WO2024071274A1

WO2024071274A1 - Surface modification composition, surface modification layer, surface modification sheet, multilayer body, surface-modified member, coated article, method for producing surface-modified member, method for producing coated article, member with functional layer, and method for producing member with functional layer

Info

Publication number: WO2024071274A1
Application number: PCT/JP2023/035320
Authority: WO
Inventors: 一輝笹原; 涼平大幡; 絵里子中尾; 明日香遠藤
Original assignee: 日東電工株式会社
Priority date: 2022-09-28
Filing date: 2023-09-27
Publication date: 2024-04-04

Abstract

The purpose of the present invention is to provide a surface modification composition which enables a surface treatment to be performed simultaneously with molding of a resin member, and which is capable of forming a surface modification layer that has high adhesion and excellent coverage, while being suppressed in covering variation. The present invention relates to a surface modification composition containing a polymer component, wherein the loss tangent (tanδ) of a surface modification layer that is formed of this surface modification composition is 1.06 or less at 145°C as determined by dynamic viscoelasticity measurement, and the number average molecular weight of the polymer component is 20,000 or more.

Description

Surface modification composition, surface modification layer, surface modification sheet, laminate, surface modification member, coated article, method for manufacturing surface modification member, method for manufacturing coated article, member with functional layer, and method for manufacturing member with functional layer

The present invention relates to a surface modification composition, a surface modification layer, a surface modification sheet, a laminate, a surface modification member, a coated article, a method for manufacturing a surface modification member, a method for manufacturing a coated article, a member with a functional layer, and a method for manufacturing a member with a functional layer.

In recent years, lightweight, impact-resistant resins have been used in components for transportation equipment such as railroad cars, aircraft, ships, and automobiles, electronic devices, and housing equipment, with adherends of various materials being bonded to their surfaces. In addition, coatings with various functions are formed on resin components. For example, resin components that use unsaturated polyester resin, a type of thermosetting resin, as the matrix resin are used for bathtubs and automobile exteriors, and when used for automobile exteriors in particular, unsaturated polyester resin components with a coating made of paint are used.

When joining a resin member to a metal or other resin, sufficient adhesion is required. Conventionally, rubber-epoxy curable resin compositions have been known as such adhesives. However, resin members are poorly compatible with adhesives, and sufficient adhesive strength cannot be obtained even when conventional adhesives or adhesive sheets are used. In addition, resin members with excellent strength, such as fiber composite materials, require a high level of adhesive strength.
For this reason, the adhesion of resin members requires the application of a primer solution, and prior to the application of the primer solution, various surface treatments such as sandblasting, corona treatment, and plasma treatment are required as pretreatments. Such surface treatment methods increase the number of manufacturing steps, lowering productivity and creating problems in terms of cost. They also increase the burden on the working environment and the external environment.

On the other hand, one method for treating resin components to make them more adhesive and provide them with sufficient adhesive strength is to use a technology that uses a surface-modified composition in sheet form. Normally, the above-mentioned surface treatment is performed on samples after molding, but for example, Patent Document 1 describes a technology in which surface treatment is performed simultaneously with molding, such as a surface-modified sheet that can provide sufficient adhesive strength to thermoplastic resins. Furthermore, Patent Document 2 describes a surface-modified sheet that can provide sufficient adhesive strength to thermosetting resins such as thermosetting elastomers.

Japanese Patent Publication No. 2017-128722 Japanese Patent Publication No. 2019-194015

When molding a resin part, a resin material that is small compared to the area of the mold may be used. In this case, the resin material flows significantly inside the mold during molding, making it extremely difficult to perform surface treatment using a surface modification sheet at the same time as molding the resin part. With conventional techniques, the surface modification layer flows, which can reduce the uniformity of the coverage rate and thickness of the surface modification layer on the treated surface of the resin part, resulting in uneven coverage, making it impossible to obtain a sufficient surface treatment effect.

The present invention provides a surface modification composition that can be used to perform surface treatment simultaneously with molding of a resin member by controlling the fluidity of the surface modification composition, and can form a surface modification layer that has excellent coverage and reduced coating variation and has high adhesion. It also provides a surface modification layer, a surface modification sheet, a laminate, a surface modification member, a coated article, a method for manufacturing a surface modification member, a method for manufacturing a coated article, a member with a functional layer, and a method for manufacturing a member with a functional layer that uses the same.

The means for solving the above problems are as follows.
[1]
A surface modification composition comprising a polymer component,
The surface modification layer formed from the surface modification composition has a loss tangent (tan δ) at 145 ° C. obtained by dynamic viscoelasticity measurement of 1.06 or less;
The surface modification composition, wherein the polymer component has a number average molecular weight of 20,000 or more.
[2]
The surface modification composition according to [1], wherein the polymer component comprises a polymer, partial polymer, or copolymer of a (meth)acrylic monomer.
[3]
The surface modification composition according to [2], wherein the (meth)acrylic monomer is a methacrylic acid alkyl ester.
[4]
The surface modification composition according to claim 1, wherein the polymer component contains a hydroxyl group.
[5]
The surface modification composition according to claim 4, wherein the polymer component further comprises an unsaturated hydrocarbon group.
[6]
A surface modification layer formed from the surface modification composition according to any one of [1] to [5].
[7]
A surface-modified sheet having a surface-modified layer according to [6].
[8]
A surface modified sheet comprising the surface modified layer according to [6] and a release sheet.
[9]
A laminate comprising the surface modification layer according to [6] laminated on at least a part of the surface of a resin material.
[10]
The surface modification layer according to [6] is laminated on at least a part of a surface of a resin member,
A surface-modified member in which the resin member and the surface-modified layer are covalently bonded together by a chemical reaction.
[11]
The surface-modified member according to claim 10, wherein the resin member contains an unsaturated hydrocarbon group-containing thermosetting resin.
[12]
The surface modified member according to [11], wherein the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin.
[13]
A coated article having a coating film on at least a part of the surface modified member according to [10].
[14]
A method for producing a surface modified member using the surface modified layer according to [6],
A method for producing a surface-modified member, comprising: laminating the surface-modified layer onto a resin member by hot molding.
[15]
The method for producing a surface-modified member according to [10], wherein the resin member contains an unsaturated polyester resin.
[16]
A method for producing a surface-modified member using the surface-modified sheet according to [7].
[17]
A method for producing a coated article using the surface modification layer according to [6],
A method for producing a surface-modified member, comprising: laminating the surface-modified layer on a resin member by hot molding; and forming a coating film on the surface-modified layer side of the surface-modified member.
[18]
The method for producing a coated article according to [17], wherein the resin member contains an unsaturated polyester resin.
[19]
A method for producing a coated article using the surface modified sheet according to [7].
[20]
A functional layer-attached member having a functional layer on at least a portion of the surface of the surface-modified layer side of the surface-modified member described in [10].
[21]
A method for producing a functional layer-attached member according to [20],
A method for manufacturing a member with a functional layer, comprising: a step of manufacturing a surface-modified member by laminating the surface-modified layer onto the resin member by hot molding; and a step of forming the functional layer on the surface-modified layer side of the surface-modified member.
[22]
A method for producing a functional layer-attached member using the surface modification layer according to [6],
A method for manufacturing a member with a functional layer, comprising: a step of manufacturing a surface-modified member by laminating the surface-modified layer onto a resin member by hot molding; and a step of forming a functional layer on the surface-modified layer side of the surface-modified member.
[23]
The method for producing a member with a functional layer according to [22], wherein the resin member contains an unsaturated polyester resin.
[24]
A method for producing a functional layer-attached member using the surface modified sheet according to [7].

The surface modification composition according to an embodiment of the present invention is capable of simultaneously performing surface treatment on a resin member during molding and processing, and can form a surface modification layer that has excellent coverage, suppresses coating variation, and has high adhesion. In addition, the present invention provides a surface modification layer, a surface modification sheet, a laminate, a surface modification member, a coated article, a method for manufacturing a surface modification member, a method for manufacturing a coated article, a member with a functional layer, and a method for manufacturing a member with a functional layer, which use the same.

FIG. 1 is a schematic cross-sectional view showing an example of a surface modification member. FIG. 2 is a schematic cross-sectional view showing another example of the surface modified member. FIG. 3 is a schematic cross-sectional view showing another example of the surface modification member. FIG. 4 is a schematic cross-sectional view showing an example of a laminate of a surface-modified member and a resin member. FIG. 5 is a schematic cross-sectional view showing an example of a surface modified sheet. FIG. 6 is a schematic cross-sectional view showing a form in which the surface modification layer side of a surface modification sheet, which is a laminate of a release sheet and a surface modification layer, is placed on at least a part of the surface of a resin material. FIG. 7 is a schematic cross-sectional view showing an example of a coated article. FIG. 8 is a schematic cross-sectional view showing an example of a functional layer-attached member.

The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be modified as desired without departing from the gist of the present invention. In addition, the use of "to" to indicate a numerical range means that the numerical values before and after it are included as the lower and upper limits. In addition, in the following drawings, components and parts that perform the same function may be described using the same reference numerals, and duplicate descriptions may be omitted or simplified. In addition, the embodiments shown in the drawings are schematic in order to clearly explain the present invention, and do not necessarily accurately represent the size or scale of actual devices, etc.

[Surface Modification Composition]
A surface modification composition according to an embodiment of the present invention is a surface modification composition containing a polymer component, wherein a surface modification layer formed from the surface modification composition has a loss tangent (tan δ) at 145°C obtained by dynamic viscoelasticity measurement of 1.06 or less, and the number average molecular weight of the polymer component is 20,000 or more.

As described above, when molding a resin part using a resin material that is small compared to the area of the mold, the resin material flows significantly within the mold during molding, making it extremely difficult to perform surface treatment at the same time as molding the resin part.
When a surface-modified member is integrally molded using a resin material and a surface-modified sheet, the surface-modified layer flows in a mold in a conventional method, and there are areas on the treated surface of the resin member that are not covered by the surface-modified layer, or the thickness uniformity is reduced, resulting in coating variations. In addition, the adhesion between the resin member and the surface-modified layer and the adhesion between the surface-modified layer and the coating film were insufficient.
The surface modification composition according to an embodiment of the present invention has a loss tangent (tan δ) of 1.06 or less at 145°C of the surface modification layer formed using the surface modification composition, thereby controlling the fluidity of the surface modification layer near the molding temperature of the resin material, enabling surface treatment to be performed simultaneously with molding of the resin part, and forming a surface modification layer that has excellent coverage, suppresses coating variation, and has high adhesion.

(tan δ)
In the surface modification composition according to the embodiment of the present invention, the loss tangent (tan δ) at 145° C. of the surface modification layer formed using the surface modification composition is 1.06 or less.
If the loss tangent (tan δ) exceeds 1.06, the fluidity of the surface modification layer near the molding temperature of the resin material increases, making it difficult to perform surface treatment simultaneously with molding processing of the resin part, reducing the coverage rate, causing coating variations, and making it impossible to form a surface modification layer with high adhesion.
The loss tangent (tan δ) is desirably 1.06 or less, and although there is no particular limitation on the lower limit, it is preferably 1.00 or less, more preferably 0.90 or less, more preferably 0.80 or less, more preferably 0.70 or less, more preferably 0.60 or less, more preferably 0.50 or less, more preferably 0.40 or less, more preferably 0.30 or less, more preferably 0.20 or less, more preferably 0.10 or less, and even more preferably 0.05 or less.
By setting the loss tangent (tan δ) to 1.06 or less, the fluidity of the surface modification layer near the molding temperature of the resin material can be controlled, and the surface treatment can be performed simultaneously with the molding process of the resin part. It is possible to form a surface modification layer that has excellent coverage, suppresses coverage variation, and has high adhesion.

The loss tangent (tan δ) can be determined, for example, by measuring the dynamic viscoelasticity using a dynamic viscoelasticity measuring device (Advanced Rheometric Expansion System (ARES)) manufactured by Rheometric Scientific, or by measuring the dynamic viscoelasticity using an RSA-G2 manufactured by TA Instruments.

Dynamic viscoelasticity measurements use a surface modification layer formed by volatilizing the volatile components of the surface modification composition as a sample, and can obtain the shear storage modulus G', shear loss modulus G'', and complex shear modulus G within the measurement temperature range (e.g., 145°C), and can also determine the loss tangent tan δ (shear loss modulus G''/shear storage modulus G') at 145°C.

Furthermore, the surface modification layer formed by volatilizing the volatile components of the surface modification composition can be used as a sample, and the tensile storage modulus E', tensile loss modulus E", and complex tensile modulus E can be obtained as the tensile modulus of the sample at each temperature (e.g., 145°C). The obtained tensile modulus (E, E', E") can be converted to the shear modulus G based on the relationship E = 3G by assuming a Poisson's ratio of 0.5. Therefore, the loss tangent (tan δ) can also be obtained from the tensile modulus as (tensile loss modulus E"/tensile storage modulus E').

More specifically, dynamic viscoelasticity can be measured by laminating the surface-modified layers constituting the part to be measured to a thickness of 1.5 mm, autoclaving (0.5 MPa, 50°C, 15 minutes), adhering each layer to each other, and using the laminate as the measurement sample, and measuring in the following manner.
The laminate is punched out into a disk shape with a diameter of 7.9 mm to prepare a test specimen. Dynamic viscoelasticity measurement is performed under the following conditions using an Advanced Rheometric Expansion System (ARES) manufactured by Rheometric Scientific. From the measurement results, the shear storage modulus G' and complex shear modulus G of the sample at 145°C are obtained.
[Measurement condition]
Deformation mode: torsion Measurement frequency: 1 Hz
Temperature range: 20℃ to 150℃
Heating rate: 5°C/min. Shape: Parallel plate 7.9mmφ

Alternatively, the surface modified layer having a thickness of 25 μm is punched out to a size of 70 mm×10 mm, and this is used as a measurement sample.
Using a TA Instruments RSA-G2, dynamic viscoelasticity measurements are performed under the following conditions with the sample in a state without plastic deformation or deflection. From the measurement results, the tensile storage modulus E' and complex tensile modulus E of the sample at 145°C are obtained. The obtained tensile modulus (E, E') can be converted to the shear modulus G based on the relational equations E = 3G, E' = 3G' by assuming a Poisson's ratio of 0.5.
[Measurement condition]
Deformation mode: Tensile Measurement frequency: 1 Hz
Temperature range: 20℃ to 150℃
Heating rate: 5° C./min

The loss tangent (tan δ) can be adjusted to the desired range by adjusting the type, composition, and number average molecular weight of the polymer components, adjusting the molecular weight based on the application of external stimuli, introducing components other than the polymer components (e.g., low molecular weight components such as crosslinkers, monomers, and plasticizers, as well as other additives and fillers), and physical treatments such as active energy ray curing, as well as other commonly known elastic modulus adjustment methods.

(Number average molecular weight of polymer component)
In the surface modification composition according to an embodiment of the present invention, the number average molecular weight of the polymer component is 20,000 or more.

By making the number average molecular weight of the polymer component 20,000 or more, the fluidity of the surface modification layer can be controlled, a surface modification layer with high coverage and reduced coating variation can be formed on the surface of the resin member, and a surface modification member with excellent adhesion can be obtained. If the number average molecular weight of the polymer component is less than 20,000, it becomes easy to flow, the coverage rate on the surface of the resin member decreases, the coating variation increases, and excellent adhesion cannot be obtained. The number average molecular weight of the polymer component is not particularly limited, but is preferably 20,000 or more, preferably 50,000 or more, preferably 100,000 or more, preferably 250,000 or more, preferably 500,000 or more, preferably 750,000 or more, preferably 1,000,000 or more, preferably 2,500,000 or more, preferably 5,000,000 or more, preferably 7,500,000 or more, and may be 10,000,000 or more.

The number average molecular weight of the polymer component is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

(Polymer Component)
The surface modification composition includes a polymer component.
The polymer component is not particularly limited, but examples thereof include publicly known and commonly used polymers such as (meth)acrylic polymers, rubber polymers, silicone polymers, styrene polymers, polyester polymers, urethane polymers, polyamide polymers, epoxy polymers, vinyl alkyl ether polymers, and fluorine polymers. Among these, (meth)acrylic polymers are preferred from the viewpoints of transparency, weather resistance, etc. These polymer components may be used alone or in combination of two or more.
That is, the polymer component contained in the surface modification composition (which may be the surface modification layer) according to the embodiment of the present invention preferably contains a (meth)acrylic polymer.
In the present invention, the (meth)acrylic polymer refers to an acrylic polymer and/or a methacrylic polymer, and the (meth)acrylate refers to an acrylate and/or a methacrylate.

The polymer component may contain a polymer, partial polymer, or copolymer of the monomer component corresponding to the polymer component.

The polymer component contained in the surface modification composition (which may be the surface modification layer) according to the embodiment of the present invention preferably contains a (meth)acrylic polymer, and the (meth)acrylic polymer preferably contains a polymer, partial polymer, or copolymer of a (meth)acrylate monomer. The (meth)acrylate monomer is preferably a methacrylate monomer.

The surface modification composition according to the embodiment of the present invention may also contain a monomer component.

The surface modification composition according to the embodiment of the present invention is preferably an acrylic surface modification composition mainly composed of a (meth)acrylic polymer. The specific content of the (meth)acrylic polymer is not particularly limited, but is preferably 25% by mass or more (e.g., 25 to 99.9% by mass) relative to the total amount of the surface modification composition according to the embodiment of the present invention (total mass, 100% by mass), 50% by mass or more (e.g., 50 to 99.9% by mass), 60% by mass or more (e.g., 60 to 99.9% by mass), 70% by mass or more (e.g., 70 to 99.9% by mass), 75% by mass or more (e.g., 75 to 99.9% by mass), 80% by mass or more (e.g., 80 to 99.9% by mass), 85% by mass or more (e.g., 85 to 99.9% by mass), and more preferably 90% by mass or more (e.g., 90 to 99.9% by mass).

　(Meth)acrylic polymers are not particularly limited, but methacrylic polymers can be used preferably. The use of a higher ratio of methacrylic components in the polymer components (including all of partial polymers, copolymers, and polymers) is more preferable. The ratio of methacrylic monomers to the total monomer components forming the polymer is not particularly limited, but may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 30% by mass or less. The lower limit is not particularly limited, but may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more.

The (meth)acrylic polymer can be obtained, for example, by polymerizing a (meth)acrylic monomer component.
The (meth)acrylic monomer is not particularly limited in composition, but examples thereof include hydroxyl group-free (meth)acrylic monomers and hydroxyl group-containing (meth)acrylic monomers.

The (meth)acrylic polymer is not particularly limited, but in cases where the coating material contains an isocyanate group, it is preferable to form the polymer from a monomer component that contains a non-hydroxyl group-containing (meth)acrylic monomer or a hydroxyl group-containing (meth)acrylic monomer, and it is more preferable to form the polymer from a monomer component that contains a non-hydroxyl group-containing (meth)acrylic monomer and a hydroxyl group-containing (meth)acrylic monomer. The above composition is one example, and can be adjusted according to the composition of the coating material and the composition of the resin.

Examples of the hydroxyl group-free (meth)acrylic monomer include (meth)acrylic acid alkyl esters, isocyanate group-containing monomers, epoxy group-containing monomers, amino group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, heterocycle-containing monomers having a heterocycle with only nitrogen atoms as heteroatoms, heterocycle-containing monomers having a heterocycle with nitrogen atoms and oxygen atoms as heteroatoms, heterocycle-containing monomers having a heterocycle containing nitrogen atoms and sulfur atoms as heteroatoms, (meth)acrylic acid esters having an alicyclic hydrocarbon group, methacrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an alicyclic ring-containing group, (meth)acrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an aromatic ring-containing group, heterocycle-containing monomers, carboxyl group-containing monomers, and (meth)acrylic acid alkoxyalkyl esters having an alkoxy group having 5 or less carbon atoms. Examples of the monomers include substituted methylene compounds in which all carbons of the repeating unit of the main chain have side chains, (meth)acrylic acid alkoxyalkyl esters, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, vinyl esters (vinyl acetate, vinyl propionate, etc.), aromatic vinyl compounds (styrene, vinyl toluene, etc.), olefins or dienes (ethylene, propylene, butadiene, isoprene, isobutylene, etc.), vinyl ethers (vinyl alkyl ethers, etc.), vinyl chloride, vinyl alcohol, macromonomers with a weight average molecular weight of 30,000 or less, polyfunctional monomers having two or more polymerizable functional groups, and (meth)acrylic acid esters having aromatic hydrocarbon groups, among which (meth)acrylic acid alkyl esters, amide group-containing monomers, and (meth)acrylic acid esters having alicyclic hydrocarbon groups are preferred, and (meth)acrylic acid alkyl esters are more preferred. These may be used alone or in combination of two or more.
In this specification, the term "(meth)acrylic acid" refers to acrylic acid and/or methacrylic acid.

Examples of (meth)acrylic acid alkyl esters include (meth)acrylic acid alkyl esters having a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples of such (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl acrylate, isotridodecyl (meth)acrylate, tetradecyl (meth)acrylate, and isotetradecyl (meth)acrylate. [0113] Examples of the acrylates include pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, bornyl (meth)acrylate, and Examples of this include isobornyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and 6-(1,1'-biphenyl-4-yloxy)hexyl (meth)acrylate.

From the viewpoint of improving adhesion, the (meth)acrylic acid alkyl ester is not particularly limited, but preferred examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.

Examples of isocyanate group-containing monomers include 2-isocyanatoethyl (meth)acrylate.

Examples of epoxy group-containing monomers include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and 2-ethyl glycidyl ether (meth)acrylate, and glycidyl ether (meth)acrylate.

Examples of amino group-containing monomers include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate.

Examples of nitrile group-containing monomers include (meth)acrylonitrile.

Examples of amide group-containing monomers include (meth)acrylamide; N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di(n-butyl) (meth)acrylamide, and N,N-di(t-butyl) (meth)acrylamide; N-alkyl (meth)acrylamides such as N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, and N-n-butyl (meth)acrylamide; monomers having a hydroxyl group and an amide group, such as N-(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N-hydroxyalkyl (meth)acrylamides such as N-(1-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl) (meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide, and N-(4-hydroxybutyl) (meth)acrylamide; monomers having an alkoxy group and an amide group, such as N-alkoxyalkyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide; and others such as N,N-dimethylaminopropyl (meth)acrylamide and N-(meth)acryloylmorpholine.

(Meth)acrylamides also include various N-alkoxyalkyl(meth)acrylamides, such as N-methoxymethyl(meth)acrylamide and N-butoxymethyl(meth)acrylamide.

Examples of heterocycle-containing monomers having a heterocycle with only nitrogen atoms as heteroatoms include N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, and N-vinylpyrazole.

Examples of heterocycle-containing monomers having a heterocycle with a nitrogen atom and an oxygen atom as heteroatoms include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-(meth)acryloyl-2-pyrrolidone, N-vinyloxazole, N-vinylisoxazole, N-vinylmorpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-vinyl-1,3-oxazine-2- ion, N-vinyl-3,5-morpholinedione, N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene succinimide, N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N-lauryl itaconimide, etc.

Examples of heterocycle-containing monomers having a heterocycle containing a nitrogen atom and a sulfur atom as heteroatoms include N-vinyl thiazole and N-vinyl isothiazole.

Examples of (meth)acrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an alicyclic ring-containing group include (meth)acrylic acid cycloalkyl esters having a cycloalkane ring (cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc.), (meth)acrylic acid esters having a bicyclic hydrocarbon ring (pinane, pinene, bornane, norbornane, norbornene, etc.), and (meth)acrylic acid esters having a tricyclic or higher aliphatic hydrocarbon ring (dicyclopentane ring, dicyclopentene ring, adamantane ring, tricyclopentane ring, tricyclopentene ring, etc.).

Examples of (meth)acrylic acid cycloalkyl esters include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate.

Examples of (meth)acrylic acid esters having a bicyclic hydrocarbon ring include bornyl (meth)acrylate and isobornyl (meth)acrylate.

Examples of (meth)acrylic acid esters having three or more hydrocarbon rings include dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

(Meth)acrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an aromatic ring-containing group include, for example, compounds having an aromatic carbon ring (for example, a monocyclic carbon ring such as a benzene ring, or a condensed carbon ring such as a naphthalene ring), and specific examples include benzyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and 6-(1,1'-biphenyl-4-yloxy)hexyl (meth)acrylate.

Heterocycle-containing monomers are copolymerizable monomers having heterocycles such as heterocycles having only nitrogen atoms as heteroatoms (pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, pyrimidine, pyrroline, piperazine, pyrazine, etc.), heterocycles having nitrogen and oxygen atoms (pyrrolidone, oxazole, isoxazole, morpholine, morpholinone, piperidone, lactam, oxazine, morpholinedione, succinimide, itaconimide, etc.), heterocycles having nitrogen and sulfur atoms (thiazole, isothiazole, thiazine), heterocycles having oxygen atoms (lactone, tetrahydrofuran, furan, tetrahydropyran, dioxane, etc.), and heterocycles having sulfur atoms (tetrahydrothiophene, thiophene, tetrahydrothiopyran, thiopyran, etc.).

Examples of carboxyl group-containing monomers include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. The carboxyl group-containing monomers also include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride. They may also be derivatives formed by ester bonding with itaconic acid, for example.

Examples of (meth)acrylic acid alkoxyalkyl esters having an alkoxy group with 5 or less carbon atoms include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate.

Examples of the sulfonic acid group-containing monomer include sodium vinyl sulfonate.

　Macromonomers are high molecular weight monomers formed by polymerizing multiple monomer components. When a macromonomer is used, the constituent units derived from the monomer components that make up the macromonomer are present in the base polymer in a certain degree of continuity. Therefore, by using a macromonomer, a high-order structure derived from the macromonomer can be introduced into the base polymer, and the properties required of a surface modifier (adhesive strength, cohesive strength, optical properties, fluidity, step-following ability, etc.) can be easily adjusted. The weight-average molecular weight of the macromonomer is not particularly limited, but is preferably 3,000 to 35,000, more preferably 4,000 to 30,000, even more preferably 5,000 to 25,000, and even more preferably 6,000 to 20,000.

Examples of the polyfunctional monomer having two or more polymerizable functional groups include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, polyester acrylate, urethane acrylate, etc. The polyfunctional monomers can be used alone or in combination of two or more.

The non-hydroxyl group-containing (meth)acrylic monomers may be used alone or in combination of two or more types.

In addition, in the surface modification composition according to the embodiment of the present invention, the polymer component preferably contains a hydroxyl group. The polymer component contains a hydroxyl group and may further contain an unsaturated hydrocarbon group. By containing a polymer component having a hydroxyl group or having a hydroxyl group and an unsaturated hydrocarbon group, the surface modification composition according to the embodiment of the present invention can form a surface modification layer that has better adhesion to the coating film, the resin, or both the resin and the coating film.

In the surface modification composition according to an embodiment of the present invention, the polymer component having a hydroxyl group and an unsaturated hydrocarbon group may include an addition reaction product between a polymer having a unit derived from a hydroxyl group-containing monomer and an unsaturated hydrocarbon group-containing compound.
That is, the polymer component preferably contains a hydroxyl group-containing monomer, more preferably a hydroxyl group-containing (meth)acrylic monomer, as a constituent monomer component. Among the hydroxyl group-containing (meth)acrylic monomers, a hydroxyl group-containing (meth)acrylic acid alkyl ester is preferred.

The polymer component of the surface modification composition according to the embodiment of the present invention more preferably contains a polymer having a unit derived from a non-hydroxyl group-containing (meth)acrylic monomer and a unit derived from a hydroxyl group-containing (meth)acrylic monomer, or an addition reaction product of the polymer and an unsaturated hydrocarbon group-containing compound.

Examples of the hydroxyl group-containing (meth)acrylic acid alkyl ester include (meth)acrylate compounds containing a crosslinkable functional group having a hydroxyl group.
Examples of the crosslinkable functional group-containing (meth)acrylate compound having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, and 4-hydroxymethylcyclohexyl (meth)acrylate; polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polybutylene glycol mono(meth)acrylate; but are not limited thereto.
Alternatively, a hydroxyl group may be added to the (meth)acryloyl group by addition reaction, etc. Therefore, the chain length from the main chain to the hydroxyl group located at the end of the side chain can be adjusted as desired.
The hydroxyl group-containing (meth)acrylic acid alkyl esters may be used alone or in combination of two or more kinds.
The hydroxyl group-containing (meth)acrylic acid alkyl ester is preferably at least one member selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

In the surface modification composition according to an embodiment of the present invention, the content of the hydroxyl group-containing monomer, such as the hydroxyl group-containing (meth)acrylic acid alkyl ester, is preferably 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, 5 mol or more, 10 mol or more, or may be 15 mol or more, based on 100 mol parts of the total monomer components. Also, it is preferably 50 mol or less, more preferably 40 mol or less, 30 mol or less, or 20 mol or less. If the hydroxyl group-containing monomer is 1 mol part or more, an amount of hydroxyl groups suitable for interacting with the paint is obtained, and adhesion to the paint is good. Also, if the hydroxyl group-containing monomer is 50 mol parts or less, gelation that occurs during the polymerization process of the polymer, which makes production difficult, can be prevented.

The monomer component may contain, in addition to the above-mentioned hydroxyl group-free (meth)acrylic monomer and hydroxyl group-containing monomer, one or more other monomers copolymerizable therewith (copolymerizable monomers).
Examples of the copolymerizable monomer include a monomer having a nitrogen atom-containing ring, a sulfonic acid group-containing monomer, an aromatic vinyl compound, and a (meth)acrylic acid ester having an aromatic hydrocarbon group.

　Examples of monomers having a nitrogen atom-containing ring include N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, and N-vinylisothiazole.

Examples of sulfonic acid group-containing monomers include styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic acid.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, and vinyltoluene.

Examples of (meth)acrylic acid esters having an aromatic hydrocarbon group include carbon aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate, methoxybenzyl (meth)acrylate, ethoxylated phenol (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxybutyl (meth)acrylate, cresyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and chlorobenzyl (meth)acrylate. p) acrylates: bromine-substituted aromatic ring-containing (meth)acrylates such as 2-(4,6-dibromo-2-s-butylphenoxy)ethyl (meth)acrylate, 2-(4,6-dibromo-2-isopropylphenoxy)ethyl (meth)acrylate, 6-(4,6-dibromo-2-s-butylphenoxy)hexyl (meth)acrylate, 6-(4,6-dibromo-2-isopropylphenoxy)hexyl (meth)acrylate, 2,6-dibromo-4-nonylphenyl acrylate, and 2,6-dibromo-4-dodecylphenyl acrylate; Phenoxybenzyl (meth)acrylate (e.g., m-phenoxybenzyl (meth)acrylate), thiophenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, o-phenylphenol (meth)acrylate, biphenyl methyl (meth)acrylate, 1-naphthyl methyl (meth)acrylate (also known as 1-naphthalene methyl (meth)acrylate), hydroxyethylated β-naphthol acrylate, 2-naphthoethyl (meth)acrylate, 2-naphthoxyethyl acrylate, 2-(4-methoxyethyl)-2-naphthyl acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (meth)acrylate, (meth)acryloyloxymethyl dinaphthothiophene, (meth)acryloyloxyethyl dinaphthothiophene, (meth)acryloyl group-containing dinaphthothiophene, (meth)allyloxy dinaphthothiophene, (meth)acryloyl group-containing dibenzothiophene, and vinyl group-containing dibenzothiophene.

In the surface modification composition according to an embodiment of the present invention, when the monomer component contains the copolymerizable monomer, the content of the copolymerizable monomer, as the total amount together with the hydroxyl group-containing (meth)acrylic acid alkyl ester, relative to 100 molar parts of the (meth)acrylic acid alkyl ester, is preferably 1 molar part or more, 2 molar parts or more, 3 molar parts or more, 4 molar parts or more, 5 molar parts or more, 6 molar parts or more, 7 molar parts or more, 8 molar parts or more, 9 molar parts or more, 10 molar parts or more, 15 molar parts or more, 20 molar parts or more, 25 molar parts or more, and is preferably 50 molar parts or less, more preferably 40 molar parts or less, 30 molar parts or less.

The (meth)acrylic polymer can be obtained by mixing the above-mentioned monomer components or polymerizing them by a known or conventional polymerization method. The polymerization method is not particularly limited, but includes, for example, solution polymerization, bulk polymerization, polymerization by active energy ray irradiation (active energy ray polymerization method) and emulsion polymerization. Among them, the solution polymerization method and the active energy ray polymerization method are preferred in terms of transparency, cost, etc. of the surface modification composition.
In solution polymerization, for example, a monomer component and a polymerization initiator are mixed in a solvent to prepare a reaction solution, and then the reaction solution is heated. Then, a polymer solution can be obtained by subjecting the monomer component to a polymerization reaction in the reaction solution. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used depending on the polymerization method. The polymerization initiator can be used alone or in combination of two or more kinds. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.001 to 10.0 parts by mass, more preferably 0.01 to 5.0 parts by mass, based on 100 parts by mass of the monomer component.

The active energy rays irradiated during the active energy ray polymerization (photopolymerization) include, for example, ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron beams, as well as ultraviolet rays, with ultraviolet rays being particularly preferred. Furthermore, there are no particular limitations on the irradiation energy, irradiation time, irradiation method, etc. of the active energy rays, as long as they can activate the photopolymerization initiator and cause a reaction of the monomer components.

Thermal polymerization initiators include, for example, azo polymerization initiators, peroxide polymerization initiators, and persulfates such as potassium persulfate. Azo polymerization initiators include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, and 2,2'-azos(2-amidinopropane) dihydrochloride. Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, redox polymerization initiators, and lauroyl peroxide. Among these, the azo polymerization initiators disclosed in JP 2002-69411 A are preferred.

The amount of the thermal polymerization initiator used, for example, in the case of the azo-based polymerization initiator, is preferably 0.05 to 0.5 parts by mass, and more preferably 0.1 to 0.3 parts by mass, per 100 parts by mass of all constituent units of the polymer component.

The photopolymerization initiator is not particularly limited, but examples thereof include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. The photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is not particularly limited, but is preferably 0.001 to 10.0 parts by mass, and more preferably 0.01 to 5.0 parts by mass, per 100 parts by mass of all structural units of the polymer component.

(Unsaturated Hydrocarbon Group)
An unsaturated hydrocarbon group may be introduced into the polymer component contained in the surface modification composition according to the embodiment of the present invention.
The polymer component contained in the surface modification composition according to the embodiment of the present invention may include a polymer having a hydroxyl group and an unsaturated hydrocarbon group.

As described above, the polymer component contained in the surface modification composition according to the embodiment of the present invention may include an addition reaction product between a polymer having a unit derived from a hydroxyl group-containing (meth)acrylic monomer and an unsaturated hydrocarbon group-containing compound. Furthermore, it is more preferable that the polymer component in the surface modification composition according to the embodiment of the present invention is an addition reaction product between a polymer having a unit derived from a non-hydroxyl group-containing (meth)acrylic monomer and a unit derived from a hydroxyl group-containing (meth)acrylic monomer and an unsaturated hydrocarbon group-containing compound.

　The unsaturated hydrocarbon group-containing compound has a specific functional group that can react with and bond to a hydroxyl group, and the hydroxyl group in the polymer reacts with the functional group in the unsaturated hydrocarbon group-containing compound. This introduces a side chain containing an unsaturated hydrocarbon group derived from the unsaturated hydrocarbon group-containing compound into the polymer, and a polymer having a hydroxyl group and an unsaturated hydrocarbon group can be obtained.

The functional group contained in the unsaturated hydrocarbon group-containing compound is preferably an isocyanate group. In other words, the unsaturated hydrocarbon group-containing compound is preferably an unsaturated hydrocarbon group-containing isocyanate compound.

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

In the surface modification composition according to an embodiment of the present invention, when the polymer component includes an addition reaction product between a polymer and an unsaturated hydrocarbon group-containing compound, the addition reaction product is preferably obtained by addition reacting the polymer and the unsaturated hydrocarbon group-containing compound in amounts such that the hydroxyl groups in the polymer and the functional groups in the unsaturated hydrocarbon group-containing compound are in a predetermined ratio.

In the above addition reaction, the reaction temperature is, for example, 40°C to 60°C, and the reaction time is, for example, 4 to 10 hours. An addition reaction catalyst may be used in the reaction. When the functional group in the unsaturated hydrocarbon group-containing compound is an isocyanate group, for example, dibutyltin dilaurate can be used as the addition reaction catalyst. The amount of the addition reaction catalyst used is, for example, 0.3 to 0.6 parts by mass per 100 parts by mass of the unsaturated hydrocarbon group-containing compound.
The polymer component can be obtained, for example, as a polymer solution containing a polymer having a hydroxyl group and an unsaturated hydrocarbon group by preparing a reaction solution in which an unsaturated hydrocarbon group-containing compound and an addition reaction catalyst are added to a polymer solution containing the above-mentioned polymer, and then undergoing the above-mentioned addition reaction in the reaction solution.

In the polymer component contained in the surface modification composition according to the embodiment of the present invention, the molar ratio of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer used in the polymer synthesis (unsaturated hydrocarbon group-containing compound/hydroxyl group-containing monomer) is preferably 0.01 or more and less than 0.5.
If the ratio is less than 0.01, the unsaturated hydrocarbon group is not sufficiently introduced into the polymer component, and the adhesion between the surface-modified layer formed by the surface-modified composition and the resin member is not improved. If the molar ratio is 0.5 or more, the hydroxyl group in the polymer is excessively consumed in the addition reaction, and the amount of hydroxyl group in the polymer component is insufficient, and the adhesion between the surface-modified layer formed by the surface-modified composition and the coating film is not improved. In the embodiment of the present invention, by setting the molar ratio of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer within the above range, both the adhesion between the resin member and the surface-modified layer and the adhesion between the surface-modified layer and the coating film are good.
From the viewpoint of adhesion to the resin member, the ratio is preferably 0.02 or more, more preferably 0.05 or more, more preferably 0.1 or more, more preferably 0.2 or more, and more preferably 0.3 or more. Also, from the viewpoint of adhesion to the paint, the ratio is preferably 0.48 or less, more preferably 0.45 or less, and even more preferably 0.4 or less.

The above ratio is the molar ratio of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer used in the polymer synthesis, and is not the molar ratio of the unsaturated hydrocarbon group to the hydroxyl group contained in the polymer component.
When X parts by mole of the hydroxyl group-containing monomer and Y parts by mole of the unsaturated hydrocarbon group-containing compound are used, the molar ratio of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer is Y/X, and the molar ratio of the unsaturated hydrocarbon groups to the hydroxyl groups in the obtained polymer component is Y/(X-Y).
When the molar ratio Y/X of the unsaturated hydrocarbon group-containing compound to the hydroxyl group-containing monomer is less than 0.5, the molar ratio Y/(XY) of the unsaturated hydrocarbon groups to the hydroxyl groups in the polymer component is calculated to be less than 1.0.

As described above, the molar ratio of the unsaturated hydrocarbon group to the hydroxyl group in the polymer component can be calculated from the amount of the hydroxyl group-containing monomer and the amount of the unsaturated hydrocarbon group-containing compound used in the polymerization. This calculated value is close to the measured value.
The measured values can be obtained by analyzing the molecular weights and composition ratios of the polymer components using GPC, FT-IR, FT-NMR, or the like.

For example, when the molecular weight and composition ratio of the polymer components of the sample specimens shown below were measured by the method described below, the composition ratio of the monomers and the composition ratio of the constituent units derived from the monomers were found to be almost the same. From this result, it can be said that the composition ratio of the constituent units derived from the monomers in the polymer components can be calculated from the charged composition ratio (molar ratio) of the monomers used in polymerization. In other words, it can be said that the molar ratio of unsaturated hydrocarbon groups to hydroxyl groups in the obtained polymer components can be calculated from the amount of hydroxyl group-containing monomer and the amount of unsaturated hydrocarbon group-containing compound.

(Method of measuring molecular weight and composition ratio of polymer components)
1) 1.0 g of a sample solution prepared in the same manner as in Polymer Component 7 in Example was poured into a screw bottle and purged with nitrogen at 60° C. for 3 hours to remove the ethyl acetate solvent, and then an air-dried sample was obtained.

2) A 1.0 g/L THF solution of the air-dried sample was prepared and allowed to stand overnight. The solution was then filtered through a 0.45 μm membrane filter, and the filtrate was subjected to GPC measurement. As a result, the number average molecular weight (Mw) was 8.45× ¹⁰⁴ .
(GPC measurement conditions)
Column: TSKgel GMH-H(S) x 2
Column size: 7.8 mm ID x 300 mm
Eluent: THF
Flow rate: 0.5 mL/min
Detector: RI
Column temperature: 40°C
Injection volume: 100 μL
*Molecular weight was calculated in terms of polystyrene.

3) The sample solution was placed on the prism and immediately thereafter FT-IR measurement was performed.
(FT-IR measurement conditions)
Measurement method: Single reflection ATR method (Smart iTR, Dia 45°)
Resolution: 4 cm ^-1
Detector: DTGS
Number of times: 64

4) 8.62 mg of the air-dried sample was dissolved in 0.6 mL of CDCl ₃ and subjected to ¹ H-NMR measurement.
(FT-NMR measurement conditions)
Observation frequency: 600MHz
Measurement solvent: _CDCl3
Measurement temperature: room temperature Chemical shift reference: 7.25 ppm (measurement solvent)

Polymerization was carried out with the monomers charged as follows: MMA (methyl methacrylate) monomer (100 parts by mole): hydroxyl group-containing monomer (4HBA: 4-hydroxybutyl acrylate) (X parts by mole) = 100:10. When an unsaturated hydrocarbon group-containing monomer (MOI) (Y parts by mole) was blended therein so that it was 0.2 equivalents relative to X parts by mole, and an addition reaction was carried out to obtain polymer component 7, the polymer component was calculated to have a ratio of MMA-derived structural unit (100 parts by mole): amount of hydroxyl groups (X-Y parts by mole): amount of unsaturated hydrocarbon groups (Y parts by mole) = 100:8:2 (parts by mole).
When the above-mentioned measurements were performed on the obtained polymer component 7, the result was that the constitutional units derived from MMA: the amount of hydroxyl groups: the amount of unsaturated hydrocarbon groups = 100:9:1 (parts by mole), and the calculated value was close to the measured value.

In the surface modification composition according to an embodiment of the present invention, the number average molecular weight of the polymer component is 20,000 or more. In addition, when the polymer component contains a polymer having a hydroxyl group and an unsaturated hydrocarbon group, the number average molecular weight of the polymer before the introduction of the unsaturated hydrocarbon group is regarded as the number average molecular weight of the polymer component.

The surface modification composition (which may be a surface modification layer) may contain other components as necessary in addition to the polymer component. Examples of other components include known additives such as pH adjusters, crosslinking agents, crosslinking accelerators, crosslinking retarders, viscosity adjusters (thickeners, etc.), leveling agents, release adjusters, plasticizers, softeners, fillers, colorants (pigments and dyes, etc.), surfactants, antistatic agents, preservatives, anti-aging agents, softeners, UV absorbers, chain transfer agents, antioxidants, rust inhibitors, organic fine particles, inorganic fine particles, silane coupling agents, titanium coupling agents, and light stabilizers. These may be used alone or in combination of two or more.

A crosslinking catalyst may be used to promote the crosslinking reaction more effectively. Examples of crosslinking catalysts include metal-based crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, zirconium tetraacetylacetonate, nursem ferric, butyltin oxide, and dioctyltin dilaurate. Among these, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferred. The amount of crosslinking catalyst used is not particularly limited. The amount of crosslinking catalyst used relative to 100 parts by mass of all constituent units constituting the polymer component can be, for example, in the range of approximately 0.0001 parts by mass to 1 part by mass, and preferably in the range of 0.001 parts by mass to 0.5 parts by mass, taking into consideration the balance between the speed of the crosslinking reaction and the length of the pot life of the surface modification composition.

The surface modification composition may contain a compound that generates keto-enol tautomerism as a crosslinking retarder. This may extend the pot life of the surface modification composition. For example, a compound that generates keto-enol tautomerism may be preferably used in a surface modification composition containing an isocyanate-based crosslinking agent. As a compound that generates keto-enol tautomerism, various β-dicarbonyl compounds may be used. For example, β-diketones (acetylacetone, 2,4-hexanedione, etc.) and acetoacetate esters (methyl acetoacetate, ethyl acetoacetate, etc.) may be preferably used. The compound that generates keto-enol tautomerism may be used alone or in combination of two or more. The amount of the compound that generates keto-enol tautomerism may be, for example, 0.1 to 20 parts by mass, or may be 0.5 to 10 parts by mass, or may be 1 to 5 parts by mass, relative to 100 parts by mass of all the structural units that constitute the polymer component.

The crosslinking reaction can be adjusted by using the crosslinking retarders and crosslinking catalysts mentioned above.

The surface modification composition (which may be the surface modification layer) may contain a crosslinking agent. The surface modification composition (which may be the surface modification layer) has a crosslinked structure due to the crosslinking agent, and this allows the shear storage modulus G', shear loss modulus G'', and complex shear modulus G of the surface modification layer to be adjusted. The crosslinking agent is not particularly limited, but examples thereof include polyfunctional (meth)acrylates and thermosetting crosslinking agents, which are copolymerizable crosslinking agents (photocurable crosslinking agents) of all constituent units constituting the polymer component. The surface modification composition (which may be the surface modification layer) may have a crosslinked structure derived only from the polyfunctional (meth)acrylate, may have a crosslinked structure derived only from the thermosetting crosslinking agent, or may have a crosslinked structure derived from both the polyfunctional (meth)acrylate and the thermosetting crosslinking agent.

Examples of polyfunctional (meth)acrylates that are copolymerizable crosslinking agents (photocurable crosslinking agents) include 1,6-hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, and vinyl (meth)acrylate. As the polyfunctional (meth)acrylate for the (meth)acrylic polymer, one type of polyfunctional (meth)acrylate may be used, or two or more types of polyfunctional (meth)acrylates may be used. In this embodiment, at least one selected from the group consisting of 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, and polypropylene glycol diacrylate is preferably used as the polyfunctional (meth)acrylate for the (meth)acrylic polymer.

The amount of polyfunctional (meth)acrylate used in all the constituent units constituting the polymer component is not particularly limited, but for example, it can be preferably in the range of 0.001% by mass to 5% by mass relative to 100 parts by mass of (meth)acrylic polymer. More preferably, it is 0.01% by mass to 1% by mass. In some embodiments, the amount of crosslinking agent used relative to 100 parts by mass of (meth)acrylic polymer is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and may be 1.0 parts by mass or less, 0.5 parts by mass or less, or 0.2 parts by mass or less. In addition, from the viewpoint of appropriately exerting the effect of using the crosslinking agent, in some embodiments, the amount of crosslinking agent used relative to 100 parts by mass of (meth)acrylic polymer may be, for example, 0.005 parts by mass or more, 0.01 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, or 0.4 parts by mass or more. These configurations regarding the proportion of polyfunctional (meth)acrylate are suitable for achieving appropriate hardness and adhesion in a surface modification composition (which may be a surface modification layer) containing the polymer component, and suppressing poor appearance when integrally molded with a resin molded product.

Examples of thermosetting crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, metal chelate-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, and amine-based crosslinking agents. Other examples of crosslinking agents include monomers having two or more ethylenically unsaturated groups in one molecule, i.e., polyfunctional monomers. The crosslinking agents can be used alone or in combination of two or more.

Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, bisphenol A di(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, butyl diol (meth)acrylate, hexyl diol di(meth)acrylate, etc. The polyfunctional monomers can be used alone or in combination of two or more.

In some embodiments, at least a portion of the crosslinking agent is a bifunctional crosslinking agent having two crosslinking reactive groups (e.g., isocyanate groups) per molecule. By using a bifunctional crosslinking agent, it is easy to form a flexible crosslinked structure. The bifunctional crosslinking agent can be used alone or in combination of two or more types. The bifunctional crosslinking agent may also be used in combination with a trifunctional or higher crosslinking agent.

Examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
As the isocyanate-based crosslinking agent, for example, a bifunctional or higher isocyanate compound can be used, for example, aliphatic polyisocyanates such as trimethylene diisocyanate, 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and dimer acid diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate. alicyclic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), and the like; modified polyisocyanates obtained by modifying the above-mentioned isocyanate compounds with an allophanate bond, a biuret bond, an isocyanurate bond, a uretdione bond, a urea bond, a carbodiimide bond, a uretonimine bond, an oxadiazinetrione bond, or the like (for example, an isocyanurate of HDI, an allophanate of HDI, and the like); Examples of commercially available products include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N, Takenate D178NL, Takenate D-110N (all manufactured by Mitsui Chemicals, Inc.), Sumidur T80, Sumidur L, Desmodur N3400 (all manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, trimethylolpropane/tolylene diisocyanate adduct (trade name "Coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.), Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate adduct (trade name "Coronate HL", manufactured by Nippon Polyurethane Industry Co., Ltd.), Coronate HX, Coronate 2770 (all manufactured by Tosoh Corporation), and Duranate A201H (all manufactured by Asahi Kasei Corporation).
The isocyanate compounds may be used alone or in combination of two or more. A bifunctional isocyanate compound may be used in combination with a trifunctional or higher isocyanate compound.

Examples of epoxy crosslinking agents (polyfunctional epoxy compounds) include N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o -phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl)isocyanurate, resorcinol diglycidyl ether, and bisphenol-S-diglycidyl ether, bisphenol A, epichlorohydrin type epoxy resins, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane. Epoxy crosslinking agents include epoxy resins having two or more epoxy groups. In addition, epoxy crosslinking agents include commercially available products such as "Tetrad C" (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
These may be used alone or in combination of two or more.

(Filler)
The surface modification composition (which may be the surface modification layer) may contain a filler. The type and amount of the filler to be added are not particularly limited.
By including a filler in the surface modification composition (which may be the surface modification layer), the shear storage modulus G', shear loss modulus G'', and complex shear modulus G of the surface modification layer can be adjusted.

The proportion of the filler in the surface modification composition (which may be the surface modification layer) is not particularly limited, and is preferably 0.1% to 50% by mass, 0.5% to 40% by mass, more preferably 1% to 30% by mass, more preferably 5% to 21% by mass, and more preferably 10% to 20% by mass, relative to 100 parts by mass of the surface modification composition. If the proportion is less than 0.1 parts by mass, a sufficient improvement in the elastic modulus cannot be obtained. If the content exceeds 50 parts by mass, it becomes difficult to form the surface modification layer.

The filler is not particularly limited, and may be non-particulate such as fibrous, bundle-shaped, plate-shaped, layered, needle-shaped, spike-shaped, or amorphous, fine particles, secondary particles (aggregates) of fine particles, solid particles, or hollow particles. It may be organic fine particles or inorganic fine particles, and is not limited thereto.

((Inorganic fine particles))
Examples of inorganic fine particles that can be incorporated into the surface modification composition of the present invention include metal oxides such as silica, alumina, zirconia, and titania; metal salts such as aluminum borate and aluminum hydroxide; minerals such as mica; and inorganic fine particles having a hollow structure such as hollow nanosilica. These can be used alone or in combination of two or more.

(Organic Fine Particles)
Examples of organic fine particles that can be incorporated into the surface modification composition of the present invention include polymers such as styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride resins, vinylidene chloride resins, amide resins, urethane resins, phenol resins, styrene-conjugated diene resins, acrylic-conjugated diene resins, olefin resins, and fluorine resins, or fine particles composed of crosslinked bodies of these polymers, and further fine particles composed of these polymer-polymer crosslinked bodies to have a hollow structure. These can be used alone or in combination of two or more types.

The inorganic fine particles may be surface-treated in terms of dispersibility in the surface modification composition. Any known or conventional surface treatment agent may be used without limitation, and examples of such agents include silane coupling agents, titanium coupling agents, organic acids, polyols, and silicones. Silane coupling agents are preferred. Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, vinyl-tris(2-methoxy)silane, vinyltriacetoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, triethoxyphenylsilane, trimethoxyphenylsilane, dimethoxydiphenylsilane, methyldiethoxyphenylsilane, and dimethoxymethylphenylsilane.

Furthermore, there are no particular limitations on the surface of the filler. As an example, the filler may be untreated or may have been surface-treated, but it is preferable that the surface of the filler is untreated or that the functional group on the surface of the filler is at least one type of group selected from the group consisting of a silanol group, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, an isocyanate group, and an epoxy group.

Examples of fillers include silica particles such as fumed silica, colloidal silica, and precipitated silica, as well as silica-based fillers such as silica gel, silica aerogel, quartz glass, and glass fiber. Among these, fumed silica and colloidal silica are preferred from the viewpoint of easy mixing into the surface modification composition.

The average primary particle diameter of the filler is preferably 1 nm to 1 μm, more preferably 5 nm to 500 nm, 7 nm to 100 nm, 10 nm to 50 nm, and even more preferably 10 nm to 22 nm. The average primary particle diameter can be measured, for example, by SEM (scanning electron microscope), TEM (transmission electron microscope), DLS (dynamic light scattering), static light scattering, etc.

The surface modification composition may be a solution in which a material for forming the surface modification layer is dissolved in water or an organic solvent.
The organic solvent may be any organic compound that is used as a solvent, and examples of the organic solvent include hydrocarbon solvents such as cyclohexane, hexane, heptane, and methylcyclohexane; aromatic solvents such as toluene and xylene; ester solvents such as butyl acetate, ethyl acetate, and methyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and alcohol solvents such as methanol, ethanol, propanol, butanol, and isopropyl alcohol. The organic solvent may be a mixed solvent containing two or more organic solvents.

As the surface modification composition, a polymer solution containing the polymer component obtained in the synthesis of the polymer component may be used as is.

The solid content concentration in the surface modification composition can be set appropriately depending on the purpose. From the viewpoint of thickness accuracy of the surface modification layer, the mass percentage is preferably 1 mass% to 60 mass%, more preferably 10 mass% to 50 mass%, even more preferably 15 mass% to 40 mass%, even more preferably 20 mass% to 35 mass%, and even more preferably 25 mass% to 30 mass%.

The surface modification composition may contain other components that can be contained in the surface modification layer in addition to the above-mentioned polymer component, if necessary.
For example, the addition of a colorant makes the surface modification layer visible, making it easier to determine whether the surface of the resin part has already been modified, which is advantageous in terms of process management. It also functions as a base for improving the color development of the paint.
The colorant may be, for example, a dye or a pigment, or may be a fluorescent material that is visible under black light.

[Surface modified layer and surface modified sheet]
The surface modification layer according to the embodiment of the present invention is formed from the surface modification composition according to the embodiment of the present invention.
The surface modified sheet according to the embodiment of the present invention has a surface modified layer.
The surface-modified sheet may include a release sheet, or may be a surface-modified sheet in a form that does not include a release sheet. That is, the surface-modified sheet according to the embodiment of the present invention may be composed of only a surface-modified layer, or may include a surface-modified layer and a release sheet.

The loss tangent (tan δ) at 145°C of the surface modification layer formed from the surface modification composition, as determined by dynamic viscoelasticity measurement, is 1.06 or less. The explanation for the loss tangent (tan δ) of the surface modification composition may be applied as is.

The state of the surface modification layer may be any of the following non-crosslinked, uncrosslinked, and crosslinked states.
Non-crosslinked: The surface modification layer or the added components do not contain any components that can crosslink.
Uncrosslinked: The surface modification layer or the added components contain components that can crosslink, but are not crosslinked.
Crosslinked: Crosslinked.

The flowability of the surface modification layer (which may be a surface modification composition) according to embodiments of the present invention can also be visualized, for example, by using a colorant.
For example, a colorant compatible with the surface-modified layer is mixed and formed on a release liner. The colorant can be changed so as to be compatible with the composition of the surface-modified layer, but within a range that does not affect the properties of the surface-modified layer. The colorant is not particularly limited, but for example, Zebra's Hi-Mackie (red) ink containing an oil-based dye may be diluted with ethyl acetate and mixed with the surface-modified composition according to the embodiment of the present invention to obtain a colorant-mixed surface-modified layer. Note that colorants or pigments that exhibit incompatible properties such as precipitation when mixed, and those that can adjust the properties of the surface-modified layer are not suitable.

The hue of the resulting colorant-mixed surface-modified layer is measured by a single surface-modified layer using a transmission method, and when expressed as L, a, and b values in the Hunter Lab color space, it is preferable that L is 88 to 93, a is 4 to 10, and b is 2 to 5. It is also preferable that the hue falls within the above ranges when heated at 145°C for 4 minutes.

The fluidity of the surface-modified layer in the surface-modified member molded using the obtained colorant-mixed surface-modified layer can be imaged, for example, using FPD8010J (FUJIFILM Corp.) software and a GT-F740 (EPSON) scanner. The image is scaled by MW and the pressure value is the sustained pressure, allowing the color shade to be distinguished.
In distinguishing the color shades, the pressure range is divided into the following regions: less than 1.0 MPa, 1.0 to less than 15.0 MPa, 15.0 to less than 20.0 MPa, 20.0 to less than 25.0 MPa, 25.0 to less than 30.0 MPa, 30.0 to less than 35.0 MPa, 35.0 to less than 40.0 MPa, 40.0 to less than 45.0 MPa, 45.0 to less than 50.0 MPa, and 50.0 MPa or more.
The pressurized area (mm ² ) of each region is calculated, and the sum of the areas of the regions determined to be 1.0 MPa or more is divided by the total measured area, thereby calculating the coverage of the resin member by the surface modification layer.

Next, the coating variation can be calculated by the following method. The median value of the pressure in each of the above-mentioned regions is defined as M (for example, the median value M is 17.5 MPa when the pressure is in the region of 15.0 or more and less than 20.0 MPa). Furthermore, the pressurized area (mm ² ) of each region is defined as N, and Mn and Mw can be calculated based on the following formula. Finally, the coating variation can be calculated by calculating Mw/Mn. The closer the coating variation is to 1, the more uniform the coating is, and the greater the coating variation is above 1, the greater the variation.

The polymer components contained in the surface modification layer according to the embodiment of the present invention can be the same as those described for the polymer components in the surface modification composition.

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, it is not applied to the surface of the resin member, but is placed on the resin material and heat-treated to be integrally molded. Therefore, it is possible to prevent unevenness due to repelling and the like, and to form a surface-modified layer with a uniform thickness on the surface of the resin member. In addition, when providing a surface-modified layer on a part of the surface of the resin member, it is possible to suppress a decrease in yield due to overflow and the like.
In addition, the surface-modified sheet according to the embodiment of the present invention may be composed of only a surface-modified layer. Therefore, the surface-modified layer (surface-modified sheet) may be formed by, for example, applying a surface-modified composition to at least a part of the surface of the resin member. The surface-modified composition applied to at least a part of the surface of the resin member may be formed into a surface-modified layer by, for example, drying, and the formed surface-modified layer may be protected by, for example, a release sheet and subjected to molding. In this case, integral molding is possible in the same manner as in the case of placing a surface-modified sheet having a surface-modified layer and a release sheet on a resin material and performing a heat treatment.

As described below, the surface-modified sheet according to the embodiment of the present invention is suitable for use in the manufacture of a surface-modified member using a resin member containing an unsaturated hydrocarbon group-containing thermosetting resin. The surface-modified sheet according to the embodiment of the present invention has a loss tangent (tan δ) at 145°C obtained by dynamic viscoelasticity measurement of the surface-modified layer of 1.06 or less, thereby controlling the fluidity of the surface-modified layer and forming a surface-modified member with a high coverage rate and reduced coating variation. Furthermore, the number-average molecular weight of the polymer component contained in the surface-modified layer is 20,000 or more, thereby controlling the fluidity of the surface-modified layer and forming a surface-modified member with a high coverage rate and reduced coating variation.

Furthermore, when the polymer component contains, for example, a hydroxyl group, and the coating film applied on the surface modification layer contains a paint having functional groups that can react or interact with the hydroxyl groups, such as a urethane-based paint, the hydroxyl groups in the polymer component and the functional groups in the paint can form chemical bonds or interact with each other at the interface between the surface modification layer and the coating film, thereby improving the adhesive strength between the surface modification layer and the coating film.
Examples of chemical bonds include covalent bonds, ionic bonds, and metallic bonds. Examples of intermolecular interactions include hydrogen bonds, acid/base interactions, electrostatic interactions, aromatic ring interactions, van der Waals interactions, and the like. The strength of the bonding force is covalent bonds > ionic bonds > metallic bonds > intermolecular interactions, and from the viewpoint of improving the adhesion between the surface modification layer and the coating film, it is preferable to form covalent bonds at the interface between the surface modification layer and the coating film.

The thickness of the surface modification layer is not particularly limited, and is 0.01 μm to 2000 μm, more preferably 0.1 μm to 1000 μm, further preferably 0.5 μm to 200 μm, and particularly preferably 1 μm to 100 μm.
The thickness of the surface modified layer is measured by measuring the thickness of the surface modified sheet with a dial thickness gauge (for example, Peacock GC-9), measuring the thickness of the release sheet from which the surface modified layer at that location has been removed, and measuring the difference as the thickness of the surface modified layer. Can be measured.
The average thickness of the surface modification layer is the average value of measurements at 10 points.
The surface modification layer may be formed by applying a surface modification composition to at least a part of the surface of the resin material before molding, or by applying a surface modification composition to a release sheet.

(Release sheet)
The release sheet is not particularly limited, but preferably has a heat resistance of 100° C. or higher and a tensile modulus at 100° C. of 1 GPa or less.
The release sheet may be any conventional release paper, and is not particularly limited. Examples of the release sheet include a substrate having a release treatment layer, a low-adhesion substrate made of a fluoropolymer, and a low-adhesion substrate made of a non-polar polymer.
Examples of the substrate having a release treatment layer include plastic films and papers that have been surface-treated with a release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide-based release treatment agent.
Examples of the fluorine-based polymer in the low-adhesion substrate made of a fluorine polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. Examples of the non-polar polymer include olefin-based resins (e.g., polyethylene, polypropylene, etc.), and polyester-based substrates (polyethylene terephthalate-based substrates, polyethylene naphthalate-based substrates, polybutylene terephthalate-based substrates, etc.) are also used.

More specifically, examples of release sheets that can be used for the surface modified sheet include unstretched polyamide 6, unstretched polyamide 66, biaxially oriented polyamide 6, biaxially oriented polyamide 66, biaxially oriented polypropylene, biaxially oriented polyethylene terephthalate, biaxially oriented polybutylene terephthalate, easily molded polyethylene terephthalate, cast molded polytetrafluoroethylene, unstretched extruded tetrafluoroethylene-ethylene copolymer (ETFE), unstretched extruded tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), unstretched extruded tetrafluoroethylene-hexafluoropropylene co-polymer (FEP), and laminates having these as the main layer.
The release sheet can be formed by a known or commonly used method.
The release sheet may be a commercially available product, and examples thereof include a fluorine-based resin sheet film (Nitto Denko Corporation, Nitoflon), a polyester-based resin sheet, a polymethylpentene-based resin sheet (Mitsui Chemicals Tocello, Opulent (registered trademark)), a polystyrene-based resin sheet (Kurabo, Eudis (registered trademark)), a polyamide-based resin sheet, and a polyolefin-based resin sheet.

The thickness of the release sheet is not particularly limited, but from the viewpoint of shape conformability, it is preferably 1 μm to 1000 μm, more preferably 10 μm to 500 μm, even more preferably 20 μm to 300 μm, and particularly preferably 30 μm to 100 μm.
If necessary, the surface of the release sheet on the side of the surface-modified layer or on both sides of the release sheet may be subjected to a release treatment using an appropriate release treating agent such as silicone.

[Production of surface modified sheet]
The surface-modified sheet can be produced by any suitable method. For example, a method of dipping a release sheet into a solution (surface-modifying composition) containing a material for the surface-modifying layer and a solvent, followed by drying as necessary, a method of brushing a solution containing a material for the surface-modifying layer and a solvent on the surface of a release sheet and then drying as necessary, a method of applying a solution containing a material for the surface-modifying layer and a solvent to the surface of a release sheet using various coaters and then drying as necessary, a method of spraying a solution containing a material for the surface-modifying layer and a solvent on the surface of a release sheet and then drying as necessary, and the like.

[Laminate]
The laminate according to the embodiment of the present invention is a laminate in which the surface modification layer is laminated on at least a part of the surface of a resin material.
The laminate, which is the resin material with a surface modification layer in the embodiment of the present invention, can be produced by laminating the surface modification layer side of the surface modification sheet on at least a part of the surface of the resin material before molding. It may also be produced by forming a surface modification layer by applying a surface modification composition to at least a part of the surface of the resin material before molding.

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

Examples of thermoplastic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), POM (polyacetal), PEEK (polyether ether ketone), PC (polycarbonate), PES (polyether sulfide), and EP (epoxy). Among these resins, thermoplastic resins that can advantageously exhibit the effects of the present invention include PPS (polyphenylene sulfide), PA (polyamide), PES (polyether sulfide), and EP (epoxy).

As the thermoplastic resin, a fiber reinforced thermoplastic resin (FRTP) can be adopted.
Examples of fiber reinforced thermoplastic resins (FRTP) include carbon fiber reinforced thermoplastic resins (CFRTP) and glass fiber reinforced thermoplastic resins (GFRTP).

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

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

The resin contained in the resin material is preferably a thermosetting resin, and from the viewpoint of improving the adhesion between the resin member and the surface modification composition or the surface modification layer, it is preferably an unsaturated hydrocarbon group-containing thermosetting resin.
Examples of the unsaturated hydrocarbon group-containing thermosetting resin include unsaturated polyester resins and vinyl ester resins, with unsaturated polyester resins being preferred.
The unsaturated hydrocarbon group-containing thermosetting resin contained in the resin material includes at least a portion of the unsaturated hydrocarbon group-containing thermosetting resin in an uncured state.

The resin material may include a fiber-reinforced resin, and the thermosetting resin may be a fiber-reinforced thermosetting resin.
Examples of the fiber-reinforced thermosetting resin include carbon fiber-reinforced thermosetting resin and glass fiber-reinforced thermosetting resin.

The resin material preferably contains a reactive monomer, a curing agent, and glass fiber in addition to the unsaturated hydrocarbon group-containing thermosetting resin. The unsaturated hydrocarbon group-containing thermosetting resin, such as an unsaturated polyester resin, is polymerized (three-dimensionally crosslinked) by radical polymerization of the unsaturated hydrocarbon group in the thermosetting resin and the reactive monomer in the presence of the curing agent, to obtain a cured product.
When the resin contained in the resin material is an unsaturated polyester resin, for example, styrene is preferably used as the reactive monomer, and benzoyl peroxide (BPO) is preferably used as the curing agent.

The shape of the resin material is not particularly limited, but examples thereof include a plate having a flat surface, a plate having a curved surface, a plate having irregularities, a sheet, and a film.
The thickness of the resin material is not particularly limited, but is, for example, 0.001 mm to 30 mm.

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

The above explanation can be used as is for the surface-modified sheet and surface-modified layer.

[Surface modification material]
The surface-modified member according to the embodiment of the present invention is a member in which the surface-modified layer according to the embodiment of the present invention is laminated on at least a part of the surface of a resin member, and the resin member and the surface-modified layer are covalently bonded by a chemical reaction. Since the resin member and the surface-modified layer form a covalent bond, the adhesive strength between the resin member and the surface-modified layer is excellent.
The surface modification layer may be formed by coating at least a part of the surface of the resin member, or may be formed using a surface modification sheet in the form of a sheet.

The above explanations can be used for the surface modification layer and the resin material. The resin member is obtained by molding the resin material, and the preferred shape and thickness of the resin member are the same as those of the resin material.

Note that "at least a part of the surface of the resin member" means at least a part of all the surfaces that the resin member has. For example, if the resin member is in the form of a plate, sheet, or film, it means a part of at least one of the surfaces, or the entirety of at least one of the surfaces.

In the surface-modified member according to the embodiment of the present invention, the surface-modified layer 10 may be a single layer or multiple layers. When the surface-modified member has multiple surface-modified layers 10, the respective surface-modified layers 10 may be the same or different.
For example, as shown in FIG. 1, the surface-modified member may be a resin member 100 having a surface-modified layer 10 provided on one surface thereof, or as shown in FIG. 2, the surface-modified member may be a resin member 100 having a surface-modified layer 10 and a surface-modified layer 11 provided on both surfaces thereof.
Alternatively, as shown in FIG. 3, the surface-modified member may be a resin member 100 having a plurality of surface-modified

layers

10, 11 provided on one surface thereof.
When the surface-modified member has a plurality of surface-modified layers, at least one of the surface-modified layers and the resin member 100 may be covalently bonded by a chemical reaction. The surface-modified layers may be the same or different. For example, in the resin member shown in FIG. 3, the surface-modified layer 11 increases the adhesion to the resin member 100, and the surface-modified layer 10 suppresses the fluidity to increase the coverage of the resin member 100. The composition, physical properties, additives, crosslinking form, and processing method of each surface-modified layer may be changed according to the application.

In the surface modified member according to the embodiment of the present invention, as an example, the resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and the unsaturated hydrocarbon group-containing thermosetting resin is preferably an unsaturated polyester resin.
That is, in the surface-modified member according to the embodiment of the present invention, the unsaturated hydrocarbon group-containing thermosetting resin in the resin member and the polymer component in the surface-modified layer are preferably covalently bonded to each other.
The unsaturated hydrocarbon group-containing thermosetting resin contained in the resin member includes a cured state unsaturated hydrocarbon group-containing thermosetting resin, that is, a resin from which the unsaturated hydrocarbon groups have been consumed.

The molding of the resin member is preferably performed by hot molding. Hot molding may be performed simultaneously with lamination of the resin material and the surface-modified sheet, or after lamination of the surface-modified sheet on the resin material. Alternatively, it may be performed after applying a surface-modifying composition to the surface of the resin material to form a surface-modified layer.
By performing the surface treatment of the resin member in this manner, it is possible to impart sufficient adhesive strength to the resin member, and the surface-modified member can be produced with high productivity and low cost. The method for producing a surface-modified member can also be a method for treating the surface of a resin member (a method for surface-treating a resin).

The surface-modified member according to the embodiment of the present invention can suitably cover at least a part of the surface of a resin member and can impart sufficient adhesive strength to the resin member, so that the resin members can be bonded to each other with excellent adhesive strength. For example, as shown in Fig. 4, the

resin members

100 and 101 can be bonded via the surface-modified layer 10 in the surface-modified member. Fig. 4 is a schematic cross-sectional view showing an example of a laminate of a surface-modified member and a resin member.
4 may be, for example, a resin material 100/surface modification layer 10/resin material 101 laminated together and then heated to form a surface modification member, or a resin material 101 may be laminated on the surface modification layer side of a surface modification member formed from the resin material 100 and the surface modification layer 10, and then heated to form a surface modification member. That is, the heat molding may be performed simultaneously with the lamination of the resin material 100, the surface modification sheet 10, and the resin material 101, or may be performed after the surface modification sheet is laminated on one of the resin materials.
By performing the surface treatment of the resin member in this manner, it is possible to impart sufficient adhesive strength to the resin member, and the surface-modified member can be produced with high productivity and low cost. The method for producing a surface-modified member can also be a method for treating the surface of a resin member (a method for surface-treating a resin).

[Method for manufacturing surface modified member]
Although there is no particular limitation on the manufacturing method of the surface-modified member according to the embodiment of the present invention, for example, the surface-modified member can be manufactured by placing the surface-modified layer side of the surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, on at least a part of the surface of the resin material and performing heat molding. In addition, the surface-modified member can be manufactured by applying a surface-modifying composition to at least a part of the surface of the resin material and performing heat molding.
The hot molding brings the interface between the surface modification layer and the resin material into contact, and the polymer component contained in the surface modification layer chemically reacts with the resin contained in the resin material, thereby forming a surface modification member in which the resin member and the surface modification layer are covalently bonded.
The heat molding may be carried out simultaneously with placing the surface-modified sheet, or may be carried out after placing the surface-modified sheet.
The component that chemically reacts with the resin material is preferably contained in the polymer component of the surface modification composition that forms the surface modification layer, but is not particularly limited thereto, and may be a component added separately from the polymer component.
By performing the surface treatment of the resin member in this manner, it is possible to impart sufficient adhesive strength to the resin member, and the surface-modified member can be produced with high productivity and low cost. The method for producing a surface-modified member can also be a method for treating the surface of a resin member (a method for treating the surface of a resin member).

The above explanations can be used as is for the resin member, surface-modified sheet, release sheet, and surface-modified layer.

In the manufacture of the surface-modified member, although not particularly limited, when the curing temperature of the thermosetting resin contained in the resin member is _T2 °C, it is preferable to provide a surface-modified layer on at least a part of the surface of the resin material containing the thermosetting resin, and to perform hot molding at a temperature of _T1 °C or higher.
The hot molding temperature is not particularly limited, but is preferably T ₁ °C to T ₃ °C, more preferably (T ₁ + 10) °C to (T ₃ - 10) °C, and even more preferably (T ₁ + 20) °C to (T ₃ - 20) °C.
The curing temperature and _T1 to _T3 are obtained from the irreversible component of the heat flow curve of the uncured thermosetting resin measured by TM-DSC (temperature modulated differential scanning calorimetry). TM-DSC is obtained under atmospheric conditions, light-shielded conditions, with a heating rate of 2°C/min, modulation conditions of ±0.3°C, and a 60 s cycle. _T1 is the temperature (°C) at which heat generation begins when the uncured thermosetting resin is measured by TM-DSC, and is the intersection point between the extension of the baseline of the irreversible component of the heat flow curve and the tangent of the maximum slope of the endothermic peak. _T2 is the endothermic peak temperature. _T3 is the temperature (°C) at which heat generation ends, and is the intersection point between the extension of the baseline of the irreversible component of the heat flow curve and the tangent of the maximum slope of the endothermic peak.

By carrying out surface treatment of the resin member in the above-mentioned manner with the heat molding temperature within the above-mentioned range, the interface between the surface modification layer and the resin member comes into contact and forms a covalent bond through a chemical reaction, providing the resin member with a surface modification layer that has excellent adhesive strength with the coating film. This can be achieved with high productivity and low cost.

A method for producing a surface-modified member according to an embodiment of the present invention is a method for producing a surface-modified member using the above-mentioned surface-modified layer, and may include a lamination step of laminating the surface-modified layer onto a resin member by hot molding.
The resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin.
The method for producing a surface modified member according to the embodiment of the present invention may be a method for producing a surface modified member using the above-mentioned surface modified sheet.

Thermal molding methods include, for example, compression molding, transfer molding, and injection molding, and are preferably performed by resin molding, more preferably compression molding. When the thermosetting resin is a fiber-reinforced thermosetting resin, molding methods include the hand lay-up method, spray-up method, filament winding method, pultrusion molding method, sheet mold compound method, bulk mold compound method, resin transfer method, and vacuum-assisted resin transfer method.

In the compression molding, for example, the surface modification layer side of the surface modification sheet is placed on at least a part of the surface of the resin member in a molding machine (e.g., a press machine, etc.), and molding processing involving heating (e.g., integral molding by a heated press) is performed. According to such an embodiment, the surface treatment of the resin member and molding processing of the resin member can be performed simultaneously, so that high productivity and low cost can be provided. The molding pressure during compression molding is not particularly limited, but is preferably 1 MPa or more from the viewpoint of deforming the molded product with a mold, more preferably 2 MPa or more, more preferably 3 MPa or more, more preferably 5 MPa or more, and even more preferably 10 MPa or more. Also, from the viewpoint of retaining the resin amount in the molded product, it is preferably 30 MPa or less, more preferably 25 MPa or less, more preferably 20 MPa or less, and even more preferably 15 MPa or less.

The molding process for the resin member may be injection molding.
For example, an injection molding machine equipped with a movable mold and a fixed mold can be used for injection molding. For example, a surface modified sheet is accommodated in a recess of a cavity of the movable mold so that a release sheet faces the recess, and the movable mold and the fixed mold are clamped. Then, molten resin is injected into the cavity.
After the resin is cooled and solidified in the mold, the movable mold and the fixed mold are separated from each other, thereby obtaining a surface-modified member in which the surface-modified sheet and the resin member are integrated.

In addition, by peeling off the release sheet from the surface-modified member, a surface-modified member having a surface-modified layer on its surface can be obtained. The method for peeling off the release sheet is not particularly limited, and may include peeling it off by hand or using dedicated peeling equipment. The release sheet can be left in place until just before painting. This can prevent contamination of the surface of the surface-modified layer.

The surface-modified layer side of the surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is placed on at least a part of the surface of a resin member (which may be a resin material), and after heat molding, the release sheet is preferably removed. By removing the release sheet in this manner, the surface-modified layer is transferred to the surface of the resin member, and a surface-modified member (sometimes referred to as a laminate member of a resin member and a surface-modified layer) is obtained.
As described above, it is preferable that the resin and the polymer component of the surface modification layer are covalently bonded to each other between the resin member and the surface modification layer.

By using the above manufacturing method, a surface-modified layer 10 is provided on the surface of the resin member 100, as shown in Figure 1, and a surface-modified member is obtained.

The surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is surface-modified sheet 200, which is a laminate of release sheet 20 and surface-modified layer 10, as shown in FIG. 5.

In the manufacturing method of the surface-modified member according to an embodiment of the present invention, the surface-modified layer side of the surface-modified sheet, which is a laminate of a release sheet and a surface-modified layer, is placed on at least a part of the surface of the resin material in such a manner that the surface-modified sheet 200 is placed on the surface of the resin material 400 such that the surface-modified layer 10 side of the surface-modified sheet 200 is the surface side of the resin material 400, as shown in FIG. 6.

[Coated object and method for producing coated object]
The coated article according to the embodiment of the present invention has a coating film on at least a part of the surface-modified member, and preferably has a coating film on at least a part of the surface of the surface-modified layer side of the surface-modified member.
As an example of a coated article according to an embodiment of the present invention, FIG. 7 shows a coated article 300 having a coating film 30 on the surface of a surface-modified member in which a surface-modified layer 10 is provided on the surface of a resin member 100.

The coating film is not particularly limited, but may be at least one selected from, for example, a coating layer, a printing layer, a vapor deposition layer, a sputtering layer, an atomic layer deposition (ALD) layer, a CVD (chemical vapor deposition) layer, a spin-coated layer, a dip-coated layer, an alternating lamination layer, a Langmuir-Blodgett layer, and a plating layer.

From the viewpoint of the adhesion improving effect by applying the surface modified sheet of the present invention, the coating film preferably contains a paint, and more preferably contains a paint having a functional group that forms a chemical bond with a hydroxyl group or interacts with an intermolecular group.
From the viewpoint of improving adhesion, the functional group is preferably a functional group that forms a covalent bond with a hydroxyl group, and is preferably an isocyanate group or an amino group.

The paint contained in the coating film is preferably a urethane-based paint, a urethane-based paint such as an acrylic-urethane paint, an acrylic paint, an epoxy paint, a silicone paint, a polyester resin-melamine resin paint or a fluorine paint, and a urethane-based paint is more preferable.
Urethane paint is a general term for paints that combine a resin (polyol) with multiple hydroxyl groups as the base agent and a polyisocyanate as a curing agent. The polyisocyanate is not particularly limited as long as it is a compound with two or more isocyanate groups, and examples thereof include aromatic compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate, aliphatic compounds such as hexamethylene diisocyanate, alicyclic compounds such as isophorone diisocyanate, and monomers thereof and polymers such as biuret type, nurate type, adduct type, and allophanate type.

When the surface modification layer is formed using a sheet-like surface modification sheet rather than being applied to the surface of the member, it is possible to more suitably prevent the occurrence of unevenness due to repelling, etc. Therefore, the surface modification 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 film thickness.
In addition, by providing a surface modification layer on the surface of a resin member in a molten or softened state, the surface modification layer and the resin member are chemically bonded by the heat of the surface of the resin member, and the adhesive strength between the surface modification layer and the resin member is increased, so that a coating film with excellent adhesion can be formed. In addition, the hydroxyl group in the polymer component contained in the surface modification layer and the functional group in the paint contained in the coating film form a chemical bond or have an intermolecular interaction, so that the adhesive strength between the surface modification layer and the coating film is also increased, and a coating film with excellent adhesiveness can be formed.
Furthermore, when forming a coated product, the surface modification layer and the resin component can be molded as a single unit. This eliminates the need for a cleaning process using an organic solvent to remove the release agent before forming the coating, a polishing process, or a process to repair defective parts, resulting in superior safety and reduced environmental and work loads.

The thickness of the coating is not particularly limited, but is generally 0.001 to 10,000 μm, 0.01 to 5,000 μm, more preferably 0.1 to 1,000 μm, even more preferably 0.5 to 500 μm, and particularly preferably 1 to 200 μm.

The method for producing a coated article according to an embodiment of the present invention is a method for producing a coated article using the above-mentioned surface modification composition or surface modification layer,
A step of laminating the surface modification layer onto a resin member by hot molding to produce a surface modification member;
and forming a coating film on the surface-modified layer side of the surface-modified member.
The method for producing a coated article according to an embodiment of the present invention may be a method for producing a coated article using the above-mentioned surface modified sheet.

The resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin.
The coating film preferably contains a coating material having a functional group that forms a chemical bond with a hydroxyl group or that has an intermolecular interaction with the hydroxyl group.

The above explanations may be used as they are for the surface modification composition, resin member, surface modification sheet, surface modification layer, and surface modification member. In addition, the explanation in the above [Method of manufacturing surface modification member] may be used as they are for the process of forming the surface modification member.

There are no particular limitations on the method of applying the coating film, and known methods such as brush coating, roller coating, spray coating, and various coater coating can be used, and the amount applied is not particularly limited. In addition, the time and temperature for heating the coating film, the pressure of the surrounding environment, whether or not to irradiate with active energy rays, the gas atmosphere, etc. can also be appropriately determined depending on the coating material used, the amount applied, etc.

[Member with functional layer and manufacturing method of member with functional layer]
A member with a functional layer according to an embodiment of the present invention includes a functional layer on at least a portion of the surface of the surface-modified member on the side of the surface-modified layer.
As an example of a functional layer-attached member according to an embodiment of the present invention, Figure 8 shows a functional layer-attached member 500 having a functional layer 40 on the surface of the surface-modified layer side of a surface-modified member having a surface-modified layer 10 provided on the surface of a resin member 100.

Functional layers in the functional layer-attached member according to the embodiment of the present invention include, for example, a hard coat layer, an optical adjustment layer, a rough surface-imparting layer, a smoothness-imparting layer, an anti-reflection layer, a conductive layer, a static electricity-removing layer, a power-generating layer, a photovoltaic power-generating layer, a heat-transfer layer, a heat-storage layer, a heat-dissipating layer, a moisture-absorbing layer, a moisture-permeable layer, a gas-permeability-adjusting layer, a porous layer, a metal layer, a semiconductor layer, a dielectric layer, a composite material layer, a metamaterial layer, an elastic modulus-adjusting layer, a design layer, a decorative layer, a surface protection layer, a sliding-resistant layer, an impact-absorbing layer, a puncture-strength-adjusting layer, an anti-fouling layer, a biocompatible layer, a chromic layer, a weather-resistance-adjusting layer, a snow-proof layer, a friction-adjusting layer, a tacky adhesive layer, a sustained-release component-retaining layer, an oil/water-absorbing layer, an anti-fingerprint layer, an anti-rust layer, a display device layer, an input device layer, a touch sensor layer, and the like. They can be selected according to the type of functional layer and the use and purpose of the functional layer-attached member.

From the viewpoint of improving adhesion, the functional layer is preferably a layer having a functional group that forms a chemical bond with a hydroxyl group or that has an intermolecular interaction. From the viewpoint of improving adhesion, the functional group is preferably a functional group that forms a covalent bond with a hydroxyl group, and is preferably an isocyanate group or an amino group.

When the surface modification layer is formed using a sheet-like surface modification sheet rather than being applied to the surface of the member, it is possible to prevent unevenness due to repelling, etc. Therefore, the surface modification layer can be formed with a uniform thickness on the surface of the resin member, and the functional layer can be applied with a uniform film thickness.
In addition, by providing a surface modification layer on the surface of a resin member in a molten or softened state, the surface modification layer and the resin member are chemically bonded by the heat of the surface of the resin member, and the adhesive strength between the surface modification layer and the resin member is increased, so that a functional layer with excellent adhesion can be formed. In addition, the hydroxyl group in the polymer component contained in the surface modification layer and the functional group of the component contained in the functional layer form a chemical bond or have an intermolecular interaction, so that the adhesive strength between the surface modification layer and the functional layer is also increased, and a functional layer with excellent adhesiveness can be formed.
Furthermore, when forming a component with a functional layer, it is possible to integrally mold the surface modification layer and the resin component, so there is no need for a cleaning process using an organic solvent or a polishing process to remove the release agent before forming the functional layer, which is safer and reduces the environmental and workload burdens.

The thickness of the functional layer is not particularly limited, and is 0.001 to 10,000 μm, 0.01 to 5,000 μm, more preferably 0.1 to 1,000 μm, even more preferably 0.5 to 500 μm, and particularly preferably 1 to 200 μm.

The method for producing a member with a functional layer according to an embodiment of the present invention is a method for producing a member with a functional layer using the above-mentioned surface modification layer,
A step of laminating the surface modification layer onto a resin member by hot molding to produce a surface modification member;
and forming a functional layer on the surface-modified layer side of the surface-modified member.
The method for producing a member with a functional layer according to an embodiment of the present invention may be a method for producing a member with a functional layer using the above-mentioned surface modification sheet.

The resin member preferably contains an unsaturated hydrocarbon group-containing thermosetting resin, and more preferably contains an unsaturated polyester resin.

The above explanations may be used as is for the resin member, surface-modified sheet, surface-modified layer, and surface-modified member. In addition, the explanation in the above [Method of manufacturing surface-modified member] may be used as is for the process of forming the surface-modified member.

There are no particular limitations on the method for forming the functional layer, and known methods such as bonding, pasting, coating, vapor deposition, printing, fusion, ultrasonic bonding, ultrasonic fusion, active energy ray irradiation, compression, etc. can be used.

[Process control method]
In the manufacture of the surface-modified sheet according to the embodiment of the present invention, the manufacture of the surface-modified member, the manufacture of the coated object, and the manufacture of the member with the functional layer, for example, by adding an additive such as a colorant (dye, pigment) or a crystalline substance to the surface-modified composition or the surface-modified layer, the surface-modified layer is visualized, making it easier to manage the manufacturing process. For example, whether or not the resin member was uniformly covered by the surface-modified layer can be visualized, and it can be easily quantified as the coverage rate as described above.

The above explanations can be used as is for the surface modification composition, surface modification sheet, coating, and additives.

Process control methods include, for example, visually checking the surface-treated and colored parts, or recognizing and distinguishing images taken with a camera, or identifying the surface or cross section using known analytical methods. Examples include, but are not limited to, observation in real space using an optical microscope or electron microscope, methods using reciprocal space such as X-ray reflectance methods, spectroscopic methods such as infrared and Raman spectroscopy, contact angle methods, atomic force microscopes, nanoindentation methods, and surface analysis methods such as X-ray photoelectron spectroscopy, TOF-SIMS, and sum frequency generation spectroscopy. These methods may be used alone or in combination.

As explained above, this specification discloses the following:

[1]
A surface modification composition comprising a polymer component,
The surface modification layer formed from the surface modification composition has a loss tangent (tan δ) at 145 ° C. obtained by dynamic viscoelasticity measurement of 1.06 or less;
The surface modification composition, wherein the polymer component has a number average molecular weight of 20,000 or more.
[2]
The surface modification composition according to [1], wherein the polymer component comprises a polymer, partial polymer, or copolymer of a (meth)acrylic monomer.
[3]
The surface modification composition according to [2], wherein the (meth)acrylic monomer is a methacrylic acid alkyl ester.
[4]
The surface modification composition according to claim 1 or 2, wherein the polymer component contains a hydroxyl group.
[5]
The surface modification composition according to claim 4, wherein the polymer component further comprises an unsaturated hydrocarbon group.
[6]
A surface modification layer formed from the surface modification composition according to any one of [1] to [5].
[7]
A surface-modified sheet having a surface-modified layer according to [6].
[8]
A surface modified sheet comprising the surface modified layer according to [6] and a release sheet.
[9]
A laminate comprising the surface modification layer according to [6] laminated on at least a part of the surface of a resin material.
[10]
The surface modification layer according to [6] is laminated on at least a part of a surface of a resin member,
A surface-modified member in which the resin member and the surface-modified layer are covalently bonded together by a chemical reaction.
[11]
The surface-modified member according to claim 10, wherein the resin member contains an unsaturated hydrocarbon group-containing thermosetting resin.
[12]
The surface modified member according to [11], wherein the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin.
[13]
A coated article having a coating film on at least a part of the surface modified member according to [10].
[14]
A method for producing a surface modified member using the surface modified layer according to [6],
A method for producing a surface-modified member, comprising: laminating the surface-modified layer onto a resin member by hot molding.
[15]
The method for producing a surface-modified member according to [10], wherein the resin member contains an unsaturated polyester resin.
[16]
A method for producing a surface-modified member using the surface-modified sheet according to [7].
[17]
A method for producing a coated article using the surface modification layer according to [6],
A method for producing a surface-modified member, comprising: laminating the surface-modified layer on a resin member by hot molding; and forming a coating film on the surface-modified layer side of the surface-modified member.
[18]
The method for producing a coated article according to [17], wherein the resin member contains an unsaturated polyester resin.
[19]
A method for producing a coated article using the surface modified sheet according to [7].
[20]
A functional layer-attached member having a functional layer on at least a portion of the surface of the surface-modified layer side of the surface-modified member described in [10].
[21]
A method for producing a functional layer-attached member according to [20],
A method for manufacturing a member with a functional layer, comprising: a step of manufacturing a surface-modified member by laminating the surface-modified layer onto the resin member by hot molding; and a step of forming the functional layer on the surface-modified layer side of the surface-modified member.
[22]
A method for producing a functional layer-attached member using the surface modification layer according to [6],
A method for manufacturing a member with a functional layer, comprising: a step of manufacturing a surface-modified member by laminating the surface-modified layer onto a resin member by hot molding; and a step of forming a functional layer on the surface-modified layer side of the surface-modified member.
[23]
The method for producing a member with a functional layer according to [22], wherein the resin member contains an unsaturated polyester resin.
[24]
A method for producing a functional layer-attached member using the surface modified sheet according to [7].

The present invention will be explained in detail below with reference to examples, but the present invention is not limited to these examples in any way.

Example 1
(Synthesis of Polymer Components)
A reaction vessel equipped with a separable cover, a separating funnel, a thermometer, a nitrogen inlet tube, a Liebig cooler, a vacuum seal, and a stirrer was charged with a mixture of 100 mol parts of methyl acrylate (MA), 20 mol parts of 4-hydroxybutyl acrylate (4HBA), 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and ethyl acetate as a polymerization solvent so that the monomer component was 25% by mass. Nitrogen gas was flowed while gently stirring, and nitrogen replacement was performed for about 1 hour while stirring. Thereafter, the reaction vessel was heated to 60 ° C. ± 1 ° C. and reacted for 5 hours. Furthermore, the reaction vessel was heated to 75 ° C. ± 1 ° C. and reacted for 2 hours. As a result, a polymer solution (surface modification composition) 1 containing a hydroxyl group-containing acrylic polymer (polymer component) was obtained.
During the polymerization, ethyl acetate was appropriately added dropwise to control the temperature during the polymerization and to prevent a sudden increase in viscosity due to hydrogen bonding caused by polar groups on the monomer side chains.

(Preparation of surface modified sheet (1))
The prepared polymer solution (surface modification composition) 1 was filtered through a nylon mesh having an opening of 188 μm, and then coated with an applicator on a polyethylene terephthalate (PET) separator (product name "MRF38", manufactured by Mitsubishi Chemical Corporation) so that the final thickness (thickness of the surface modification layer) was 25 μm. The resulting mixture was dried at 80 ° C. for 2 minutes in a constant temperature dryer, and a PET separator (product name "MRE38", manufactured by Mitsubishi Chemical Corporation) was provided on the coating layer to produce a surface-modified sheet (1), which is a release sheet having a surface modification layer.

(Preparation of surface modified member (1))
The light separator MRF38 of the surface modified sheet (1) prepared above was peeled off, and the surface of the surface modified layer was placed on an unsaturated polyester resin-containing resin sheet (Kyocera Corporation, Kyocera Premix AP212SK2) (thickness 1 mm), and the surface modified member (1) was produced by compression molding with a press (molding pressure 10 MPa, upper mold 145 ° C., lower mold 135 ° C., 4 minutes). The dimensions of the lower mold were width 150 mm x length 120 mm, and the unsaturated polyester resin-containing resin sheet was subjected to molding so that the area ratio (mold charge rate) was 50% relative to the area of the lower mold. The mold charge rate of the surface modified sheet was 100%. At this time, the unsaturated polyester resin-containing resin sheet was in contact with the lower mold, and the surface modified sheet was arranged on the upper mold side. The above heating and pressing was started within 30 s after the unsaturated polyester resin-containing resin sheet and the surface modified sheet came into contact with the lower mold. In addition, the unsaturated polyester resin-containing resin sheet and the surface-modified sheet were heated and pressed within 2 minutes after lamination. All of the above operations were performed under atmospheric conditions, and no irradiation with active energy rays or preheating was performed before the heating and pressing operation.

(Preparation of coated object (1))
After peeling off the release sheet from the surface-modified member (1) prepared above, Kansai Paint Co., Ltd.'s Soflex 5100 and Soflex 5200 (two-component curing urethane paint) were applied to the surface-modified layer with a casting knife, and the coating was dried at room temperature (25 ° C.) for 15 minutes, and further heated at 80 ° C. for 30 minutes to harden, thereby producing a coated object (1).

Example 2
(Synthesis of Polymer Components)
Next, a reaction solution containing the polymer solution (surface modification composition) 1 containing the hydroxyl group-containing acrylic polymer prepared above, 2-methacryloyloxyethyl isocyanate (MOI) (product name "Kalends MOI", manufactured by Showa Denko K.K.), and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) as an addition reaction catalyst was stirred at 50°C for 10 hours in the atmosphere (addition reaction). In the reaction solution, the blending amount of MOI was 0.2 equivalents relative to the above-mentioned 4-hydroxybutyl acrylate. In addition, in the reaction solution, the blending amount of dibutyltin dilaurate was 0.06 parts by mass relative to 100 parts by mass of the polymer solution (surface modification composition) 1 containing the hydroxyl group-containing acrylic polymer. By this addition reaction, a polymer solution (surface modification composition) 2 containing an acrylic polymer (polymer component) having a hydroxyl group and an unsaturated hydrocarbon group (C=C group) in the side chain was obtained.

A surface-modified sheet (2), a surface-modified member (2), and a coated object (2) were produced in the same manner as in Example 1, except that polymer solution (surface-modified composition) 1 was changed to polymer solution (surface-modified composition) 2. In addition, taking into consideration the reaction of unsaturated hydrocarbon groups (C=C groups), the surface-modified sheet (2) and the surface-modified member (2) were kept in a light-shielded condition until molding.

[Examples 3, 4, and 8, and Comparative Example 1]
In the synthesis of the polymer component, the polymer solutions (surface modification compositions) 3, 4, 8, and r1 of Examples 3, 4, 8, and Comparative Example 1 were obtained in the same manner as in Example 1, except that the type and amount of the monomer were changed to the amounts listed in Table 1. Surface modified sheets (3), (4), (8), (r1), surface modified members (3), (4), (8), (r1), and coated objects (3), (4), (8), and (r1) were prepared in the same manner as in Example 1, except that polymer solution 1 was changed to polymer solutions (surface modification compositions) 3, 4, 8, and r1, respectively.

[Examples 5 and 9, Comparative Examples 2 and 3]
In the synthesis of the polymer component, the polymer solutions (surface modified compositions) 5, 9, r2, and r3 of Examples 5 and 9 and Comparative Examples 2 and 3 were obtained in the same manner as in Example 2, except that the type and amount of the monomer were changed to the amounts listed in Table 1. Surface modified sheets (5), (9), (r2), (r3), surface modified members (5), (9), (r2), (r3), and coated objects (5), (9), (r2), and (r3) were prepared in the same manner as in Example 2, except that the polymer solution 2 was changed to polymer solutions 5, 9, r2, and r3, respectively. In addition, in Comparative Example 2, the mold charge rate was changed to 100% and the unsaturated polyester resin-containing resin sheet and the surface modified sheet (r2) were subjected to molding.

Example 6
A reaction vessel equipped with a separable cover, a separating funnel, a thermometer, a nitrogen inlet tube, a Liebig cooler, a vacuum seal, and a stirrer was charged with a mixture of 100 mol parts of methyl methacrylate (MMA), 10 mol parts of 4-hydroxybutyl acrylate (4HBA), 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and ethyl acetate as a polymerization solvent so that the monomer component was 70% by mass. Nitrogen gas was flowed while gently stirring, and nitrogen replacement was performed for about 1 hour while stirring. Thereafter, the reaction vessel was heated to 72 ° C. ± 1 ° C. and reacted for 5 hours. Furthermore, the reaction vessel was heated to 80 ° C. ± 1 ° C. and reacted for 2 hours. Thus, a polymer solution (surface modification composition) 6 containing a hydroxyl group-containing methacrylic polymer (polymer component) was prepared. In addition, ethyl acetate was appropriately dropped during the polymerization to prevent a sudden increase in viscosity due to hydrogen bonding due to polar groups of the monomer side chains, etc., in order to control the temperature during polymerization.

A surface-modified sheet (6), a surface-modified member (6), and a coated object (6) were produced in the same manner as in Example 1, except that polymer solution (surface-modifying composition) 1 was changed to polymer solution (surface-modifying composition) 6.

Example 7
(Synthesis of Polymer Components)
A reaction solution containing a polymer solution (surface modification composition) 6 containing a hydroxyl group-containing methacrylic polymer prepared in the same manner as in Example 6, 2-methacryloyloxyethyl isocyanate (MOI) (product name "Kalends MOI", manufactured by Showa Denko K.K.), and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) as an addition reaction catalyst was stirred at 50°C for 10 hours in the atmosphere (addition reaction). In the reaction solution, the blending amount of MOI was 0.2 equivalents relative to the above-mentioned 4-hydroxybutyl acrylate. In addition, in the reaction solution, the blending amount of dibutyltin dilaurate was 0.06 parts by mass relative to 100 parts by mass of the polymer solution (surface modification composition) 1 containing a hydroxyl group-containing methacrylic polymer. By this addition reaction, a polymer solution (surface modification composition) 7 containing a methacrylic polymer (polymer component 7) having a hydroxyl group and an unsaturated hydrocarbon group (C=C group) in the side chain was obtained.

A surface-modified sheet (7), a surface-modified member (7), and a coated object (7) were produced in the same manner as in Example 1, except that polymer solution (surface-modifying composition) 1 was changed to polymer solution (surface-modifying composition) 7.

[Examples 10, 12, and 14]
In the synthesis of the polymer component, the polymer solutions (surface modification compositions) 10, 12, and 14 of Examples 10, 12, and 14 were obtained in the same manner as in Example 6, except that the type and amount of the monomer were changed to the amounts listed in Table 1. Surface modified sheets (10), (12), and (14), surface modified members (10), (12), and (14), and coated objects (10), (12), and (14) were prepared in the same manner as in Example 6, except that polymer solution 6 was changed to polymer solutions 10, 12, and 14, respectively.

[Examples 11, 13, and 15]
In the synthesis of the polymer component, the polymer solutions (surface modification compositions) 11, 13, and 15 of Examples 11, 13, and 15 were obtained in the same manner as in Example 7, except that the type and amount of the monomer were changed to the amounts listed in Table 1. Surface modified sheets (11), (13), and (15), surface modified members (11), (13), and (15), and coated objects (11), (13), and (15) were prepared in the same manner as in Example 7, except that polymer solution 7 was changed to polymer solutions 11, 13, and 15, respectively.

Comparative Example 4
On an unsaturated polyester resin-containing resin sheet (Kyocera Corporation, Kyocera Premix AP212SK2) (thickness 1 mm), Soflex 6800 primer was applied with a casting knife, and dried at room temperature to form a dried primer film, and a surface-modified member (r4) was prepared as a two-layer sample of an unsaturated polyester resin-containing resin sheet and a dried primer film. In addition, Soflex 5100 and Soflex 5200 (two-component curing urethane paint) manufactured by Kansai Paint Co., Ltd. were applied with a casting knife to the dried primer film of the surface-modified member, and the coating film was dried at room temperature (25 ° C) for 15 minutes, and further heated at 80 ° C for 30 minutes to harden, and a coated object (r4) was prepared.

〔evaluation〕
<Adhesion 1>
The release sheets of the surface modified members prepared in the examples and comparative examples were peeled off, and cross-cut evaluation (checkerboard peeling) was performed by the cross-cut method described in JIS K5600-5-6, and the number of unpeeled surface modified layers (attached number) was counted and listed in Table 1. When the number of unpeeled surface modified layers is 50 or more out of 100, the adhesion between the resin member and the surface modified layer is good (○), and when it is 49 or less, it can be judged to be poor (×).
・Cutting interval: 2mm
・Number of cross-cuts: 100 squares ・Removal tape: (Nichiban) Cellophane tape (registered trademark) 24 mm wide

<Adhesion 2>
The coated objects prepared in the Examples and Comparative Examples were subjected to cross-cut evaluation (grid peeling) by the cross-cut method described in JIS K5600-5-6, and the number of unpeeled coating films (attached number) was counted and shown in Table 1. When the number of unpeeled coating films was 50 or more out of 100, the adhesion between the surface modified layer and the coating film was judged to be good (◯), and when the number was 49 or less, it was judged to be poor (×).
・Cutting interval: 2mm
・Number of cross-cuts: 100 squares ・Removal tape: (Nichiban) Cellophane tape (registered trademark) 24 mm wide

<Viscoelasticity (tan δ) measurement 1>
(Shear storage modulus G', complex shear modulus G and loss tangent tan δ)
The surface modified layers of each example prepared in Examples 1 to 5, 8, and 9 and Comparative Examples 1 to 3 were laminated to a thickness of about 1.5 mm, and then autoclaved (0.5 MPa, 50° C., 15 minutes) to adhere each layer. The thus obtained product was punched into a disk shape with a diameter of 7.9 mm, which was used as a measurement sample. Dynamic viscoelasticity measurement was performed under the following conditions using a dynamic viscoelasticity measuring device (Advanced Rheometric Expansion System (ARES)) manufactured by Rheometric Scientific. From the measurement results, the shear storage modulus G', shear loss modulus G'', and complex shear modulus G of the sample at each temperature (such as 145° C.) were obtained. In addition, the loss tangent tan δ (shear loss modulus G''/shear storage modulus G') in the above dynamic viscoelasticity measurement was obtained.

[Measurement condition]
Deformation mode: torsion Measurement frequency: 1 Hz
Temperature range: 20℃ to 150℃
Heating rate: 5°C/min. Shape: Parallel plate 7.9mmφ

<Viscoelasticity (tan δ) measurement 2>
(Shear storage modulus G', complex shear modulus G and loss tangent tan δ)
The surface modified layers having a thickness of 25 μm produced in each of Examples 6, 7, and 10 to 15 were punched out to a size of 70 mm×10 mm, which was used as a measurement sample.
Using RSA-G2 manufactured by TA Instruments, dynamic viscoelasticity measurements were performed under the following conditions without plastic deformation or deflection of the sample. From the measurement results, the tensile storage modulus E', tensile loss modulus E'', and complex tensile modulus E of the sample at each temperature (e.g., 145°C) were obtained. In addition, the loss tangent tan δ (tensile loss modulus E''/tensile storage modulus E') in the dynamic viscoelasticity measurements was obtained. The obtained tensile modulus (E, E', E'') can be converted to shear modulus G based on the relational equation E = 3G by assuming a Poisson's ratio of 0.5.

[Measurement condition]
Deformation mode: Tensile Measurement frequency: 1 Hz
Temperature range: 20℃ to 150℃
Heating rate: 5° C./min

<Liquidity assessment>
10 ml of Zebra Hi-Mackie (red) ink containing an oil-based dye was diluted with 50 ml of ethyl acetate and mixed with 10 ml of the surface-modifying composition solution to obtain a colored surface-modifying composition solution.
The prepared colored surface modified composition solution was filtered through a nylon mesh having an opening of 188 μm, and then coated with an applicator on a polyethylene terephthalate (PET) separator (product name "MRF38", manufactured by Mitsubishi Chemical Corporation) so that the final thickness (thickness of the surface modified layer) was 25 μm. The resulting mixture was dried in a thermostatic dryer at 80 ° C. for 2 minutes to produce a colored surface modified sheet having a surface modified layer on a release sheet.

Then, the sample was molded in the same manner as in the manufacture of the surface-modified member (1) in Example 1, and the release liner was peeled off to obtain a colored surface-modified member in which the surface-modified layer containing the colorant and the resin sheet (resin member) were integrated. The colored surface-modified member was photographed and imaged using FPD8010J (manufactured by FUJIFILM Corp.) software and a GT-F740 (manufactured by EPSON Corporation) scanner, and the fluidity of the surface-modified layer was evaluated.

The image was scaled to MW, and the pressure value was the sustained pressure, and the color shade was determined. In identifying the color shade, the pressure range was divided into the following regions: less than 1.0 MPa, 1.0 to less than 15.0 MPa, 15.0 to less than 20.0 MPa, 20.0 to less than 25.0 MPa, 25.0 to less than 30.0 MPa, 30.0 to less than 35.0 MPa, 35.0 to less than 40.0 MPa, 40.0 to less than 45.0 MPa, 45.0 to less than 50.0 MPa, and 50.0 MPa or more.

The pressurized area ( ^mm2 ) of each region was calculated, and the sum of the areas of the regions judged to be 1.0 MPa or more was divided by the total measured area to calculate the coverage rate (%). Next, the coverage variation was calculated by the following method.
The median value of the pressure in each of the above-mentioned regions was taken as M (for example, the median value M for a region of 15.0 to less than 20.0 MPa was 17.5 MPa). Furthermore, the pressurized area ( ^mm2 ) of each region was taken as N, and Mn and Mw were calculated based on the following formula. Finally, Mw/Mn was calculated to obtain the coating variation.

The closer the coating variation is to 1, the more uniform the coating is, and the greater the value is above 1, the greater the variation.

The examples and comparative examples are shown in the table below.

The materials listed in Table 1 are as follows:

(Non-hydroxyl group-containing (meth)acrylic monomer)
MA: Methyl acrylate MMA: Methyl methacrylate IBXA: Isobornyl acrylate ACMO: 4-acryloylmorpholine CHMA: Cyclohexyl methacrylate 2EHA: 2-ethylhexyl acrylate

(Hydroxyl Group-Containing (Meth)Acrylic Monomer)
4HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate

(Unsaturated Hydrocarbon Group-Containing Compound)
MOI: 2-methacryloyloxyethyl isocyanate (product name "Kalends MOI", manufactured by Showa Denko K.K.)

　The coated article using the surface modification sheet according to the embodiment of the present invention had good adhesion between the resin member and the surface modification layer, and between the surface modification layer and the coating film, and the coating film had very high adhesive strength. In addition, according to the surface modification sheet according to the embodiment of the present invention, the surface modification layer can be formed on the resin member with a high coverage rate, and the coating variation can be suppressed. On the other hand, the coated article of Comparative Example 1 has a number average molecular weight of less than 20,000 of the polymer component in the surface modification composition, and the tan δ of the surface modification layer is greater than 1.06, so the fluidity is high, the coverage rate is poor, there is a lot of coating variation, and the adhesion is poor. The coated articles of Comparative Examples 2 and 3 have a surface modification layer with a tan δ of greater than 1.06, so the fluidity is high, and Comparative Example 2, in which the charging area to the mold is 100%, had excellent adhesion, but the coverage rate and coating variation were inferior to those of the examples. Comparative Example 3, in which the charging area to the mold is 50%, had a coverage rate and coating variation inferior to those of the examples, and the adhesion was poor. In Comparative Example 4, the coating rate, coating variation, and adhesion were inferior to those of the Examples because the material was in a solution state and had high fluidity.

The surface modification composition according to the embodiment of the present invention can form the surface modification layer according to the embodiment of the present invention. The surface modification layer according to the embodiment of the present invention can be surface treated simultaneously with the molding process of the resin member, and the surface modification layer can be formed on the resin member with a high coverage rate and reduced coverage variation to obtain a surface modification member with excellent adhesion. The surface modification sheet according to the embodiment of the present invention can form the surface modification layer, and the surface modification layer and the resin member can be integrally molded when forming the surface modification member and the member with a functional layer.

The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.
This application is based on a Japanese patent application (Patent Application No. 2022-155383) filed on September 28, 2022, the contents of which are incorporated herein by reference.

Reference Signs List

10, 11 Surface modified layer 20 Release sheet 30

Coating film

100, 101 Resin member 200 Surface modified sheet 300 Coating 400 Resin material 500 Member with functional layer

Claims

A surface modification composition comprising a polymer component,
The surface modification layer formed from the surface modification composition has a loss tangent (tan δ) at 145 ° C. obtained by dynamic viscoelasticity measurement of 1.06 or less;
The surface modification composition, wherein the polymer component has a number average molecular weight of 20,000 or more.
The surface modification composition according to claim 1, wherein the polymer component comprises a polymer, partial polymer, or copolymer of a (meth)acrylic monomer.
The surface modification composition according to claim 2, wherein the (meth)acrylic monomer is an alkyl methacrylate ester.
The surface modification composition according to claim 1, wherein the polymer component contains a hydroxyl group.
The surface modification composition according to claim 4, wherein the polymer component further comprises an unsaturated hydrocarbon group.
A surface modification layer formed from the surface modification composition according to any one of claims 1 to 5.
A surface-modified sheet having the surface-modified layer according to claim 6.
A surface-modified sheet comprising the surface-modified layer according to claim 6 and a release sheet.
A laminate in which the surface modification layer according to claim 6 is laminated on at least a portion of the surface of a resin material.
The surface modification layer according to claim 6 is laminated on at least a part of a surface of a resin member,
A surface-modified member in which the resin member and the surface-modified layer are covalently bonded together by a chemical reaction.
The surface-modified member according to claim 10, wherein the resin member contains a thermosetting resin containing an unsaturated hydrocarbon group.
The surface-modified member according to claim 11, wherein the unsaturated hydrocarbon group-containing thermosetting resin is an unsaturated polyester resin.
A coated article having a coating film on at least a portion of the surface-modified member according to claim 10.
A method for producing a surface modified member using the surface modified layer according to claim 6,
A method for producing a surface-modified member, comprising: laminating the surface-modified layer onto a resin member by hot molding.
The method for manufacturing a surface-modified member according to claim 10, wherein the resin member contains an unsaturated polyester resin.
A method for manufacturing a surface-modified member using the surface-modified sheet according to claim 7.
A method for producing a coated article using the surface modification layer according to claim 6,
A method for producing a surface-modified member, comprising: laminating the surface-modified layer on a resin member by hot molding; and forming a coating film on the surface-modified layer side of the surface-modified member.
The method for producing a coated article according to claim 17, wherein the resin member contains an unsaturated polyester resin.
A method for producing a coated object using the surface-modified sheet according to claim 7.
A functional layer-attached member having a functional layer on at least a portion of the surface of the surface-modified layer side of the surface-modified member according to claim 10.
A method for producing a functional layer-attached member according to claim 20, comprising the steps of:
A method for manufacturing a member with a functional layer, comprising: a step of manufacturing a surface-modified member by laminating the surface-modified layer onto the resin member by hot molding; and a step of forming the functional layer on the surface-modified layer side of the surface-modified member.
A method for producing a functional layer-attached member using the surface modification layer according to claim 6,
A method for manufacturing a member with a functional layer, comprising: a step of manufacturing a surface-modified member by laminating the surface-modified layer onto a resin member by hot molding; and a step of forming a functional layer on the surface-modified layer side of the surface-modified member.
The method for producing a member with a functional layer according to claim 22, wherein the resin member contains an unsaturated polyester resin.
A method for manufacturing a member with a functional layer using the surface-modified sheet according to claim 7.