, acrylonitrile units, amide units, (meth)acrylic acid ester units, hydroxyethyl (meth)acrylate units, maleic anhydride units, and the like. mentioned. Only one type of polar unit may be used, or two or more types may be used.
  • the polymer component that may be included in the surface modified layer (which may be the material of the surface modified layer) is selected from methoxymethyl group-containing polymers, hydroxyl group-containing polymers, carboxyl group-containing polymers, amino group-containing polymers, and amide group-containing polymers. It may be at least one kind.
  • Such polymer components that the surface-modifying layer (which may be the material of the surface-modifying layer) may comprise are preferably addition-type curing agents, more preferably addition-type curing agents that react with epoxy groups. is.
  • any suitable polymer containing a methoxymethyl group ( --CH.sub.2-- OCH.sub.3 ) can be employed as long as it does not impair the effects of the present invention.
  • methoxymethyl group-containing polymers include methoxymethyl group-containing polyamide resins.
  • a commercial product may be adopted as the methoxymethyl group-containing polymer. Examples of such commercially available products include "Fine Resin” (registered trademark) series (manufactured by Narimichi Co., Ltd.).
  • the number of methoxymethyl group-containing polymers may be one, or two or more.
  • the methoxymethyl group-containing polymer preferably has a weight average molecular weight (Mw) of more than 7,000 and not more than 1,000,000, more preferably more than 7,000 and not more than 500,000, and still more preferably It is more than 7,000 and 100,000 or less, particularly preferably more than 7,000 to 70,000, and most preferably 10,000 to 50,000.
  • Mw weight average molecular weight
  • any appropriate polymer can be adopted as long as it is a polymer containing a hydroxyl group (--OH), as long as it does not impair the effects of the present invention.
  • hydroxyl group-containing polymers include hydroxyl group-containing acrylic polymers.
  • Commercially available products may be used as the hydroxyl group-containing polymer. Examples of such commercial products include "ARUFON (registered trademark) UH-2000 series” (manufactured by Toagosei Co., Ltd.).
  • the number of hydroxyl group-containing polymers may be one, or two or more.
  • the hydroxyl group-containing polymer preferably has a weight average molecular weight (Mw) of more than 7,000 and 1,000,000 or less, more preferably more than 7,000 and 500,000 or less, still more preferably more than 7,000, in that the effects of the present invention can be more expressed. It is 100,000 or less, particularly preferably more than 7,000 and 70,000 or less, and most preferably more than 7,000 and 50,000 or less.
  • Mw weight average molecular weight
  • any suitable polymer containing a carboxyl group (--COOH) can be employed as long as it does not impair the effects of the present invention.
  • carboxyl group-containing polymers include carboxyl group-containing acrylic polymers.
  • Commercially available products may be employed as the carboxyl group-containing polymer. Examples of such commercial products include "ARUFON (registered trademark) UC-3000 series” (manufactured by Toagosei Co., Ltd.).
  • the number of carboxyl group-containing polymers may be one, or two or more.
  • the carboxyl group-containing polymer preferably has a weight average molecular weight (Mw) of more than 7,000 and not more than 1,000,000, more preferably more than 7,000 and not more than 500,000, still more preferably 7,000, in that the effects of the present invention can be more expressed. It is more than 100,000 or less, particularly preferably more than 7,000 and 70,000 or less, most preferably more than 7,000 and 50,000 or less.
  • Mw weight average molecular weight
  • amino group-containing polymer any appropriate polymer containing an amino group (--NH 2 ) can be employed as long as it does not impair the effects of the present invention.
  • Commercially available products may be employed as the amino group-containing polymer.
  • One type of amino group-containing polymer may be used, or two or more types may be used.
  • the surface modification layer (which may be a material for the surface modification layer) may contain at least one selected from tertiary amine-containing compounds and strong acids.
  • Such tertiary amine-containing compounds and strong acids that may be included in the surface modification layer are preferably catalytic curing agents, and more preferably react with epoxy groups. It is a catalyst-type curing agent that
  • any suitable compound containing a tertiary amine can be employed as long as it does not impair the effects of the present invention.
  • tertiary amine-containing compounds include imidazole derivatives and polyethyleneimine.
  • a commercially available product may be employed as the tertiary amine-containing compound. Examples of such commercially available products include, for example, imidazole derivatives such as the "Curesol” series (imidazole-based epoxy resin curing agent, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and polyethyleneimine such as the "Epomin” (registered trademark) series. (manufactured by Nippon Shokubai Co., Ltd.).
  • the tertiary amine-containing compound may be one kind, or two or more kinds.
  • any appropriate strong acid can be adopted as long as the effects of the present invention are not impaired.
  • strong acids include trifluoroborane, ionic liquids, and Nafion.
  • ionic liquids include BF 3 —C 2 H 5 NH 2 and HMI-PF 6 .
  • a commercial product may be adopted as the strong acid.
  • One type of strong acid may be used, or two or more types may be used.
  • any suitable polymer containing an amide group (--CO--NH.sub.2) can be employed as long as it does not impair the effects of the present invention.
  • amide group-containing polymers include polyamide copolymer resins.
  • Commercially available products may be used as the amide group-containing polymer. Examples of such commercial products include "Amilan CM8000" (manufactured by Toray Industries, Inc.). One type of amide group-containing polymer may be used, or two or more types may be used.
  • the amide group-containing polymer preferably has a weight average molecular weight (Mw) of more than 7,000 and not more than 1,000,000, more preferably more than 7,000 and not more than 500,000, still more preferably 7,000, in that the effects of the present invention can be more expressed. It is more than 200,000 or less, particularly preferably 10,000 to 100,000, most preferably 20,000 to 70,000.
  • the surface modification layer (which may be the material of the surface modification layer) may further contain a cross-linking agent as an additive.
  • the cross-linking agent may be contained in the surface modification layer in the form after the cross-linking reaction, the form before the cross-linking reaction, the form in which the cross-linking reaction is partially performed, an intermediate form or a composite form thereof, and the like.
  • the surface-modified layer contains a cross-linking agent, the polymer has a three-dimensional network structure, so that the surface-modified layer has high elasticity, and it is easy to obtain the effect of suppressing changes in appearance even in a high-temperature, high-humidity environment.
  • cross-linking agents examples include isocyanate cross-linking agents, epoxy cross-linking agents, amine cross-linking agents, thiol cross-linking agents, unsaturated cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, carbodiimide cross-linking agents, and metal chelate cross-linking agents.
  • Cross-linking agents, peroxide-based cross-linking agents and the like can be mentioned, and epoxy-based cross-linking agents and peroxide-based cross-linking agents are preferred.
  • the number of cross-linking agents that can be contained in the surface modification layer may be one, or two or more.
  • the content of the cross-linking agent that can be contained in the surface modification layer is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the polymer, from the viewpoint of increasing elasticity. Preferably, it is more preferably 0.1 parts by mass or more. From the viewpoint of imparting high surface tension, the amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.
  • the type, combination, content, etc. of the cross-linking agent that can be contained in the surface-modified layer can be appropriately set according to the purpose and desired properties.
  • the cross-linking agent when it is a peroxide-based cross-linking agent, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.1 More preferably, it is at least 1 part by mass. From the viewpoint of imparting high surface tension, the amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.
  • the surface-modifying layer (which may be the material of the surface-modifying layer) may further contain fine particles as an additive.
  • fine particles By including fine particles in the surface-modified layer, a high elastic modulus can be imparted, so that the effect of suppressing appearance change can be easily obtained even in a high-temperature and high-humidity environment.
  • the fine particles may be inorganic fine particles or organic fine particles.
  • inorganic fine particles examples include silicon oxide fine particles (e.g., fumed silica, colloidal silica, precipitated silica, silica gel, silica airgel, quartz glass, glass fiber, etc.), titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, and tin oxide. fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles, and the like.
  • silicon oxide fine particles e.g., fumed silica, colloidal silica, precipitated silica, silica gel, silica airgel, quartz glass, glass fiber, etc.
  • titanium oxide fine particles aluminum oxide fine particles, zinc oxide fine particles, and tin oxide.
  • fine particles calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles, and the like.
  • organic fine particles examples include polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, and polyester resin powder. , polyamide resin powder, polyimide resin powder, polyethylene fluoride resin powder, carbon fiber, cellulose fiber, and the like.
  • the fine particles may be surface-treated as necessary.
  • the fine particles are preferably inorganic fine particles from the viewpoint of heat resistance, and more preferably silicon oxide fine particles from the viewpoint of the dispersion stability of the coating liquid.
  • the fine particles that can be contained in the surface-modified layer may be of only one type, or may be of two or more types.
  • the content of fine particles that can be contained in the surface-modified layer is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the polymer, from the viewpoint of increasing elasticity. More preferably, it is at least 1 part by mass. From the viewpoint of film-forming properties, the amount is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the type, combination, content, etc. of fine particles that can be contained in the surface-modified layer can be appropriately set according to the purpose and desired properties.
  • the average thickness of the surface modified layer is preferably 0.1 to 50 ⁇ m.
  • examples of the method for separating the polymer component and the oligomer component contained in a mixed state in the surface-modified layer and confirming the molecular weight of each component examples of the method for separating the polymer component and the oligomer component include solid-phase extraction and liquid chromatography. An extraction method, a solvent extraction method, and the like can be mentioned. By using the GPC method for each component separated by the above separation method, the molecular weight of each component can be confirmed.
  • composition information is required for identification of each component, nuclear magnetic resonance methods such as 1 H-NMR and 13 C-NMR, infrared spectroscopy (IR), gas chromatograph mass spectrometry (GC-MS), matrix It can be identified by a combination of analytical methods such as assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS).
  • nuclear magnetic resonance methods such as 1 H-NMR and 13 C-NMR, infrared spectroscopy (IR), gas chromatograph mass spectrometry (GC-MS), matrix It can be identified by a combination of analytical methods such as assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS).
  • IR infrared spectroscopy
  • GC-MS gas chromatograph mass spectrometry
  • MALDI-TOFMS assisted laser desorption ionization time-of-flight mass spectrometry
  • the thickness of the surface-modified layer is not particularly limited, and is preferably 0.01 ⁇ m to 2000 ⁇ m, more preferably 0.1 to 1000 ⁇ m, still more preferably 0.1 to 50 ⁇ m, particularly preferably 1 to 30 ⁇ m. be.
  • the thickness of the surface-modified layer is determined by measuring the thickness of the surface-modified sheet with a dial thickness gauge (eg, Peacock GC-9), measuring the thickness of the release sheet after removing the surface-modified layer at that point, and calculating the difference. can be measured as the thickness of the surface modification layer.
  • the average thickness of the surface modified layer is the average value obtained by measuring 10 points.
  • the release sheet is not particularly limited, but preferably has a heat resistance of 100° C. or higher and a tensile elastic modulus at 100° C. of 1 GPa or lower.
  • it may be a non-silicone resin sheet or a silicone resin sheet, but it is preferably a non-silicone resin sheet.
  • polyester-based resin sheet manufactured by Nitoflon
  • polymethylpentene-based resin sheet manufactured by Mitsui Chemicals Tohcello, Opulan (registered trademark)
  • polystyrene-based resin sheet manufactured by Kurabo Industries, Oidis (registered trademark)
  • polyamide-based A resin sheet a polyolefin-based resin sheet, and the like are included.
  • the release sheet that can be used for the surface-modified sheet includes, for example, unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide 66, biaxially stretched polypropylene, and biaxially stretched polyethylene.
  • EFE unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer
  • PFA polymer
  • FEP unstretched extruded tetrafluoroethylene-hexafluoropropylene joint
  • the thickness of the release sheet is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, still more preferably 10 ⁇ m to 300 ⁇ m, and particularly preferably 10 ⁇ m to 100 ⁇ m, from the viewpoint of conformability.
  • the surface of the release sheet on the surface modification layer side or both surfaces may be subjected to a release treatment with an appropriate release agent such as silicone.
  • a surface-modified sheet may be manufactured by any suitable method. For example, a method of dipping a release sheet in a solution (surface-modifying composition) containing a material for the surface-modifying layer and a solvent (surface-modifying composition) followed by drying as necessary, and a method of applying the material for the surface-modifying layer to the surface of the release sheet. A method of drying if necessary after applying a solution containing a solvent and a brush, and a method of drying if necessary after applying a solution containing the material of the surface modification layer and a solvent to the surface of the release sheet with various coaters. , a method of spray coating a solution containing the material for the surface-modifying layer and a solvent onto the surface of the release sheet, followed by drying as necessary.
  • Examples of the surface-modifying composition include a solution obtained by dissolving the material of the surface-modifying layer in a solvent.
  • solvents include water; alcohols such as methanol, ethanol, and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic, and aromatic hydrocarbons; halogenated hydrocarbons; sulfoxides such as dimethyl sulfoxide; ethers such as dimethyl ether and tetrahydrofuran; and the like.
  • Ethanol or a mixed solvent of ethanol, isopropyl alcohol and water is preferable in order to suppress the formation of gelled substances. Only one kind of solvent may be used, or two or more kinds thereof may be used.
  • the solid content concentration in the surface-modifying composition can be appropriately set according to the purpose.
  • the mass ratio is preferably 1% to 40% by mass, more preferably 10% to 35% by mass, and still more preferably 15% to 30% by mass. is.
  • the surface modification composition may contain a pH adjuster, a cross-linking agent, a viscosity adjuster (thickener, etc.), a leveling agent, a release adjuster, a plasticizer, a softening agent, a filler, a coloring agent (pigment , dyes, etc.), surfactants, antistatic agents, preservatives, anti-aging agents, UV absorbers, antioxidants, light stabilizers, and other additives.
  • a coloring agent pigment , dyes, etc.
  • surfactants include, for example, dyes and pigments. Further, the colorant may be a fluorescent material that can be visually recognized under black light.
  • a laminate according to an embodiment of the present invention is a laminate in which the surface-modified layer of the surface-modified sheet is laminated on at least part of the surface of a resin material containing a thermosetting epoxy resin.
  • the laminate which is the resin material with a surface modified layer according to the embodiment of the present invention, can be produced by laminating the surface modified layer side of the surface modified sheet on at least part of the surface of the resin material before molding. can.
  • thermosetting epoxy resin contained in the resin material is not particularly limited.
  • the HSP distance (Ra) between the oligomer component and bisphenol A-type glycidyl ether is used as an index of compatibility between the oligomer component in the surface-modified layer and the thermosetting epoxy resin contained in the resin member.
  • the bisphenol A-type glycidyl ether is merely a compound used as an indicator, and may or may not be contained in the resin material.
  • thermosetting epoxy resins include bisphenol A-type glycidyl ether, bisphenol F-type glycidyl ether, bisphenol AD-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, glycidylamine-type epoxy resin, alicyclic epoxy resin, Dicyclopentadiene type epoxy resins, polyether type epoxy resins, silicone modified epoxy resins and the like can be mentioned.
  • the resin material may be prepreg.
  • the prepreg is made by impregnating a reinforcing material such as carbon fiber or glass fiber with a resin mixed with an additive such as a curing agent and heating or drying it to a semi-cured state.
  • the resin material may contain a fiber-reinforced resin
  • the thermosetting epoxy resin may be a fiber-reinforced thermosetting epoxy resin.
  • Fiber-reinforced thermosetting epoxy resins include, for example, carbon fiber-reinforced thermosetting epoxy resins and glass fiber-reinforced thermosetting epoxy resins.
  • Examples of the shape of the resin material include a plate shape having a flat surface, a plate shape having a curved surface, a sheet shape, a film shape, and the like.
  • the thickness of the resin material is, for example, 0.001 mm to 10 mm.
  • At least part of the surface of the resin material means at least part of all the surfaces of the resin material.
  • the resin material is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.
  • the above description can be used as it is.
  • a surface-modified member according to an embodiment of the present invention is obtained by laminating a surface-modified layer of a surface-modified sheet on at least part of the surface of a resin member containing a thermosetting epoxy resin.
  • the surface-modified member according to the embodiment of the present invention is a surface-modified member in which a surface-modified layer 10 is provided on the surface of a resin member 100 as shown in FIG. 2 by molding a resin material with a surface-modified layer. A material is obtained.
  • a mixed layer in which the resin member and the surface modification layer are mixed is preferably provided between the resin member and the surface modification layer.
  • the resin member is obtained by molding a resin material, and the preferable shape and thickness of the resin member are the same as those of the resin material.
  • At least part of the surface of the resin member means at least part of all the surfaces of the resin member.
  • the resin member is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.
  • the mixed layer is a layer in which the resin member and the surface-modified layer are mixed. It is a layer of a mixed part obtained by fusion-bonding or chemical bonding of the interfaces of members.
  • the formation of the mixed layer improves the adhesive strength between the resin member and the surface modified layer.
  • the resin contained in the resin member and the polymer component constituting the surface modified layer are bonded by a chemical reaction such as a covalent bond.
  • the interface between the resin member and the surface modified layer disappears due to a chemical reaction such as covalent bonding, and the resin member and the surface modified layer are integrated with each other, resulting in higher adhesive strength.
  • the surface-modified member according to the embodiment of the present invention uses a surface-modified sheet containing an oligomer component having low compatibility with the thermosetting epoxy resin, excessive adhesion between the resin member and the surface-modified layer Mixing is suppressed.
  • the thickness of the mixed layer can be appropriately determined according to the conditions of thermoforming and the type of the resin member and surface modification layer.
  • the thickness of the mixed layer is preferably 1.5 nm or more, more preferably 2.0 nm or more, from the viewpoint of improving adhesive strength.
  • the upper limit is about 10 ⁇ m.
  • the thermoforming may be performed simultaneously with lamination of the resin material and the surface-modified sheet, or may be performed after lamination of the surface-modified sheet on the resin material.
  • surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member, and to manufacture the surface-modified member with high productivity and low cost.
  • the method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (resin surface treatment method).
  • a surface-modified member can be manufactured by placing the surface-modified layer side of the surface-modified sheet, which is the body, and performing heat molding.
  • the polymer component contained in the surface modified layer melts into contact with the thermosetting epoxy resin contained in the resin material, melts and mixes or reacts and chemically bonds, thereby forming a bond between the surface modified layer and the resin material.
  • the interfaces can be melt-contacted and fused-mixed or chemically bonded to form a surface-modified member.
  • Heat molding may be performed simultaneously with placing the surface-modified sheet, or may be performed after placing the surface-modified sheet.
  • the method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (method for surface treatment of a resin member).
  • the resin member As for the resin member, the resin material, the surface-modified sheet, the release sheet, and the surface-modified layer, the above descriptions can be used as they are.
  • the curing temperature of the thermosetting epoxy resin contained in the resin member is T 2 ° C.
  • at least a part of the surface of the resin material containing the thermosetting epoxy resin is surface-modified. It is preferable to provide a layer and perform thermoforming at a temperature of T 1 °C or higher.
  • the curing temperature is the temperature within the exothermic temperature range of the heat flow curve measured by DSC for the uncured thermosetting epoxy resin.
  • the thermoforming temperature is preferably T 1 ° C. to T 3 ° C., more preferably (T 1 +10) ° C. to (T 3 -10) ° C., still more preferably (T 1 +20) ° C. to (T 3 -20)°C.
  • T1 is the temperature (°C) at which heat generation begins when an uncured thermosetting epoxy resin is measured by DSC
  • T3 is the temperature ( °C) at which heat generation ends.
  • the interface between the surface modified layer and the resin member melts and contacts and is welded and mixed or chemically bonded to the resin member. Adhesive strength can be imparted. And such provision can be performed with high productivity and low cost.
  • a surface modification layer can be provided on the surface of the resin member in the melted or softened state.
  • the surface modification layer is welded and mixed or chemically bonded by the heat of the surface of the resin member, thereby imparting sufficient adhesive strength to the resin member. can be done.
  • the "melted state” is a state in which at least a portion of the surface of the resin member is melted, preferably by heating the resin member to a temperature equal to or higher than its melting point.
  • the "softened state” is a state in which at least a portion of the surface of the resin member is softened, preferably by heating the resin member to a temperature equal to or higher than its softening temperature.
  • a "chemical bond” can be formed by chemically forming a covalent bond between the resin member and the material of the surface modification layer.
  • heat molding methods include oven heating, infrared heating, high-frequency heating, and heat press. Resin molding is preferable, and heat press (press molding) is more preferable.
  • the heat molding time is preferably 1 second to 10 minutes.
  • a method for producing a surface-modified member according to an embodiment of the present invention is a method for producing a surface-modified member using a surface-modified sheet, wherein the surface-modified layer is heated and pressed to contain a thermosetting epoxy resin.
  • a lamination step of laminating on the resin member may be included.
  • the surface-modified layer side of the surface-modified sheet is placed on at least part of the surface of the resin member (which may be a resin material) in a molding machine (for example, a press machine). It is a mode in which a molding process accompanied by heating (for example, integral molding by a hot press) is performed. According to this aspect, since molding of the resin member can be performed simultaneously with the surface treatment of the resin member, high productivity and low cost can be provided.
  • the molding pressure during press molding is preferably 1 MPa or more, more preferably 2 MPa or more, and even more preferably 3 MPa or more, from the viewpoint of deforming the molded product by the mold.
  • it is preferably 30 MPa or less, more preferably 20 MPa or less, and even more preferably 10 MPa or less.
  • peeling off the release sheet from the surface-modified member a surface-modified member having a surface-modified surface provided with the surface-modified layer can be obtained. Peeling of the release sheet is not particularly limited, and may be performed manually, using a dedicated peeling equipment, or the like.
  • the release sheet is removed.
  • the surface-modified layer is transferred to the surface of the resin member, and a surface-modified member (sometimes referred to as a laminated member of the resin member and the surface-modified layer) is obtained.
  • 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.
  • the surface modified layer 10 is provided on the surface of the resin member 100 to obtain the surface modified member.
  • the surface modified layer 10 is laminated on the surface of the resin member 100.
  • the resin member and the surface modified layer 10 are laminated. It has a mixed layer (not shown) in which the layers are mixed.
  • a coated article according to an embodiment of the present invention includes a coating film on at least a portion of a surface modifying member, and includes a coating film on at least a portion of the surface of the surface modifying member on the surface modification layer side. It is preferable that the The coating film may be at least one selected from coating, printing layer, vapor deposition layer, and plating layer.
  • a coating film 30 is provided on the surface of the surface-modified member on the surface-modified layer side of the surface-modified member in which the surface-modified layer 10 is provided on the surface of the resin member 100 shown in FIG. 3 shows a painted object 300.
  • the surface-modifying layer is formed using a sheet-like surface-modifying sheet rather than coating the surface of the member, it is possible to prevent the occurrence of unevenness due to repelling or the like. Therefore, the surface modified layer can be formed with a uniform thickness on the surface of the resin member, and the coating film can be applied with a uniform thickness. Further, by providing the surface modified layer on the surface of the resin member in a molten or softened state, the surface modified layer is welded and mixed or chemically bonded by the heat of the surface of the resin member, and the surface modified layer and the resin member are bonded together. Since the adhesive strength increases, a coating film with excellent adhesion can be formed.
  • the surface modified layer and the resin member since it is possible to integrally mold the surface modified layer and the resin member when forming the coated object, a cleaning treatment process using an organic solvent to remove the mold release agent before forming the coating film and polishing are performed. It does not require a treatment process, is highly safe, and can reduce the environmental load and workload. Further, by using the surface-modified sheet according to the embodiment of the present invention, the appearance of the coated article obtained is less likely to change even when exposed to a high-temperature and high-humidity environment.
  • the coating film is not particularly limited, and examples thereof include various coating films such as epoxy-based, polyester-melamine-based, alkyd-melamine-based, acrylic-melamine-based, acrylic-urethane-based, and acrylic-polyacid curing agent-based coatings. .
  • the thickness of the coating film is not particularly limited, and is preferably 0.01 to 2000 ⁇ m, more preferably 0.1 to 1000 ⁇ m, even more preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 200 ⁇ m.
  • a method for producing a coated object according to an embodiment of the present invention is a method for producing a coated object using the surface-modified sheet according to the embodiment of the present invention, wherein the surface-modified layer is heated and pressed to form a thermosetting epoxy resin. and a step of forming a coating film on the surface modified layer side of the surface modified member.
  • the coating method of the coating film there are no particular restrictions on the coating method of the coating film, and general methods such as brush coating, roller coating, spray coating, and various coater coatings can be used, and the coating amount is not particularly limited.
  • the time and temperature for heating the coating film can be appropriately determined depending on the coating material to be used, the coating amount, and the like.
  • the resin member As for the resin member, the surface-modified sheet, the surface-modified layer, and the surface-modified member, the above descriptions can be used as they are.
  • the description in the above [Method for manufacturing surface-modified member] can be used as it is.
  • the surface-modifying composition or the surface-modifying layer may contain a dye, a pigment, or a crystalline substance. By containing such additives, the surface modified layer is visualized, making it easier to manage the manufacturing process.
  • the surface-modifying composition As for the surface-modifying composition, the surface-modifying sheet, the coated article, and the additive, the above descriptions can be used as they are.
  • a process control method for example, there is a method of visually confirming the surface-treated and colored part, or a method of recognizing and discriminating images taken with a camera.
  • the weight-average molecular weight (Mw) of the oligomer component was a polymethyl methacrylate conversion value obtained from a calibration curve prepared using standard polystyrene using a gel permeation chromatography (GPC) method.
  • Ra ⁇ 4 ⁇ ( ⁇ D1 ⁇ D2 ) 2 +( ⁇ P1 ⁇ P2 ) 2 +( ⁇ H1 ⁇ H2 ) 2 ⁇ 1/2 (1)
  • ⁇ D1 is the dispersion force of the oligomer component
  • ⁇ P1 is the permanent dipole intermolecular force of the oligomer component
  • ⁇ H1 is the hydrogen bonding force of the oligomer component
  • ⁇ D2 is the dispersion force of the bisphenol A-type glycidyl ether.
  • ⁇ P2 represents the permanent dipole intermolecular force of bisphenol A-type glycidyl ether
  • ⁇ H2 represents the hydrogen bonding force of bisphenol A-type glycidyl ether.
  • ⁇ Thickness of Surface Modified Layer The film thickness of the surface modified layer was measured with a dial gauge (GC-9 manufactured by Peacock). The thickness of the surface-modified sheet was measured, the thickness ( ⁇ m) of the release sheet from which the surface-modified layer was removed at that location was measured, and the difference was taken as the thickness ( ⁇ m) of the surface-modified layer.
  • the average thickness ( ⁇ m) is the average value obtained by measuring 10 points.
  • the average glossiness is the average value obtained by measuring 5 points.
  • the 60° glossiness was measured after holding for 24 hours in a constant temperature and humidity bath set under an environment of 85°C temperature and 85% RH. Using the 60° glossiness at room temperature (25°C) and the 60° glossiness after holding for 24 hours in an environment with a temperature of 85°C and a humidity of 85% RH, the 60° glossiness reduction rate is calculated by the following formula. did.
  • Glossiness decrease rate (%) [(glossiness (25°C) - glossiness (85°C / 85% RH)) / glossiness (25°C)] ⁇ 100
  • 60° glossiness decrease rate was 3% or less, it was judged that the change in appearance of the coating film could be suppressed.
  • fluororesin sheet film polytetrafluoroethylene (PTFE) (thickness 0.05 mm, dimensions : width 250 mm ⁇ length 450 mm))
  • PTFE polytetrafluoroethylene
  • Carbon fiber reinforced thermosetting epoxy resin prepreg bisphenol A type glycidyl ether system, manufactured by Toray Industries, Inc., Torayca, FK6244C-84K) (dimensions: width 150 mm ⁇ length 120 mm ⁇ 1 mm thick) and heat-welded by press working (forming pressure 3 MPa, 150° C., 5 minutes) to produce a surface-modified member (1).
  • Example 8 A surface-modified sheet (8), a surface-modified member (8), and a coated article (8) were produced in the same manner as in Example 2, except that the thickness of the surface-modified layer was changed to 30 ⁇ m.
  • Example 12 A coated article (r12) was produced in the same manner as in Example 1, except that a release sheet was used to produce a surface-modified member without providing a surface-modified layer.
  • the surface-modified sheet according to the embodiment of the present invention has excellent adhesive strength, prevents the occurrence of unevenness, can form a smooth surface-modified layer with a uniform thickness, and does not change in appearance even in a high-temperature and high-humidity environment. This makes it possible to integrally mold the surface-modified layer and the resin member when forming the surface-modified member.

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  • Laminated Bodies (AREA)
PCT/JP2022/011435 2021-03-25 2022-03-14 表面改質シート、積層体、表面改質部材、塗装物、表面改質部材の製造方法、及び塗装物の製造方法 Ceased WO2022202455A1 (ja)

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KR1020237032370A KR20230161446A (ko) 2021-03-25 2022-03-14 표면 개질 시트, 적층체, 표면 개질 부재, 도장물, 표면 개질 부재의 제조 방법, 및 도장물의 제조 방법
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