WO2023163076A1

WO2023163076A1 - Surface-modifying sheet, multilayer object, surface-modified member, coated object, bonded object, method for producing surface-modified member, method for producing coated object, and method for producing bonded object

Info

Publication number: WO2023163076A1
Application number: PCT/JP2023/006602
Authority: WO
Inventors: 絵里子中尾; 佳世下川; 明日香遠藤; 涼平大幡
Original assignee: 日東電工株式会社
Priority date: 2022-02-28
Filing date: 2023-02-22
Publication date: 2023-08-31
Also published as: TW202402508A

Abstract

The present invention provides a surface-modifying sheet excellent in terms of temporary fixation, a multilayer object obtained using said surface-modifying sheet, a surface-modified member, a coated object, a bonded object, a method for producing the surface-modified member, a method for producing the coated object, and a method for producing the bonded object. The present invention relates to: a surface-modifying sheet comprising a surface-modifying layer, a release sheet, and a pressure-sensitive adhesive layer in this order; a multilayer object, a surface-modified member, a coated object, and a bonded object which are each obtained using said surface-modifying sheet; a method for producing the surface-modified member; a method for producing the coated object; and a method for producing the bonded object.

Description

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

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

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

When joining a resin member to metal or other resin, it is necessary to sufficiently bond the member. However, the resin member is difficult to be compatible with the adhesive, and sufficient adhesive strength cannot be obtained even if the conventional adhesive or adhesive sheet is used. In addition, a high level of adhesive strength is required for a resin member having excellent strength such as a fiber composite material.
For this reason, adhesion of resin members requires application of a primer solution, and prior to application of the primer solution, various surface treatments such as sandblasting, corona treatment, and plasma treatment are required as pretreatments. In such a surface treatment method, the number of steps is increased and productivity is lowered, so there is a problem in terms of cost.

　There is a technology that uses a surface-modified sheet as one of the means for applying easy-adhesion treatment to resin members to give them sufficient adhesive strength. For example, Patent Literature 1 describes a surface-modified sheet capable of imparting sufficient adhesive strength to a thermoplastic resin.

On the other hand, Patent Document 2 describes an adhesive spray system containing an adhesive and a propellant.

Japanese Patent Application Laid-Open No. 2017-128722 Japanese Patent Application Laid-Open No. 2016-000396

However, in the conventional technology, when manufacturing a surface-modified member using a surface-modified sheet and a resin material, the method of installing the surface-modified sheet in the molding apparatus may be a problem. For example, in the case of molding using a mold with a lateral tightening mechanism, the surface modified sheet cannot be installed and may fall as it is. In addition, in the case of autoclave molding, when laminating the resin material on the surface-modified sheet, the surface-modified sheet previously placed in the mold is not fixed, so it shifts, resulting in poor workability and the desired laminate. may not be obtained.

Here, for example, it is possible to apply an adhesive to the mold using an adhesive spray system as described in Patent Document 2 and fix the surface modified sheet, but it is possible to prevent contamination outside the mold. Also, there is concern that unevenness may occur on the surface of the molded product due to the inability to obtain a uniform coating thickness. In addition, a method of fixing the surface-modified sheet placed on the mold using a vacuum system, installing rolls at both ends of the mold, and transferring the surface-modified sheet from one roll to the other A method of fixing the surface-modified sheet by means of feeding and rolls at both ends can also be used, but both of these methods require capital investment.

In view of the above problems, an object of the present invention is to provide a surface-modified sheet with excellent temporary fixability. It is also intended to provide a laminate, a surface-modified member, a coated article, a joined article, a method for producing a surface-modified member, a method for producing a painted article, and a method for producing a joined article using this surface-modified sheet. aim.

The inventor of the present invention has made intensive studies, found that the above problems can be solved by the following configuration, and completed the present invention.

Means for solving the above problems are as follows.
[1]
A surface-modified sheet comprising a surface-modified layer, a release sheet, and an adhesive layer in this order.
[2]
The surface-modified sheet according to [1], wherein a release liner is provided on the surface of the pressure-sensitive adhesive layer opposite to the release sheet.
[3]
The surface-modified sheet according to [1], wherein the pressure-sensitive adhesive layer is formed from a silicone-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, an olefin-based pressure-sensitive adhesive, or an acrylic pressure-sensitive adhesive.
[4]
The surface-modified sheet according to [1], wherein the surface-modified layer has an easy adhesion function.
[5]
A laminate in which the surface-modified sheet according to any one of [1] to [4] is laminated on at least part of the surface of a resin material.
[6]
The laminate according to [5], wherein the resin material contains a fiber-reinforced resin.
[7]
The surface-modified layer in the surface-modified sheet according to any one of [1] to [4] is laminated on at least part of the surface of a resin member, and the resin member and the surface-modified layer are laminated. Weld-blended or covalently bonded surface modification components.
[8]
A coated article comprising a coating film on at least a part of the surface-modified member according to [7].
[9]
A bonded body in which an adhesive layer is provided on at least a part of the surface modifying member according to [7], and the adherend and the surface modifying member are bonded via the adhesive layer.
[10]
A second resin member is laminated on at least a part of the surface of the surface-modified member on the surface-modified layer side of the surface-modified member according to [7], and the second resin member and the surface-modified layer are welded and mixed or covalently bonded conjugate.
[11]
[1] A method for producing a surface-modified member using the surface-modified sheet according to any one of [4].
[12]
The method for producing a surface-modified member according to [11], which includes a lamination step of laminating the surface-modified layer on the resin member by thermoforming.
[13]
[1] A method for producing a coated object using the surface-modified sheet according to any one of [4].
[14]
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
The method for producing a coated object according to [13], comprising the step of forming a coating film on the surface modification layer side of the surface modification member.
[15]
[1] A method for producing a joined body using the surface-modified sheet according to any one of [4].
[16]
The method for manufacturing a joined body according to [10], comprising the step of laminating the second resin member on at least a part of the surface of the surface-modified member on the surface-modified layer side by thermoforming,
A method for producing a conjugate.
[17]
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
forming an adhesive layer on the surface modification layer side of the surface modification member;
The method for producing a joined body according to [15], comprising the step of joining the adherend and the surface-modifying member via the adhesive layer.

According to the present invention, a surface modified sheet, a laminate, a surface modified member, a coated article, a bonded body, a method for manufacturing a surface modified member, a method for manufacturing a coated article, and a bonded body using the surface modified sheet can provide a manufacturing method of

FIG. 1 is a schematic cross-sectional view showing an example of a surface modifying member. FIG. 2 is a schematic cross-sectional view showing an example of the surface-modified member from which the pressure-sensitive adhesive layer and the release sheet are peeled off. FIG. 3 is a schematic cross-sectional view showing an example of a surface-modified sheet. FIG. 4 is a schematic cross-sectional view showing a mode in which a resin material is placed so that at least part of the surface of the resin material is in contact with the surface of the surface-modified sheet on the surface-modified layer side. FIG. 5 is a schematic cross-sectional view showing an example of a coated object. FIG. 6 is a schematic cross-sectional view showing an example of a joined body (first joined body). FIG. 7 is a schematic cross-sectional view showing an example of another joined body (second joined body).

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

[Surface modification sheet]
A surface-modified sheet according to an embodiment of the present invention includes a surface-modified layer, a release sheet, and an adhesive layer in this order.

Since the surface-modified sheet according to the embodiment of the present invention has an adhesive layer, it is excellent in temporary fixability to a molding die. Therefore, for example, when manufacturing a surface-modified member using a surface-modified sheet and a resin material, not only molding with a mold of a vertical tightening mechanism, but also molding with a mold of a horizontal tightening mechanism, autoclave molding, etc. Molding using a molding machine, which had a problem with the installation of the surface-modified sheet, has become possible. In addition, even when using a mold with a vertical tightening mechanism, the surface can be fixed by a method that has not been done in the past, such as temporarily fixing the surface modification sheet to the upper mold and placing the resin material in the lower mold for molding. It became possible to mold a modified member.
In this specification, "excellent temporary fixability to the mold" means that the surface-modified sheet can be fixed to the mold before the molding operation and can be easily peeled off from the mold after the molding operation. , or it means that it peels off naturally without performing a peeling operation.

In the surface-modified sheet according to the embodiment of the present invention, since the surface-modified layer is in the form of a sheet, the resin material and the surface-modified layer are laminated and heat-treated instead of being coated on the surface of the resin member. can be integrally molded. Therefore, it is possible to prevent unevenness caused by repelling or the like, and to form a surface modified layer with a uniform thickness on the surface of the resin member. In addition, when the surface modification layer is provided on a part of the surface of the resin member, it is possible to suppress a decrease in yield due to protrusion or the like.

<Surface modification layer>
In the embodiment of the present invention, the surface modification layer refers to a layer capable of modifying the surface of any member or material. For example, a layer that can impart functions such as easy adhesion, paintability, conductivity, colorability, decorativeness, adhesiveness, and solderability to the surface of the resin material, or a layer that can improve these functions. can.
The material used for the surface modification layer according to the embodiment of the present invention is not particularly limited, and various materials can be used depending on the function desired to be imparted or improved.

In order to impart or improve easy adhesion and paintability, it is preferable to include the polymer component described later in the surface modification layer.

For imparting or improving electrical conductivity, the surface modification layer preferably contains, for example, metal mesh, conductive fiber, metal powder, and the like.
Metal meshes include, for example, copper meshes, aluminum meshes, stainless steel meshes, and the like.
As the conductive fiber, for example, potassium titanate fiber, metal nanowire, carbon nanotube, carbon fiber, conductive carbon or white metal oxide is kneaded and composite spun polyester and nylon fiber, and the core part of the fiber is conductive Examples include core-sheath conjugate spun fibers in which organic particles are kneaded.
Examples of metal powders include metal powders such as tin oxide and carbon black, indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), and indium tin composite oxide. powders of metal oxides such as metal oxides (ITO) and antimony-tin composite oxides (ATO).

The surface modification layer preferably contains a pigment or dye to impart or improve coloring.

For imparting or improving decorativeness, a metal foil such as copper foil, a metal layer such as a continuous or discontinuous metal sputter layer, a metal vapor deposition layer, a metal plating layer, a printed layer, or the like is used as a surface modification layer. good too. Moreover, the surface of the surface modification layer may be mirror-finished, or a regular or irregular pattern may be formed. The pattern may be formed by designing, embossing, texturing, or the like to provide unevenness to the surface of the surface-modified layer.

The printed layer can be formed by commonly used screen printing, flexographic printing, gravure printing, offset printing, inkjet printing, laser printer, or the like. The ink used for the printing layer is usually based on a varnish made by dissolving pigments, dyes, oils, natural resins, synthetic resins, etc. in a solvent, and optional additives such as lubricants and hardeners. Added items are included. The hue of the ink used for the printed layer can be appropriately determined according to the use of the surface-modifying member.

The printed layer can be formed by commonly used screen printing, flexographic printing, gravure printing, offset printing, inkjet printing, laser printer, and the like. The ink used for the printing layer is usually based on a varnish made by dissolving pigments, oils, natural resins, synthetic resins, etc. things, etc. The hue of the ink used for the printed layer can be appropriately determined according to the use of the laminate.
In addition, adhesiveness may be imparted using an adhesive, or solderability may be imparted by tin plating.

More preferably, the surface-modified layer according to the embodiment of the present invention has an easy-adhesion function (easy-adhesion).
Hereinafter, in the present specification, the case where the surface modified layer contains a polymer component and has easy adhesion and paintability will be described as an example.

The surface-modified layer (which may be the material of the surface-modified layer) preferably contains a polymer component, and the polymer component more preferably has a non-polar unit and a polar unit having a polar group. The content of the polymer component in the surface modification layer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass. Yes, particularly preferably 92% by mass to 100% by mass, most preferably 95% by mass to 100% by mass.

As will be described later, in the surface-modified member according to the embodiment of the present invention, the resin member and the surface-modified layer are welded and mixed, or are covalently bonded by a chemical reaction, from the viewpoint of adhesive strength. preferable. Therefore, it is preferable to appropriately select the polymer component contained in the surface modification layer so that it can be welded, mixed, or chemically reacted with the resin contained in the resin member.

Examples of 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.

Examples of polar units having polar groups in the polymer component include epoxy groups, carboxyl groups, nitrile groups, amide groups, ester groups, hydroxyl groups, acid anhydrides, 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 the surface modification layer may contain may be at least one selected from methoxymethyl group-containing polymers, hydroxyl group-containing polymers, carboxyl group-containing polymers, amino group-containing polymers, and amide group-containing polymers.

Such a polymer component that the surface modification layer may contain is preferably an addition-type curing agent, more preferably an addition-type curing agent that reacts with the functional groups of the resin contained in the resin member described later.

As the methoxymethyl group-containing polymer, 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. Examples of such 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.

As the hydroxyl group-containing polymer, 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. Examples of such 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.

As the carboxyl group-containing polymer, any suitable polymer containing a carboxyl group (--COOH) can be employed as long as it does not impair the effects of the present invention. Examples of such 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" and "ARUFON (registered trademark) UC-3510 series" (manufactured by Toagosei Co., Ltd.).
The number of carboxyl group-containing polymers may be one, or two or more.

As the 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.

As the amide group-containing polymer, 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. Examples of such 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 polymer component that may be included in the surface-modified layer (which may be the material of the surface-modified layer) may be an unsaturated hydrocarbon group-containing polymer having unsaturated hydrocarbon groups.

(Unsaturated hydrocarbon group-containing polymer)
Examples of unsaturated hydrocarbon group-containing polymers include polymers selected from acrylic polymers, polyester polymers, urethane polymers, polyether polymers, polyamide polymers, and epoxy acrylate polymers. Those which are coalesced and have unsaturated hydrocarbon groups are included. From the viewpoint of improving adhesion, an unsaturated hydrocarbon group-containing acrylic polymer is preferred.

The unsaturated hydrocarbon group-containing polymer is obtained, for example, by reacting a prepolymer having a functional group with an unsaturated hydrocarbon group-containing compound capable of reacting with and bonding to the functional group.
The term "prepolymer" used herein means a polymer obtained by partially polymerizing the monomers that constitute the polar group-containing polymer.

• Unsaturated Hydrocarbon Group-Containing Acrylic Polymer The method for introducing unsaturated hydrocarbon groups into the prepolymer is not particularly limited, and various methods can be employed. Introducing an unsaturated hydrocarbon group to the side chain of the prepolymer is also advantageous in terms of molecular design.
As such a method, for example, a prepolymer is previously copolymerized with a monomer having a functional group, and then a compound having a functional group capable of reacting with the functional group and an unsaturated hydrocarbon group is added to the unsaturated hydrocarbon group. A method of condensation or addition reaction while maintaining the thermosetting property of is mentioned.
For example, when the unsaturated hydrocarbon group-containing polymer is an unsaturated hydrocarbon group-containing acrylic polymer, a hydroxyl group-containing acrylic polymer is used as a prepolymer, and the prepolymer and the unsaturated hydrocarbon group-containing compound are It can be preferably obtained by an addition reaction. The unsaturated hydrocarbon group-containing compound has a predetermined functional group capable of reacting and bonding with a hydroxyl group, and the hydroxyl group in the prepolymer reacts with the functional group in the unsaturated hydrocarbon group-containing compound. introduces a side chain containing an unsaturated hydrocarbon group derived from the unsaturated hydrocarbon group-containing compound into the prepolymer to obtain an unsaturated hydrocarbon group-containing polymer.

Examples of combinations of these functional groups include a carboxyl group and an epoxy group (especially a glycidyl group), a carboxyl group and an aziridyl group, a hydroxyl group and an isocyanate group, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of the ease of tracking the reaction. In addition, the functional group may be on either side of the prepolymer or the unsaturated hydrocarbon group-containing compound as long as the combination of these functional groups produces the unsaturated hydrocarbon group-containing polymer. .

For example, the prepolymer may have a hydroxyl group, and the unsaturated hydrocarbon group-containing compound may be an unsaturated hydrocarbon group-containing isocyanate compound. In that case, a hydroxyl group-containing acrylic polymer is used as the prepolymer.

Examples of unsaturated hydrocarbon group-containing isocyanate compounds include 2-methacryloyloxyethyl isocyanate (MOI) and 3-isopropenyl-α,α-dimethylbenzyl isocyanate. From the viewpoint of ease of introduction of unsaturated hydrocarbon groups into polymer side chains, the unsaturated hydrocarbon group-containing isocyanate compound is preferably MOI.

The amount of the unsaturated hydrocarbon group-containing compound used in the above reaction is not particularly limited.
Here, when the blending molar ratio of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer that is the raw material of the hydroxyl group-containing acrylic polymer is less than 1, the unsaturated hydrocarbon group-containing acrylic polymer obtained is It becomes a polymer having hydroxyl groups at the same time.

For the unsaturated hydrocarbon group-containing acrylic polymer, for example, a reaction solution is prepared by adding an unsaturated hydrocarbon group-containing compound and an addition reaction catalyst to a prepolymer solution containing the above-described prepolymer, and the addition reaction is performed in the reaction solution. Through the reaction, an unsaturated hydrocarbon group-containing acrylic polymer solution containing an unsaturated hydrocarbon group-containing acrylic polymer can be obtained.

Commercially available products may be used as the unsaturated hydrocarbon group-containing acrylic polymer.
One type of unsaturated hydrocarbon group-containing acrylic polymer may be used, or two or more types may be used.

The surface-modified layer (which may be the material of the surface-modified layer) may contain other components as necessary along with the polymer components described above. Other components include, for example, fillers such as fine particles, pH adjusters, cross-linking agents, viscosity adjusters (thickeners, etc.), leveling agents, release adjusters, plasticizers, softeners, fillers, colorants (pigments and dyes, etc.), surfactants, antistatic agents, preservatives, anti-aging agents, UV absorbers, antioxidants, and light stabilizers.

The thickness of the surface modification layer is not particularly limited, preferably 0.01 μm to 2000 μm, more preferably 0.1 to 1000 μm, still more preferably 0.5 to 200 μm, particularly preferably 1 μm to 100 μm.
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.

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

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

The thickness of the release sheet is preferably 1 μm to 1000 μm, more preferably 10 μm to 500 μm, still more preferably 20 μm to 300 μm, and particularly preferably 30 μm to 100 μm, from the viewpoint of conformability.
If necessary, the surface of the release sheet facing the surface modified layer may be subjected to a release treatment using an appropriate release agent such as silicone.
In order to improve the anchoring property of the adhesive layer, the surface of the release sheet on which the adhesive layer is laminated is preferably subjected to sputtering treatment, corona treatment, Na treatment, plasma treatment, primer treatment, or the like.

<Adhesive layer>
The adhesive layer can be formed with an adhesive.
The pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer can be appropriately selected depending on the intended use. , can be used alone or in combination of two or more, and is preferably formed of a silicone adhesive, a rubber adhesive, an olefin adhesive, or an acrylic adhesive.
For example, from the viewpoint of excellent temporary fixability to the mold even in high-temperature molding at 90 ° C. or higher, the adhesive layer is a pressure-sensitive adhesive layer formed of a silicone-based adhesive, a rubber-based adhesive, or an olefin-based adhesive. is preferred.
In addition, for example, in low-temperature molding below 90° C., even when an acrylic pressure-sensitive adhesive is used, it is possible to prevent adhesion to an adherend due to cross-linking type deterioration, which makes it impossible to peel off.
In particular, silicone pressure-sensitive adhesives are excellent in heat resistance and have strong adhesiveness, so they can be preferably used when providing a small-area pressure-sensitive adhesive layer. Rubber-based adhesives and olefin-based adhesives have easy releasability, so they can be preferably used when a large-area adhesive layer is provided.

(Silicone adhesive)
Any appropriate silicone-based pressure-sensitive adhesive can be employed as the silicone-based pressure-sensitive adhesive within a range that does not impair the effects of the present invention.
Typical examples of silicone-based pressure-sensitive adhesives include peroxide-curable silicone-based pressure-sensitive adhesives and addition reaction-type silicone-based pressure-sensitive adhesives. Only one type of silicone pressure-sensitive adhesive may be used, or two or more types may be used.

Peroxide-curable silicone-based pressure-sensitive adhesive A peroxide-curable silicone-based pressure-sensitive adhesive typically contains silicone rubber, which is a long-chain polymer of polydimethylsiloxane, and silicone resin with a three-dimensional structure. A peroxide-curable silicone pressure-sensitive adhesive may contain an organic peroxide such as benzoyl peroxide as a cross-linking agent in order to be cured by cross-linking. The number of cross-linking agents may be one, or two or more.

Examples of organic peroxides include benzoyl peroxides (t-butyl benzoate peroxide, 2,5-dimethyl-2,5-dibenzoyl hexane diperoxide, dibenzoyl peroxide, 4,4′-dimethyldibenzoyl peroxide , 3,3′-dimethyldibenzoyl peroxide, 2,2′-dimethyldibenzoyl peroxide, 2,2′,4,4′-tetrachlorodibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide), cumyl peroxide, t-butyl cumyl peroxide, t-butyl peroxide, t-butyl isobutyrate peroxide, t-butyl peroxide-2-ethylhexanoate, 2,2-bisperoxide t-butyl octane, 1,1-bis peroxide t-butyl cyclohexane and the like. Among these, benzoyl peroxides are preferable from the viewpoint that the adhesive properties can be easily adjusted by changing the amount added.

Any appropriate compounding amount can be adopted as the content of the organic peroxide in the peroxide-curable silicone pressure-sensitive adhesive within a range that does not impair the effects of the present invention. Typically, the amount of the organic peroxide compounded is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass of the solid content of the peroxide-curable silicone pressure-sensitive adhesive. 0.1 to 5 parts by mass.

Peroxide curable silicone pressure-sensitive adhesives are, for example, 30% by mass to 70% by mass organic solvent solutions (solutions of paraffinic organic solvents such as hexane, and solutions of aromatic organic solvents such as toluene and xylene). prepared or marketed as That is, the peroxide-curable silicone pressure-sensitive adhesive is preferably a solution (typically, a coating solution) containing 30% to 70% by mass of an organic solvent.

Examples of commercially available peroxide-curable silicone pressure-sensitive adhesives include YR3340, YR3286, PSA610-SM, and XR37-B6722 manufactured by Momentive Performance Materials, SE4200 and SH4280 manufactured by Dow Toray, and Shin-Etsu Chemical. KR-100, KR-101-10 (toluene solvent type), KR-120, KR-130, X-40-3287 (isoparaffin solvent type), etc. manufactured by the company.

- Addition-reactive silicone-based pressure-sensitive adhesive The addition-reactive silicone-based pressure-sensitive adhesive preferably contains a main agent, a cross-linking agent, and, if necessary, a curing catalyst. Addition-reactive silicone pressure-sensitive adhesives have the advantage that they can be used with only primary curing at low temperatures and do not require secondary curing at high temperatures. Therefore, when an addition reaction type silicone pressure-sensitive adhesive is used, the silicone pressure-sensitive adhesive layer can be produced at a relatively low temperature, resulting in excellent energy economy.

Addition-reactive silicone-based pressure-sensitive adhesives usually contain a main agent consisting of a mixture of a silicone-based resin component and a silicone-based rubber component, a hydrosilyl group (SiH group)-containing cross-linking agent, and, if necessary, a curing catalyst.

The silicone-based resin component is typically an organopolysiloxane having a network structure obtained by hydrolyzing an organochlorosilane or an organoalkoxysilane, followed by a dehydration-condensation reaction. Only one type of silicone-based resin component may be used, or two or more types may be used.

The silicone-based rubber component is typically diorganopolysiloxane having a linear structure. Only one type of silicone-based rubber component may be used, or two or more types may be used.

In both the silicone-based resin component and the silicone-based rubber component, examples of organo groups include methyl, ethyl, propyl, butyl, and phenyl groups. Some organo groups include vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth)acryloyl, (meth)acryloylmethyl, (meth)acryloylpropyl, and cyclohexenyl groups. may be substituted by any unsaturated group.

Examples of organopolysiloxanes include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd., BY23-753, BY24-162, SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Dow Toray Industries, Inc.

Examples of silicone-based rubber components include KS-3800 manufactured by Shin-Etsu Chemical Co., Ltd., BY24-162, BY24-843, and SD-7292 manufactured by Dow Toray Industries, Inc.

The number of cross-linking agents may be one, or two or more. Examples of cross-linking agents include siloxane-based cross-linking agents (silicone-based cross-linking agents). Examples of siloxane-based cross-linking agents include polyorganohydrogensiloxanes having two or more silicon-bonded hydrogen atoms in the molecule.

A curing catalyst is typically used to promote the hydrosilylation reaction between the unsaturated groups in the silicone-based resin component and silicone-based rubber component and the Si—H groups in the cross-linking agent. The curing catalyst may be of only one type, or may be of two or more types.

As the curing catalyst, for example, a platinum-based catalyst, namely, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol solution, a reaction product of chloroplatinic acid and an olefin compound, chloroplatinic acid and vinyl group-containing siloxane compounds, platinum-olefin complexes, platinum-vinyl group-containing siloxane complexes, platinum-phosphorus complexes, and the like. Specific examples of such curing catalysts are described, for example, in JP-A-2006-28311 and JP-A-10-147758. Specific commercial products include, for example, SRX-212 manufactured by Dow Toray Industries, Inc. and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the curing catalyst is preferably 5 ppm by mass to 2000 ppm by mass, more preferably 10 ppm by mass to 500 ppm by mass, in terms of platinum content with respect to the total amount of the silicone resin component and the silicone rubber component. be.

(rubber adhesive)
A rubber-based pressure-sensitive adhesive contains natural rubber or a rubber-based polymer as a base polymer.
Examples of rubber-based polymers include styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene/butylene-styrene block copolymer, styrene-butadiene rubber, polybutadiene, polyisoprene, polyisobutylene, Butyl rubber, chloroprene rubber, silicone rubber and the like.

(Olefin adhesive)
Olefin-based pressure-sensitive adhesives contain an olefin-based resin as a base polymer.
Examples of the olefin resin include α-olefin copolymers formed from at least two monomers selected from the group consisting of ethylene, propylene and α-olefin. More specifically, copolymers containing ethylene as the main monomer (ethylene-based α-olefin copolymers), copolymers containing propylene as the main monomer (propylene-based α-olefin copolymers), etc. is mentioned. The α-olefin copolymer may be random copolymer, block copolymer or graft copolymer.

(Acrylic adhesive)
Acrylic adhesives are mainly composed of (meth)acrylic acid alkyl esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, and acrylonitrile, vinyl acetate, styrene, etc. , methyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, vinylpyrrolidone, glycidyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, acrylamide, γ-methacryloxypropyltrimethoxysilane, etc. The main component is a polymer of the following monomers.

In addition, these adhesives include tackifying resins, cross-linking agents, viscosity modifiers (thickeners, etc.), leveling agents, release modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.). , surfactants, antistatic agents, preservatives, anti-aging agents, UV absorbers, antioxidants, light stabilizers and the like can be added as appropriate.

The thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more, from the viewpoint of temporary fixability. From the viewpoint of removability and moldability, the thickness is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 60 μm or less.
The thickness of the adhesive layer can be measured with a dial gauge.

The adhesive layer is preferably protected by a release liner until it is attached to the mold. That is, the surface-modified sheet in the present embodiment preferably has a release liner on the surface of the pressure-sensitive adhesive layer opposite to the release sheet.

The release liner is not particularly limited as long as it can protect the pressure-sensitive adhesive layer. Appropriate thin sheets such as laminates can be used, but plastic films are preferably used because of their excellent surface smoothness.

Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. - Vinyl acetate copolymer film and the like.

The thickness of the release liner is usually 5-200 μm, preferably 5-100 μm. For the release liner, if necessary, a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder, etc., coating type, kneading type, vapor deposition An antistatic treatment can also be applied to the mold or the like. In particular, by subjecting the surface of the release liner to a release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., the releasability from the pressure-sensitive adhesive layer can be further enhanced.

A commercially available release liner may be used, for example, a polyethylene terephthalate separator (trade name "MRF38" or "FRE38", manufactured by Mitsubishi Plastics, Inc.) whose surface is release-treated.

[Production of surface-modified sheet]
A surface-modified sheet comprising a surface-modified layer, a release sheet, and an adhesive layer in this order can be produced by any appropriate method. For example, a pressure-sensitive adhesive layer may be provided on a release sheet, and then a surface-modified layer may be provided on the opposite surface of the release sheet, or a surface-modified layer may be provided on the release sheet and then the release sheet A pressure-sensitive adhesive layer may be provided on the surface opposite to the .

<Method for Forming Surface Modified Layer>
Methods for forming the surface modified layer include, for example, a method of dipping a release sheet in a solution (surface modified composition) containing a material for the surface modified layer and a solvent (surface modified composition), followed by drying if necessary; 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 by various coaters of a solution containing the material of the surface modification layer and a solvent Examples include a method of drying after coating as necessary, and 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 and then drying as needed.

Examples of the surface-modifying composition include a solution obtained by dissolving the material of the surface-modifying layer in a solvent.
Examples of solvents include water; alcohols such as methanol, ethanol, and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone; esters such as ethyl acetate; amides such as dimethylformamide; sulfoxides such as dimethylsulfoxide; ethers such as dimethyl ether and tetrahydrofuran; Only one kind of solvent may be used, or two or more kinds thereof may be used.

As the surface-modifying composition, it is also preferable to use the polymer solution containing the polymer obtained in polymer synthesis as it is.

The solid content concentration in the surface-modifying composition can be appropriately set according to the purpose. From the viewpoint of thickness accuracy of the surface modified layer, the mass ratio is preferably 1% to 60% by mass, more preferably 10% to 50% by mass, and still more preferably 15% to 40% by mass. is.

The surface-modifying composition may optionally contain other components that may be included in the surface-modifying layer along with the polymer components described above.
For example, by adding a coloring agent, the surface modified layer becomes visible, making it easier to determine whether the surface of the resin member has already been modified, which is advantageous in terms of process control. It also functions as a base for improving the coloring of the paint.
Colorants include, for example, dyes and pigments. Further, the colorant may be a fluorescent material that can be visually recognized under black light.

<Method for Forming Adhesive Layer>
The pressure-sensitive adhesive layer can be formed, for example, by applying a solution (pressure-sensitive adhesive composition) containing a pressure-sensitive adhesive and an appropriate solvent onto a release sheet and removing the solvent and the like by drying. Alternatively, the release sheet and the adhesive layer may be formed by extrusion molding.
The pressure-sensitive adhesive layer is formed, for example, by bonding a release sheet to the surface of the pressure-sensitive adhesive layer side of the laminate of the pressure-sensitive adhesive layer and the release liner formed on the release liner from the pressure-sensitive adhesive composition. can also
At this time, it is preferable to form the pressure-sensitive adhesive layer on the surface of the release sheet that has been subjected to sputtering treatment, corona treatment, Na treatment, or the like as described above.

Various methods are used as the method of applying the adhesive composition. Specifically, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die coater, etc. A method such as an extrusion coating method can be used.

The heat drying temperature is preferably 30°C to 200°C, more preferably 40°C to 180°C, and even more preferably 80°C to 160°C. By setting the heating temperature within the above range, a pressure-sensitive adhesive layer having excellent adhesive properties can be obtained. An appropriate drying time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, even more preferably 1 minute to 8 minutes.

When the adhesive composition is an active energy ray-curable adhesive, the adhesive layer can be formed by irradiating active energy rays such as ultraviolet rays. A high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a chemical light lamp, or the like can be used for ultraviolet irradiation.

[Laminate]
A laminate according to an embodiment of the present invention is a laminate in which a surface-modified sheet according to an embodiment of the present invention is laminated on at least part of the surface of a resin material. A laminate according to an embodiment of the present invention is a laminate obtained by laminating such that the surface of the surface-modified sheet on the surface-modified layer side is in contact with at least part of the surface of the resin material.
The laminate, which is the resin material with the surface-modified sheet in 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.

<Resin material>
The resin contained in the resin material may be a thermosetting resin or a thermoplastic resin.

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

Examples of thermoplastic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), POM (polyacetal), PEEK ( polyether ether ketone), PC (polycarbonate), PES (polyether sulfide), and the like.

Also, the resin may be a fiber-reinforced resin. That is, the resin material may be a resin material containing fiber-reinforced resin. Moreover, the resin material may contain a carbon fiber reinforced resin containing a carbon fiber cloth material.

Examples of fiber-reinforced thermosetting resins include carbon fiber-reinforced thermosetting resins and glass fiber-reinforced thermosetting resins.
Examples of fiber-reinforced thermoplastic resins include carbon-fiber-reinforced thermoplastic resins and glass-fiber-reinforced thermoplastic 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. For example, when the resin material is plate-shaped, sheet-shaped, or film-shaped, it means a part of at least one surface or the entirety of at least one surface.

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

The resin material may be prepreg.
Here, 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.

[Surface modification member]
In the surface-modified member according to the embodiment of the present invention, the surface-modified layer in the surface-modified sheet according to the embodiment of the present invention is laminated on at least a part of the surface of the resin member, and the resin member and the surface It is a surface-modified member combined with a modified layer.
In the surface modified member according to the embodiment of the present invention, it is preferable that the resin member and the surface modified layer are welded and mixed, or are covalently bonded by a chemical reaction. In this case, the adhesive strength between the resin member and the surface modified layer is excellent.

As for the surface-modified sheet, the surface-modified layer, and the resin material, the above descriptions can be used as they are. 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.
Here, "molding" means processing a material into a predetermined shape, whether or not a mold is used, and "molding" means processing a material into a predetermined shape using a mold. means that

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

Heat molding 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 and the resin material.
By providing the surface-modified layer on the surface of the resin member by such a method, the resin member can be provided with sufficient adhesive strength, and the surface-modified member can be manufactured 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).

[Method for producing surface-modified member]
A method for manufacturing a surface-modified member according to an embodiment of the present invention is a method for manufacturing a surface-modified member using the surface-modified sheet described above.
The method for manufacturing the surface-modified member according to the embodiment of the present invention is not particularly limited, but preferably includes a lamination step of laminating the surface-modified layer on the resin member by thermoforming.
For example, the surface-modified sheet is temporarily fixed to the mold of the molding apparatus via the adhesive layer, and at least a part of the surface of the resin material is in contact with the surface of the temporarily-fixed surface-modified sheet on the surface-modified layer side. A surface-modified member can be manufactured by placing a resin material on a surface and performing heat molding.
In addition, for example, the surface-modified member is manufactured by temporarily fixing the surface-modified sheet to the mold of the molding device via the adhesive layer, placing the resin material on the other mold, and performing heat molding. can do.
Since the surface-modified sheet according to the embodiment of the present invention can be temporarily fixed to the mold of the molding apparatus via the adhesive layer, it is possible to prevent misalignment with the mold regardless of whether the molding apparatus is vertical or horizontal. is unlikely to occur, and a surface-modified member can be stably produced.

In the lamination step, the surface modification composition is applied to at least a part of the surface of the resin material and dried as appropriate to laminate the surface modification layer, and a release sheet and an adhesive are applied on the surface modification layer. A laminate obtained by further laminating agent layers may be prepared and heat-molded to form a surface-modified sheet on the resin material. However, from the viewpoint of uniformity of the thickness of the surface-modified layer, suppression of yield reduction due to overflow of the surface-modified composition, etc., and prevention of deformation of the resin material, after forming the surface-modified sheet according to the embodiment of the present invention, It is preferable to use it by laminating it on a resin material.

The interface between the surface modified layer and the resin material is melted and contacted by heat molding, and the polymer component contained in the surface modified layer melts and mixes with the resin contained in the resin material, or chemically reacts. It is possible to form a surface-modified member in which the modified layer is welded and mixed or covalently bonded.
The heat molding may be performed simultaneously with placing the resin material on the surface-modified sheet or placing the surface-modified sheet on the resin material, after placing the resin material on the surface-modified sheet, or It may be performed after placing the surface-modified sheet on the resin material.
By surface-treating the resin member by such a method, it is possible to impart sufficient adhesive strength to the resin member and to manufacture the surface-modified member with high productivity and low cost. The method for manufacturing a surface-modified member can also be a method for treating the surface of a resin member (method for surface treatment of a resin member).

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

In the production of the surface modified member, when the resin contained in the resin member is a thermosetting resin, when the curing temperature of the thermosetting resin is T ₂ ° C., the surface of the resin material containing the thermosetting resin It is preferable to provide a surface-modified layer on at least a part of and perform heat molding at a temperature of T ₁ ° C. or higher. The curing temperature is the temperature within the heat generation temperature range of the heat flow curve measured by DSC (differential scanning calorimetry) of the uncured thermosetting 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.
Here, _T1 is the temperature (°C) at which heat generation begins when an uncured thermosetting resin is measured by DSC, and _T3 is the temperature (°C) at which heat generation ends.

In the production of the surface-modified member, when the resin contained in the resin member is a thermoplastic resin, when the melting point of the thermoplastic resin is T ₄ ° C., at least a part of the surface of the thermoplastic resin is surface-modified. It is preferable to provide a layer and perform heat welding at a temperature of (T ₄ -50)° C. or higher. The temperature of this heat welding is preferably (T ₄ -50)° C. to (T ₄ +150)° C., more preferably (T ₄ -25)° C. to (T ₄ +100)° C., and still more preferably ( T ₄ -10)°C to (T ₄ +75)°C, particularly preferably (T ₄ )°C to (T ₄ +50)°C. With the heat molding temperature, that is, the molding temperature, within the above range, the interface between the surface modified layer and the thermoplastic resin member is melted and mixed by the above method, and sufficient adhesive strength is imparted to the thermoplastic resin member. can do. Such application can be performed with high productivity and low cost.

By setting the heat molding temperature within the above range, the interface between the surface modified layer and the resin member is melted and mixed to melt and mix, or a covalent bond is formed by a chemical reaction, and the adhesion strength between the resin member and the coating film. It is possible to provide a surface modified layer excellent in And such provision can be performed with high productivity and low cost.

Examples of heat molding methods include compression molding, transfer molding, and injection molding. Resin molding is preferable, and compression molding is more preferable. When the resin contained in the resin material is a fiber-reinforced thermosetting resin, the molding method may be a hand lay-up method, a spray-up method, a filament winding method, a pultrusion method, a sheet mold compound method, a bulk mold compound method, a resin transfer method. law, etc.

Heating and crimping in compression molding may be performed at the same time or may not be performed at the same time. Also, the heating and pressure bonding may each be performed multiple times. Crimping may be under reduced pressure or under increased pressure. For example, it may be crimped after heating, may be heated after crimping, or may be crimped after heating and further heated.
As compression bonding by reduced pressure, for example, compression bonding by evacuating the space between the surface-modified sheet and the resin member is exemplified.
The pressure-bonding includes, for example, pressure-bonding by pressing the surface-modified sheet laminated on the resin member with, for example, compressed air, a heat press head, a press machine, or the like.

As compression molding using a press machine, for example, in a molding machine, the surface-modified sheet is temporarily fixed to the mold of the molding machine via an adhesive layer, and the surface of the temporarily fixed surface-modified sheet is modified. In this mode, the resin material is placed so that at least part of the surface of the resin material is in contact with the substrate side, and a molding process involving heating (for example, integral molding by hot pressing) 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 compression molding is preferably 1 MPa or higher, more preferably 2 MPa or higher, and even more preferably 3 MPa or higher, from the viewpoint of deformation of the molded product by the mold. In addition, from the viewpoint of maintaining the amount of resin in the molded product, the viscosity is preferably 30 MPa or less, more preferably 25 MPa or less, and even more preferably 20 MPa or less.

Injection molding may be used as the molding process for the resin member.
For injection molding, for example, an injection molding machine equipped with a movable mold and a fixed mold can be used. For example, the surface-modified sheet is temporarily fixed so that the pressure-sensitive adhesive layer faces the concave portion of the cavity of the movable side mold, and the movable side mold and the fixed side mold are clamped. Then, the melted resin is injected into the cavity.
After cooling and solidifying the resin in the mold, the movable side mold and the fixed side mold are separated from each other. Thus, a surface-modified member is obtained in which the surface-modified layer of the surface-modified sheet and the resin member are integrated.

The pressure-sensitive adhesive layer and release sheet on the surface-modified member may be peeled off.
The peeling method of the pressure-sensitive adhesive layer and the release sheet is not particularly limited, and may be manual peeling, peeling using dedicated peeling equipment, or the like.
For example, when the surface-modified member is removed from the molding apparatus after hot molding, the pressure-sensitive adhesive layer and the release sheet remain temporarily fixed to the mold side, so that the surface-modified member can be removed by separating the mold. can be peeled off from At this time, the adhesive force between the surface-modified layer and the release sheet<the adhesive force between the release sheet and the pressure-sensitive adhesive layer.

Also, the pressure-sensitive adhesive layer and the release sheet on the surface-modifying member may not be peeled off.
For example, the pressure-sensitive adhesive layer and the release sheet of the temporarily fixed surface-modified sheet are not peeled off from the surface-modified layer after heat molding, and the pressure-sensitive adhesive layer is peeled off from the mold so that the surface-modified member adheres to the adhesive layer. It may be in a state in which the agent layer and the release sheet are laminated. The release sheet can be left in place until just before painting. This can prevent contamination of the surface of the surface modified layer. At this time, the adhesive strength between the surface modified layer and the release sheet>the adhesive strength between the release sheet and the pressure-sensitive adhesive layer.

In addition, if the pressure-sensitive adhesive layer and the release sheet remain temporarily fixed to the mold when the surface-modified member is taken out from the molding apparatus after heat molding, they should be removed to the extent that they can be easily peeled off from the mold. It must be fixed to the mold with adhesive force.

In this way, at least part of the surface of the resin member (which may be a resin material) is on the surface modification layer side of the surface modification sheet, which is a laminate of the surface modification layer, the release sheet, and the pressure-sensitive adhesive layer. After the resin members are placed in contact with each other and heat-molded, the pressure-sensitive adhesive layer and the release sheet are preferably removed. By removing the pressure-sensitive adhesive layer and the release sheet, 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. be done.
As described above, preferably, the resin in the resin member and the resin in the surface modification layer are welded and mixed or covalently bonded between the layers of the resin member and the surface modification layer.

By the above manufacturing method, as shown in FIG. 1, the surface-modified sheet 200 is provided on the surface of the resin member 100 to obtain the surface-modified member. Further, by peeling off the adhesive layer 40 and the release sheet 20, a surface-modified member having the surface-modified layer 10 provided on the surface of the resin member 100 is obtained as shown in FIG.

The surface-modified sheet, which is a laminate of a surface-modified layer, a release sheet, and an adhesive layer, is a laminate of a surface-modified layer 10, a release sheet 20, and an adhesive layer 40, as shown in FIG. This is the surface modified sheet 200 .

In the method for manufacturing a surface-modified member according to the embodiment of the present invention, the form in which the resin material is placed so that at least part of the surface of the resin material is in contact with the surface-modified layer side of the surface-modified sheet is As shown in FIG. 4, the resin material 400 is placed on the surface-modified sheet 200 so that the surface-modified layer 10 side of the surface-modified sheet 200 faces the surface of the resin material 400 .

[Painted article and method for producing the painted article]
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. It is preferable to provide a coating film on at least part of the surface of the surface-modifying member on the surface-modifying layer side.
As an example of a coated object according to an embodiment of the present invention, a coating film 30 is provided on the surface of the surface-modified member on the surface-modified layer side of the surface-modified member in which the surface-modified layer 10 is provided on the surface of the resin member 100 shown in FIG. 3 shows a painted object 300. FIG.

The coating film may be at least one selected from coating, printing layer, vapor deposition layer, and plating layer.

From the viewpoint of the adhesion improvement effect by applying the surface-modified sheet of the present invention, it is preferable that the coating film contains a paint, and when the polymer component contained in the surface-modified layer has a polar unit having a polar group, More preferably, the paint contains a functional group that forms a chemical bond with a polar group in the polymer component or has an intermolecular interaction.
From the viewpoint of improving adhesion, the functional group is preferably a functional group that covalently bonds with a polar group in the polymer component contained in the surface-modified layer, more preferably an isocyanate group or an amino group.

The paint contained in the coating film is preferably urethane paint such as urethane paint or acrylic/urethane paint, acrylic paint, epoxy paint, silicone paint, polyester resin, melamine resin paint or fluorine paint, more preferably urethane paint.
Urethane paint is a general term for paints that combine a resin (polyol) having multiple hydroxyl groups as a main agent and a polyisocyanate as a curing agent. The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups. Aliphatic ones such as hexamethylene diisocyanate, alicyclic ones such as isophorone diisocyanate, monomers thereof and multimers thereof such as burette type, nurate type and adduct type can be used.

Since 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.
In addition, by providing the surface modification layer on the surface of the resin member in a molten or softened state, the surface modification layer and the resin member are welded and mixed or chemically bonded by the heat of the surface of the resin member, and the surface modification layer and the resin are bonded together. Since the adhesive strength with the member increases, a coating film with excellent adhesion can be formed. In addition, the polar groups in the polymer component contained in the surface modified layer and the above functional groups in the paint contained in the coating film form chemical bonds or interact with each other, so that the surface modified layer and the paint The adhesive strength with the film is also increased, and a coating film with extremely excellent adhesion can be formed.
Furthermore, since it is possible to integrally mold the surface modified layer and the resin member when forming the coated object, a cleaning treatment process using an organic solvent to remove the mold release agent before forming the coating film and polishing are performed. It does not require a treatment process, is highly safe, and can reduce the environmental load and workload.

The thickness of the coating film is not particularly limited, preferably 0.01 to 2000 μm, more preferably 0.1 to 1000 μm, still more preferably 0.5 to 500 μm, particularly preferably 1 to 200 μm. be.

A method for manufacturing a coated object according to an embodiment of the present invention is a method for manufacturing a coated object using the surface-modified sheet described above.
A method for manufacturing a coated object according to an embodiment of the present invention is a method for manufacturing a coated object using the surface-modified sheet described above,
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
forming a coating film on the surface modification layer side of the surface modification member.
A step of peeling off the release sheet and the pressure-sensitive adhesive layer is preferably included between the step of producing the surface-modified member and the step of forming the coating film.

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. In addition, for the step of forming the surface-modified member, the description in the above [Method for producing surface-modified member] can be used as it is.

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

[Jointed body and method for manufacturing the joined body]
(first zygote)
A bonded body according to an embodiment of the present invention is a bonded body in which an adhesive layer is provided on at least a part of a surface modifying member, and the adherend and the surface modifying member are bonded via the adhesive layer.
The bonded body may be referred to as a first bonded body.
As an example of the first joined body according to the embodiment of the present invention, an adhesive layer is formed on the surface of the surface-modified member having the surface-modified layer 10 provided on the surface of the resin member 100 shown in FIG. 50, and shows a first bonded body 600 in which an adherend 500 and a surface modification member are bonded via an adhesive layer 50. FIG.

Examples of adherends that can be bonded include electronic parts, automobile exterior parts (especially flexible rubber hollow members such as weather strips), body protection parts and decorative parts.

The adhesive that forms the adhesive layer is not particularly limited, and examples thereof include rubber-based adhesives, urethane-based adhesives (acrylic urethane-based adhesives), acrylic-based adhesives, silicone-based adhesives, polyester-based adhesives, and polyamides. Known adhesives such as adhesives, epoxy adhesives, vinyl alkyl ether adhesives, and fluorine adhesives can be used. Among these, rubber-based adhesives and urethane (acrylic urethane)-based adhesives are particularly preferred. Moreover, the adhesive may be used alone or in combination of two or more.

(Method for manufacturing first joined body)
A method for manufacturing a bonded body according to an embodiment of the present invention is a method for manufacturing a bonded body using the surface-modified sheet described above. Using the surface-modified sheet described above, a first joined body and a second joined body, which will be described later, can be produced.
A method for producing a joined body (first joined body) according to an embodiment of the present invention is a method for producing a joined body using the surface-modified sheet described above,
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
forming an adhesive layer on the surface modification layer side of the surface modification member;
It is preferable to include a step of bonding the adherend and the surface modifying member via the adhesive layer.
In addition, it is preferable to include a step of peeling off the release sheet and the pressure-sensitive adhesive layer of the surface-modified member between the step of manufacturing the surface-modified member and the step of forming the adhesive layer.

(Second conjugate)
A joined body according to another embodiment of the present invention has a second resin member laminated on at least part of the surface of the surface-modified member on the surface-modified layer side, and the second resin member and the surface The modified layer is a bonded body in which the modified layer is welded and mixed or covalently bonded.

A joined body according to another embodiment of the present invention may be referred to as a second joined body.

A second joined body according to another embodiment of the present invention is such that the surface-modified layer in the surface-modified sheet according to the embodiment of the present invention is laminated on at least a part of the surface of the first resin member, A second resin member is laminated on at least a part of the surface of the laminated surface modified layer, and the first resin member and the surface modified layer are welded and mixed or covalently bonded to form the second resin. A bonded body in which the member and the surface modification layer are welded and mixed or covalently bonded may be used.
A second joined body according to another embodiment of the present invention is a joined body in which a first resin member and a second resin member are laminated via the surface modified layer of the surface modified sheet. may That is, a second bonded body according to another embodiment of the present invention is a bonded body in which a first resin member, the surface modified layer of the surface modified sheet, and the second resin member are laminated in this order. It can be a body.

As an example of a second bonded body according to another embodiment of the present invention, the surface of a surface-modified member in which a surface-modified layer 10 is provided on the surface of a resin member (first resin member) 100 shown in FIG. A second joined body 601 is shown in which the second resin member 101 is provided on the modified layer side surface, and the first resin member 100 and the second resin member 101 are bonded via the surface modified layer 10 .

As for the first resin member and the second resin member, the description of the resin member in the above [Surface-modified member] and [Manufacturing method of surface-modified member] can be used as it is. The first resin member and the second resin member may be obtained by molding the same type of resin material, or may be obtained by molding different types of resin material.

In the second joined body according to another embodiment of the present invention, the resin material used for the first resin member is a carbon fiber cloth material among the resin materials described in the section [Surface modification member] above. It is preferable to use the carbon fiber reinforced resin contained.

　Conventional carbon fiber reinforced resins containing carbon fiber cloth materials are high in strength, but have the problem of high cost. In a second joined body according to another embodiment of the present invention, a surface-modified member is manufactured using a resin material containing a carbon fiber reinforced resin containing a carbon fiber cloth material, and the surface of the surface-modified member is modified. By forming the second resin member laminated on the surface of the hard layer by thermoforming from a reinforced resin containing short fibers or glass fibers or a resin material not containing fibers, it becomes easy to achieve both high strength and low cost. In this case, the adhesion between the first resin member and the second resin member becomes a problem. high adhesion can be obtained.

As for the surface-modified sheet, the surface-modified layer, and the surface-modified member, the above descriptions can be used as they are. In addition, for the step of forming the surface-modified member, the description in the above [Method for producing surface-modified member] can be used as it is.

(Second manufacturing method of joined body)
A method for manufacturing a joined body according to another embodiment of the present invention is provided by laminating a second resin member on at least part of the surface of the surface-modified member according to the embodiment of the present invention on the side of the surface-modified layer, A method for manufacturing a joined body in which the second resin member and the surface modified layer are welded and mixed or covalently bonded, wherein the second resin member is heat-molded to modify the surface of the surface modified member. A step of laminating at least a portion of the surface of the layer side is included.

A method for manufacturing a bonded body according to another embodiment of the present invention is a method for manufacturing a bonded body using the surface-modified sheet according to the embodiment of the present invention, wherein the surface-modified layer is first formed by heat molding. A step of manufacturing a surface-modified member by laminating it on the resin member of
laminating a second resin member on at least a part of the surface of the surface-modified member on the surface-modified layer side by thermoforming,
The first resin member and the second resin member are joined via the surface modified layer, the first resin member and the surface modified layer are welded and mixed or covalently bonded, and the second The method for producing a joined body may be one in which the resin member and the surface modification layer are welded and mixed or covalently bonded to obtain a joined body.
In the step of laminating the second resin member on at least a part of the surface of the surface-modified member on the surface-modified layer side by heat-molding, the above description can be used as it is for the heat-molding method. Molding, transfer molding, injection molding, etc. are preferred, and injection molding is more preferred.

In addition, between the step of manufacturing the surface-modified member and the step of laminating a second resin member on at least a part of the surface of the surface-modified member on the surface-modified layer side by thermoforming, , the step of peeling off the release sheet and the pressure-sensitive adhesive layer of the surface-modifying member.

As for the second resin member, the surface-modified sheet, the surface-modified layer, and the surface-modified member, the above descriptions can be used as they are. In addition, for the step of forming the surface-modified member, the description in the above [Method for producing surface-modified member] can be used as it is.

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

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

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

As described above, this specification discloses the following matters.
[1]
A surface-modified sheet comprising a surface-modified layer, a release sheet, and an adhesive layer in this order.
[2]
The surface-modified sheet according to [1], wherein a release liner is provided on the surface of the pressure-sensitive adhesive layer opposite to the release sheet.
[3]
The surface-modified sheet according to [1] or [2], wherein the pressure-sensitive adhesive layer is formed from a silicone-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, an olefin-based pressure-sensitive adhesive, or an acrylic pressure-sensitive adhesive.
[4]
The surface-modified sheet according to any one of [1] to [3], wherein the surface-modified layer has an easy adhesion function.
[5]
A laminate in which the surface-modified sheet according to any one of [1] to [4] is laminated on at least part of the surface of a resin material.
[6]
The laminate according to [5], wherein the resin material contains a fiber-reinforced resin.
[7]
The surface-modified layer in the surface-modified sheet according to any one of [1] to [4] is laminated on at least part of the surface of a resin member, and the resin member and the surface-modified layer are laminated. Weld-blended or covalently bonded surface modification components.
[8]
A coated article comprising a coating film on at least a part of the surface-modified member according to [7].
[9]
A bonded body in which an adhesive layer is provided on at least a part of the surface modifying member according to [7], and the adherend and the surface modifying member are bonded via the adhesive layer.
[10]
A second resin member is laminated on at least a part of the surface of the surface-modified member on the surface-modified layer side of the surface-modified member according to [7], and the second resin member and the surface-modified layer are welded and mixed or covalently bonded conjugate.
[11]
[1] A method for producing a surface-modified member using the surface-modified sheet according to any one of [4].
[12]
The method for producing a surface-modified member according to [11], which includes a lamination step of laminating the surface-modified layer on the resin member by thermoforming.
[13]
[1] A method for producing a coated object using the surface-modified sheet according to any one of [4].
[14]
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
The method for producing a coated object according to [13], comprising the step of forming a coating film on the surface modification layer side of the surface modification member.
[15]
[1] A method for producing a joined body using the surface-modified sheet according to any one of [4].
[16]
The method for manufacturing a joined body according to [10], comprising the step of laminating the second resin member on at least a part of the surface of the surface-modified member on the surface-modified layer side by thermoforming,
A method for producing a conjugate.
[17]
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
forming an adhesive layer on the surface modification layer side of the surface modification member;
The method for producing a joined body according to [15], comprising the step of joining the adherend and the surface-modifying member via the adhesive layer.

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

〔evaluation〕

<Mold Temporary Fixability>
The surface-modified sheets produced in Examples and Comparative Examples were cut into pieces of 10 mm in width and 100 mm in length to obtain surface-modified sheet pieces. The surface of the adhesive layer side of the surface-modified sheet strip from which the release liner was peeled off was adhered to a SUS304BA plate coated with a Si release agent and subjected to baking treatment by reciprocating a 2 kg roller once. It was used as a sample for mold temporary fixability evaluation.
The measurement was performed after standing in an atmosphere of 23°C and 50% RH for 30 minutes (initial) and after heating at 150°C for 2 hours (only for Example 6, after heating at 90°C for 2 hours), cooling to room temperature, and tensile strength. Using a tester (AUTOGRAPH AGS-X, manufactured by Shimadzu Corporation), the surface-modified sheet was peeled off from a SUS304BA plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min, and the adhesive strength was measured. . 150° C.×2 hours simulates molding, but the molding time in many molding methods is several minutes. The heating time was set to 2 hours assuming the case of autoclave molding, VaRTM molding, and the like.

<Paint adhesion>
The coated objects prepared in Examples and Comparative Examples were subjected to cross-cut evaluation (cross-cut peeling) by the cross-cut method described in JIS K5600-5-6, and the number of unpeeled coating films (number of adhesion) was counted. did. When the number of unpeeled coating films is 50 or more out of 100, the adhesion between the surface modification layer and the coating film is good (○), and when it is 49 or less, it is judged to be bad (x). did.
・Cut interval: 2mm
・ Number of cross cuts: 100 squares ・ Peeling tape: (Nichiban) cellophane tape (registered trademark) 24 mm width

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

<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 is measured, the thickness (μm) of the laminate from which the surface-modified layer is removed at that location is measured, and the difference is the thickness (μm) of the surface-modified layer (average thickness (μm)). and The average thickness (μm) is the average value obtained by measuring 10 points.

<Thickness of adhesive layer>
The thickness of the pressure-sensitive adhesive layer was measured with a dial gauge (GC-9 manufactured by Peacock). The thickness of the surface-modified sheet is measured, the thickness (μm) of the laminate with the adhesive layer removed at that location is measured, and the difference is the thickness (μm) of the surface-modified layer (average thickness (μm)). did. The average thickness (μm) is the average value obtained by measuring 10 points.

[Preparation of adhesive composition]
(Silicone adhesive A)
Toluene was added to 100 parts by mass of SD4592PSA (DOWSIL SD4592PSA manufactured by Dow Toray Co., Ltd.) as a base polymer, and diluted with stirring. 0.2 parts by mass of curing agent BY24-741 (manufactured by Dow Toray Co., Ltd.) and 0.9 parts by mass of platinum catalyst SRX212 (manufactured by Dow Toray Co., Ltd.) are added and mixed to form an addition-curable silicone with a solid content of 30%. A silicone-based pressure-sensitive adhesive was prepared and designated as silicone-based pressure-sensitive adhesive A.

(Silicone adhesive B)
Toluene was added to 100 parts by mass of SD4585PSA (DOWSIL SD4585PSA manufactured by Dow Toray Co., Ltd.) as a base polymer, and diluted with stirring. 0.2 parts by mass of curing agent BY24-741 (manufactured by Dow Toray Co., Ltd.) and 0.9 parts by mass of platinum catalyst SRX212 (manufactured by Dow Toray Co., Ltd.) are added and mixed to form an addition-curable silicone with a solid content of 30%. A silicone-based pressure-sensitive adhesive B was prepared.

(Silicone adhesive C)
Toluene was added to 100 parts by mass of SH-4280 (manufactured by Dow Toray Co., Ltd.) as a base polymer, and diluted with stirring. Add 1.5 parts by mass of Nyper BMT-K-40 (manufactured by NOF Corporation, benzoyl peroxide) as a peroxide and mix to prepare a peroxide-curable silicone adhesive with a solid content of 30%. was used as silicone-based adhesive C.

(rubber adhesive)
Oppanol 80 (manufactured by BASF, polyisobutylene-based adhesive) was pulverized and dissolved in toluene heated to 60° C. to obtain a rubber-based adhesive having a solid content of 20%.

(Olefin adhesive)
vistamaxx6102 (manufactured by SSOH Co., Ltd., polypropylene adhesive) was used as the olefin adhesive.

(Acrylic adhesive)
100 mole parts of butyl acrylate (BA) and acrylic 20 mol parts of acid 4-hydroxybutyl (4HBA), 0.5 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator per 100 parts by mass of these monomer components, and 100 parts by mass of the monomer components A mixture containing 150 parts by mass of ethyl acetate as a polymerization solvent was stirred under a nitrogen atmosphere at 62° C. for 5 hours and then at 75° C. for 2 hours (polymerization reaction). To 100 parts by mass of the acrylic polymer thus obtained, 2 parts by mass of Coronate HX (manufactured by Tosoh Corporation) as a cross-linking agent was added and stirred to obtain an acrylic pressure-sensitive adhesive.

[Preparation of surface modification composition]
<Preparation of surface-modified composition A>
Polyamide copolymer resin (Amilan CM8000 manufactured by Toray Industries, Inc.) 100 parts by mass, untreated fumed silica (M5 Cab-o-sil manufactured by CABOT) 12.5 parts by mass, acrylic polymer (ARUFON UC-3510 manufactured by Toagosei Co., Ltd.) ) was dispersed and dissolved in a mixed solvent of ethanol (EtOH) / water / isopropyl alcohol (IPA) = 68% by mass / 12% by mass / 20% by mass at 40 ° C., and a solid content of 20% by mass solution (surface modification composition) was prepared.

<Preparation of surface-modifying composition B>
100 mole parts of butyl acrylate (BA) and acrylic 20 mol parts of acid 4-hydroxybutyl (4HBA), 0.5 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator per 100 parts by mass of these monomer components, and 100 parts by mass of the monomer components A mixture containing 150 parts by mass of ethyl acetate as a polymerization solvent was stirred under a nitrogen atmosphere at 62° C. for 5 hours and then at 75° C. for 2 hours (polymerization reaction). As a result, a prepolymer solution containing hydroxyl group-containing acrylic polymer A1 as a prepolymer was obtained.

Next, a prepolymer solution containing the hydroxyl group-containing acrylic polymer A1, 2-methacryloyloxyethyl isocyanate (MOI) (trade name “Karenzu MOI”, manufactured by Showa Denko KK), and dibutyltin dilaurate as an addition reaction catalyst ( Wako Pure Chemical Industries, Ltd.) was stirred at 50° C. for 10 hours under an air atmosphere (addition reaction). In the reaction solution, the amount of MOI compounded is 0.2 molar equivalents to the above 4-hydroxybutyl acrylate (4HBA). Further, in the reaction solution, the amount of dibutyltin dilaurate compounded is 0.5 parts by mass with respect to 100 parts by mass of MOI. By this addition reaction, a surface-modified composition B containing acrylic polymer A2 having hydroxyl groups and unsaturated hydrocarbon groups in side chains and having a solid content concentration of 42.2% by mass was obtained.

[Example 1]

(Surface modified sheet (1))
On one side of a release sheet (Niftron 900UL: fluororesin sheet film manufactured by Nitto Denko Corporation (polytetrafluoroethylene (PTFE) (thickness: 0.05 mm, dimensions: width 250 mm x length 450 mm)), speed: 5 m / min, Corona treatment was performed under the conditions of the number of times: once and the voltage: 0.07 kW.
The prepared silicone adhesive A was applied to the corona-treated surface of the release sheet with an applicator and dried at 120° C. for 3 minutes to form an adhesive layer having a thickness of 60 μm. A release liner was laminated on the formed adhesive layer.

After filtering the prepared surface-modified composition A through a nylon mesh with an opening of 188 μm, it was applied to the non-corona-treated surface of the release sheet with an applicator and dried in a constant temperature dryer at 100 ° C. for 2 minutes to obtain a thickness of A surface-modified sheet (1) having a surface-modified layer with a thickness of 15 μm was produced.

(Surface modification member (1))
The release liner of the surface-modified sheet (1) prepared above was peeled off, and the pressure-sensitive adhesive layer was attached to the upper mold of the press machine of the vertical tightening mechanism. A carbon fiber reinforced thermosetting epoxy resin prepreg (manufactured by Toray Industries, Inc., trading card) (dimensions: width 150 mm x length 120 mm x thickness 1 mm) is set in the mold on the lower side of the press, and compression molding is performed by the press. A surface-modified member (1) was produced under pressure of 3 MPa, 150° C., 5 minutes).
When the press machine was cooled and the surface-modified member was taken out at a take-out temperature of 40°C, peeling occurred between the release sheet and the surface-modified layer in the surface-modified member, and the pressure-sensitive adhesive layer and the release sheet were separated from metal. It remained temporarily fixed to the mold. Then, a laminate of the resin member and the surface modified layer, that is, the surface modified member having the surface modified layer on the surface was taken out.

(Painted object (1))
On the surface modified layer of the surface modified member (1) from which the pressure-sensitive adhesive layer and the release sheet prepared above were peeled off, V top H (two-liquid curing urethane paint) manufactured by Dainippon Toryo Co., Ltd. was dried to a thickness of 25 μm. and cured at room temperature (25° C.) for 3 days to prepare a coated article (1).

[Example 2]
(Surface modified sheet (2))
A surface-modified composition was obtained in the same manner as in Example 1, except that the surface-modified composition described in Table 1 was used as the surface-modified composition, and the surface-modified layer was formed to have the thickness described in Table 1. A quality sheet (2) was produced.

(Surface modification member (2))
A resin sheet containing an unsaturated polyester resin (Kyocera Primix AP212SK2 manufactured by Kyocera Corporation) (dimensions: width 150 mm × length 120 mm × thickness 1 mm) was applied to the surface modification layer side of the surface modification sheet (2) prepared above. ) and subjected to compression molding with a press (molding pressure: 3 MPa, upper mold: 145°C, lower mold: 135°C, 4 minutes) to prepare a surface-modified member (2).

(Painted object (1))
A coated article (2) was produced in the same manner as in Example 1.

[Examples 3, 5, and 7]
A surface-modified sheet (3 ) (5) (7), surface-modified members (3) (5) (7), and coated objects (3) (5) (7).

[Examples 4, 6, and 8]
A surface-modified sheet ( 4) (6) and (8), surface-modified members (4), (6) and (8), and coated objects (4), (6) and (8) were produced.

[Examples 9 and 10]
As a base resin, a propylene-based resin (manufactured by Japan Polypropylene Co., Ltd., product name: Novatec PP FY6) was used for the A and B layers of the extruder, and as an adhesive resin, a propylene-based elastomer (olefin-based adhesive) (manufactured by Exxon Mobil) was used. , trade name: Vistamaxx 6202) is put into the C layer of the extruder, and the A layer / B layer / C layer = 25 µm / 25 µm / 10 µm, with a total thickness of 60 µm, is extruded to form a film, a release sheet and an adhesive. A stack of layers was obtained.
The side opposite to the pressure-sensitive adhesive layer of the release sheet was subjected to corona treatment under conditions of speed: 5 m/min, number of times: once, and voltage: 0.07 kW.
A surface-modified composition was obtained in the same manner as in Example 1 except that the surface-modified composition described in Table 2 was used as the surface-modified composition, and the surface-modified layer was formed to have the thickness described in Table 2. Quality sheets (9) and (10) were produced.

<Conditions for forming laminate of release sheet and pressure-sensitive adhesive layer>
In Examples 9 and 10, a laminate of a release sheet and an adhesive layer was formed using a three-kind, three-layer (A layer/B layer/C layer) extrusion T-die molding machine. The extrusion temperature was carried out under the following conditions.

Layer A: 220°C
Layer B: 220°C
Layer C: 220°C
Die temperature: 220°C

After co-extrusion molding from a T-die and integration, and the obtained base material sufficiently solidifying, it was wound into a roll shape to form a roll body.

[Example 11]
As the adhesive composition, the adhesive composition described in Table 2 was used, and after forming an adhesive layer so as to have the thickness described in Table 2, it was aged at 50 ° C. for 2 days to promote crosslinking. A surface-modified sheet (11) was produced in the same manner as in Example 1.
The surface of the surface-modified sheet (11) prepared above on the surface-modified layer side is placed on a low-temperature curing epoxy resin prepreg (manufactured by ENEOS Techno Material Co., Ltd.) (dimensions: width 150 mm x length 120 mm x thickness 1 mm). A surface-modified member (11) was produced by stacking and compression molding with a press (molding pressure: 3 MPa, 90° C., 1 hour).
The coated article (11) was produced in the same manner as in Example 1.

[Comparative Example 1]
A surface-modified sheet (r1), a surface-modified member (r1), and a coated article (r1) were produced in the same manner as in Example 1, except that no pressure-sensitive adhesive layer was provided and no release liner was used. [Comparative Example 2]
A surface-modified sheet (r2), a surface-modified member (r2), and a coated article (r2) were prepared in the same manner as in Example 2, except that no pressure-sensitive adhesive layer was provided and no release liner was used.

[Comparative Example 3]
A surface-modified sheet (r3), a surface-modified member (r3), and a coated article (r3) were produced in the same manner as in Example 1, except that no surface-modified layer was provided.

[Comparative Example 4]
A surface-modified sheet (r4), a surface-modified member (r4), and a coated article (r4) were produced in the same manner as in Example 7, except that no surface-modified layer was provided.

Examples and comparative examples are shown in Tables 1 and 2 below.

It was shown that the surface-modified sheets of the present invention all have moderate adhesion to SUS plates treated with release agents, and are excellent in temporary fixability to molds. In addition, the paint adhesion was excellent, and the surface modification performance was demonstrated. On the other hand, since the surface-modified sheet of Comparative Example 1 did not have an adhesive layer, the temporary fixability was poor. Since the coated objects of Comparative Examples 2 and 3 did not have a surface modification layer, the coating adhesion was poor.

According to the present invention, a surface-modified sheet excellent in temporary fixability, a laminate using the surface-modified sheet, a surface-modified member, a coated article, a joined body, a method for producing a surface-modified member, and a coated article A manufacturing method and a manufacturing method of a joined body can be provided.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2022-029888) filed on February 28, 2022, the content of which is incorporated herein by reference.

10 Surface modification layer 20 Release sheet 30 Coating film 40 Adhesive layer 50 Adhesive layer 100 Resin member (first resin member)
101 resin member (second resin member)
200 surface-modified sheet 300 coated object 400 resin material 500 adherend 600 joined body (first joined body)
601 conjugate (second conjugate)

Claims

A surface-modified sheet comprising a surface-modified layer, a release sheet, and an adhesive layer in this order.
The surface-modified sheet according to claim 1, wherein a release liner is provided on the surface of the pressure-sensitive adhesive layer opposite to the release sheet.
The surface-modified sheet according to claim 1, wherein the pressure-sensitive adhesive layer is formed from a silicone-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, an olefin-based pressure-sensitive adhesive, or an acrylic pressure-sensitive adhesive.
The surface-modified sheet according to claim 1, wherein the surface-modified layer has an easy-adhesion function.
A laminate in which the surface-modified sheet according to any one of claims 1 to 4 is laminated on at least part of the surface of a resin material.
The laminate according to claim 5, wherein the resin material contains a fiber-reinforced resin.
The surface modified layer in the surface modified sheet according to any one of claims 1 to 4 is laminated on at least a part of the surface of the resin member, and the resin member and the surface modified layer are welded and mixed. Or a covalently bonded surface modification member.
A coated article comprising a coating film on at least a part of the surface modification member according to claim 7.
A bonded body in which an adhesive layer is provided on at least a part of the surface modifying member according to claim 7, and the adherend and the surface modifying member are bonded via the adhesive layer.
A second resin member is laminated on at least a part of the surface on the surface modification layer side of the surface modification member according to claim 7, and the second resin member and the surface modification layer are welded and mixed or covalently bonded conjugate.
A method for manufacturing a surface-modified member using the surface-modified sheet according to any one of claims 1 to 4.
The method for manufacturing a surface-modified member according to claim 11, comprising a lamination step of laminating the surface-modified layer on the resin member by thermoforming.
A method for producing a coated object using the surface-modified sheet according to any one of claims 1 to 4.
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
14. The method of manufacturing a coated object according to claim 13, comprising the step of forming a coating film on the surface modification layer side of the surface modification member.
A method for manufacturing a joined body using the surface-modified sheet according to any one of claims 1 to 4.
11. The method for manufacturing a joined body according to claim 10, comprising the step of laminating the second resin member on at least part of the surface of the surface-modified member on the surface-modified layer side by thermoforming, A method for producing a conjugate.
a step of laminating the surface-modified layer on a resin member by thermoforming to produce a surface-modified member;
forming an adhesive layer on the surface modification layer side of the surface modification member;
16. The method for producing a joined body according to claim 15, comprising the step of joining an adherend and said surface modifying member via said adhesive layer.