Laminate film and molded article

Abstract

To provide a laminate film excellent in retention of surface hydrophilicity.SOLUTION: A laminate film 1 is for three-dimensional coating molding and includes a substrate layer 10 and a surface resin layer 20. The substrate layer 10 is made of a thermoplastic resin. The surface resin layer 20 is such a layer as to be formed by ultraviolet cure of a resin composition (X). The resin composition (X) includes an ultraviolet cure resin (a), a (meth)acryloyl group-containing compound (b), a photoinitiator (c) and a silicon-containing substance (d). The (meth)acryloyl group-containing compound (b) has at least one kind of anionic hydrophilic group selected from a sulphonic acid group, a carboxylic acid group, a phosphate group and an amino group. The silicon-containing substance (d) contains at least one of silica particles (d1) having a silanol group and a silicate oligomer (d2) having the silanol group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a laminate film and a molded article, and more particularly to a laminate film having a base layer and a surface resin layer, and a molded article having this laminate film on the surface of an adherend. [Background technology]

[0002] Three-dimensional overlay method (TOM) is a technology that uses an adherend made of a component with three-dimensional irregularities, such as an automobile interior or exterior part, a home appliance part, or a building part, as an adherend, and a laminated film such as a decorative sheet. The laminated film and the adherend are pressed together under vacuum or reduced pressure conditions to obtain a molded product. This method forms a coating layer on the surface of the adherend, providing protection while also decorating it.

[0003] Patent Document 1 discloses a decorative sheet having at least a primer layer and a surface protective layer on a substrate, the surface protective layer being made of a cured product of an ionizing radiation-curable resin composition, and the primer layer being formed using a primer composition containing at least a polyol and an isocyanate. Patent Document 2 also discloses a laminate having a monolayer film formed on at least one surface of a substrate, the monolayer film being polymerized from a mixture containing a monomer composition containing a specific monomer (I) and a polyvalent monomer (II) having no sulfonic acid group, carboxyl group, or phosphate group in a specific molar ratio, the monolayer film having at least one anionic hydrophilic group selected from sulfonic acid group, carboxyl group, and phosphate group, and the ratio of the anion concentration on the outer surface to the anion concentration at a midpoint between the inner surface in contact with the substrate and the outer surface being equal to or greater than a specific value, the laminate having excellent antifogging, antifouling, and antistatic properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-016699 [Patent Document 2] Patent No. 5943918 Summary of the Invention [Problem to be solved by the invention]

[0005] Laminate films used in three-dimensional coating molding are required to have stretchability suitable for three-dimensional molding, as well as to have hydrophilic surfaces that are able to maintain this hydrophilicity for a long period of time. However, conventional laminate films such as the decorative sheet of Patent Document 1 and the laminate of Patent Document 2 may not be able to maintain the hydrophilicity of their surfaces.

[0006] An object of the present disclosure is to provide a laminated film and a molded article that are excellent in maintaining surface hydrophilicity. [Means for solving the problem]

[0007] A laminate film according to one embodiment of the present disclosure is a laminate film for three-dimensional coating molding, comprising a substrate layer and a surface resin layer. The substrate layer is made of a thermoplastic resin. The surface resin layer is a layer formed by ultraviolet curing of a resin composition. The resin composition contains an ultraviolet curable resin, a (meth)acryloyl group-containing compound, a photoinitiator, and a silicon-containing substance. The (meth)acryloyl group-containing compound has at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and an amino group. The silicon-containing substance includes at least one of silica particles having a silanol group and a silicate oligomer having a silanol group.

[0008] A molded article according to one aspect of the present disclosure includes an adherend and the laminate film disposed on a surface of the adherend. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a laminate film and a molded article that are excellent in maintaining surface hydrophilicity. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the laminated film of the present embodiment. [Figure 2] FIG. 2 is a schematic cross-sectional view showing an example of the molded product of this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0011] (1) Overview The laminate film according to this embodiment (hereinafter also referred to as laminate film 1) is for use in three-dimensional coating molding (TOM). That is, the laminate film 1 is particularly suitable for three-dimensional coating molding, in which the laminate film 1 is pressed onto the surface of an adherend 100 to obtain a molded article 2. As shown in FIG. 1, the laminate film 1 includes a base layer 10 and a surface resin layer 20. The base layer 10 is made of a thermoplastic resin (hereinafter also referred to as thermoplastic resin (A)). The surface resin layer 20 is a layer formed by ultraviolet curing of a resin composition (hereinafter also referred to as resin composition (X)). The resin composition (X) contains an ultraviolet-curable resin (hereinafter also referred to as ultraviolet-curable resin (a)), a (meth)acryloyl group-containing compound (hereinafter also referred to as (meth)acrylolyl group-containing compound (b)), a photoinitiator (hereinafter also referred to as photoinitiator (c)), and a silicon-containing substance (hereinafter also referred to as silicon-containing substance (d)). The (meth)acryloyl group-containing compound (b) has at least one anionic hydrophilic group selected from sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, and amino groups. The silicon-containing substance (d) includes at least one of silica particles having silanol groups (hereinafter also referred to as silica particles (d1)) and silicate oligomers having silanol groups (hereinafter also referred to as silicate oligomers (d2)). In this specification, "(meth)acryloyl" refers to acrylic, methacrylic, or both.

[0012] As a result of extensive research to solve the above-mentioned problems, the inventors discovered that the maintenance of the hydrophilicity of the surface can be adjusted by adding a specific substance to a resin composition containing an ultraviolet-curable resin and a compound having an anionic hydrophilic group, which forms the surface resin layer 20, and thus completed the present disclosure.

[0013] The laminate film 1 of this embodiment has excellent surface hydrophilicity retention. The reason why the laminate film 1 having the above-described configuration exhibits this effect is not entirely clear, but can be presumed, for example, as follows. The resin composition (X) used to form the surface resin layer 20 by UV curing contains, in addition to the UV-curable resin (a) and the (meth)acryloyl-containing compound (b) having an anionic hydrophilic group, silica particles (d1) having a silanol group and / or a silicate oligomer (d2) having a silanol group as the silicon-containing substance (d), so that the silicon-containing substance (d) is immobilized in the cured product of the UV-curable resin (a) in the surface layer of the surface resin layer 20. The anionic hydrophilic groups of the (meth)acryloyl-group-containing compound (b) interact with the silanol groups of the silicon-containing substance (d), thereby more strongly bonding the anionic hydrophilic groups to the surface of the surface resin layer 20, thereby further maintaining the surface hydrophilicity of the laminate film 1.

[0014] The molded article according to this embodiment (hereinafter also referred to as molded article 2) includes an adherend 100 and a laminated film 1 placed on the surface of the adherend 100, as shown in FIG.

[0015] The molded article 2 uses the above-mentioned laminated film 1, which is excellent in maintaining the surface hydrophilicity, and therefore the hydrophilicity of the surface can be maintained.

[0016] (2) Details <Laminated film> The laminated film 1 includes a base layer 10 and a surface resin layer 20. In addition to the base layer 10 and the surface resin layer 20, the laminated film 1 may also include, for example, a print / pattern layer 30, an adhesive layer 40, etc., as shown in Fig. 2, and may also include a primer layer, etc. Each component will be described below.

[0017] [Base material layer] The substrate layer 10 is a layer that serves as a support and is usually formed of a resin sheet (resin film). The substrate layer 10 is made of a thermoplastic resin (A). That is, the substrate layer (10) is composed of the thermoplastic resin (A). The substrate layer 10 is made of the thermoplastic resin (A), so that the laminated film 1 can have improved three-dimensional formability. The substrate layer 10 may contain other components, such as resins other than the thermoplastic resin (A), as long as the effects of the present disclosure are not impaired.

[0018] The thermoplastic resin (A) may be appropriately selected depending on the three-dimensional formability of the laminate film 1, its compatibility with the surface resin layer 20, and the like. Specific examples of the thermoplastic resin (A) include acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic acid ester resin; acrylic resins such as polymethyl methacrylate resin (PMMA resin); polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; and polyester resins such as polyethylene terephthalate (PET) resin. Among these, at least one of acrylic resin and vinyl chloride resin is preferred from the viewpoint of further improving three-dimensional formability, with acrylic resin being more preferred and PMMA resin being even more preferred. Only one type of thermoplastic resin (A) may be used, or two or more types may be mixed and used.

[0019] The substrate layer 10 may be formed of a single-layer sheet made of thermoplastic resin (A), or may be formed of a multi-layer sheet including a layer made of the same or different resin as the thermoplastic resin (A).

[0020] In order to improve adhesion to adjacent layers, one or both surfaces of the substrate layer 10 may be subjected to a physical or chemical surface treatment such as an oxidation method or a roughening method, as necessary. Examples of oxidation methods used to treat the surface of the substrate layer 10 include corona discharge treatment, plasma treatment, and chromium oxidation treatment. Examples of roughening methods used to treat the surface of the substrate layer 10 include sandblasting and solvent treatment. These surface treatments are selected appropriately depending on the type of thermoplastic resin (A) constituting the substrate layer 10, but corona discharge treatment is preferably used from the viewpoints of improving adhesion and ease of use.

[0021] Furthermore, the base layer 10 may be colored by blending a coloring agent or the like, or may be painted to adjust the color or the like, or a pattern may be formed to impart design or the like.

[0022] The thickness of the base layer 10 is not particularly limited and is set appropriately depending on the application of the laminated film 1, but is usually about 30 μm to 500 μm, preferably about 50 μm to 125 μm. When the thickness of the base layer 10 is within the above range, three-dimensional formability, design properties, etc. can be further improved.

[0023] [Surface resin layer] The surface resin layer 20 is a layer provided on the surface of the laminate film 1 in order to improve the surface hydrophilicity of the molded article 2 as well as the contamination resistance, scratch resistance, chemical resistance, etc. The surface resin layer 20 is a layer formed by ultraviolet curing of a resin composition (X) containing an ultraviolet-curable resin (a), a (meth)acryloyl group-containing compound (b), a photoinitiator (c), and a silicon-containing substance (d). In other words, the surface resin layer 20 is a layer made of an ultraviolet-cured product of the resin composition (X).

[0024] (Resin composition) The resin composition (X) contains an ultraviolet-curable resin (a), a (meth)acryloyl group-containing compound (b), a photoinitiator (c), and a silicon-containing substance (d). In addition to these components (a) to (d), the resin composition (X) preferably contains a silane coupling agent having a (meth)acryloyl group (hereinafter also referred to as silane coupling agent (e)). The resin composition (X) may further contain other components within a range that does not impair the effects of the present disclosure. In the resin composition (X), each of the components (a) to (d) may be used alone, or two or more may be mixed together. Each component will be described below.

[0025] (UV curing resin) The ultraviolet curable resin (a) is a resin that undergoes a polymerization reaction and hardens when irradiated with ultraviolet light. The polymerization reaction is not particularly limited, and examples thereof include radical polymerization, cationic polymerization, and anionic polymerization. By forming the surface resin layer 20 by ultraviolet curing the ultraviolet curable resin (a), ultraviolet light can be uniformly irradiated onto the ultraviolet curable resin (a), thereby enabling uniform hardening.

[0026] Examples of the ultraviolet curable resin (a) include acrylic ultraviolet curable resins such as acrylic resins, urethane ultraviolet curable resins such as urethane resins, and mixed resins thereof. These resins are preferred because they are easy to handle and process, and have excellent durability. Examples of the acrylic resin include acrylic acrylate. Acrylic acrylate is a (meth)acrylate polymer having a (meth)acryloyl group in the side chain. Examples of the urethane resin include urethane acrylate. Urethane acrylate is a (meth)acrylate polymer having a urethane group (-NHCOO-). As the ultraviolet curable resin (a), acrylic ultraviolet curable resins are preferred, and acrylic resins are more preferred.

[0027] The weight average molecular weight (Mw) of the UV-curable resin (a) is preferably 1,000 or more and 300,000 or less, more preferably 2,000 or more and 150,000 or less, and even more preferably 20,000 or more and 150,000 or less. By setting the Mw of the UV-curable resin (a) within the above range, the conformability of the laminate film 1 to the adherend 100 can be further improved in three-dimensional coating molding (TOM) under vacuum or reduced pressure conditions, making it possible to coat adherends 100 with complex shapes. Mw is preferably measured using GPC (gel permeation chromatography) and the molecular weight calculated in terms of polystyrene.

[0028] The proportion of the ultraviolet curable resin (a) relative to the resin composition (X) is, for example, 70% by mass or more, and preferably 75% by mass or more. The upper limit of the proportion of the ultraviolet curable resin (a) is not particularly limited, but is, for example, 97% by mass or less, and preferably 95% by mass or less.

[0029] ((Meth)acryloyl group-containing compound) The (meth)acryloyl group-containing compound (b) is a low molecular weight compound having at least one anionic hydrophilic group selected from a sulfonic acid group (sulfo group (-SO3H)), a carboxylic acid group (carboxy group (-COOH)), a phosphoric acid group (-OP(O)(OH)2), and an amino group (-NH2), and a (meth)acryloyl group. The anionic hydrophilic group of the (meth)acryloyl group-containing compound (b) can impart hydrophilicity to the surface of the surface resin layer 20.

[0030] Examples of the (meth)acryloyl group-containing compound (b) include 3-sulfopropyl potassium methacrylate (potassium 3-(methacryloyloxy)propanesulfonate), 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, ethylene acrylate phosphate, ethylene methacrylate phosphate, etc. Among these, the use of 3-sulfopropyl potassium methacrylate is preferred because it can more reliably improve the maintenance of the hydrophilic surface.

[0031] The proportion of the (meth)acryloyl group-containing compound (b) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the ultraviolet curable resin (a), and the proportion of the (meth)acryloyl group-containing compound (b) is preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less.

[0032] (photoinitiator) The photoinitiator (c) is a compound that generates active species such as radicals that react with ethylenically unsaturated double bonds and the like when exposed to electromagnetic waves such as ultraviolet rays or high-energy rays such as electron beams, and known photoinitiators can be used. Examples of the photoinitiator (c) include α-hydroxyalkylphenone-based photoinitiators, oxime ester-based photoinitiators, α-aminoalkylphenone-based photoinitiators, acylphosphine oxide-based photoinitiators, and thioxanthone-based photoinitiators. Among these, α-hydroxyalkylphenone-based photoinitiators are preferred.

[0033] Commercially available photoinitiators (c) can also be used. Examples of commercially available photoinitiators (c) include Irgacure-184 and Irgacure-651 (both manufactured by Ciba Specialty Chemicals). Among these, Irgacure-184 is preferred.

[0034] The proportion of the photoinitiator (c) is, for example, 1 part by mass or more and 10 parts by mass or less, and preferably 1.5 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the ultraviolet curable resin (a).

[0035] (Silicon-containing substances) The silicon-containing material (d) is a material containing silicon atoms. The silicon-containing material (d) includes at least one of silica particles (d1) having silanol groups and silicate oligomers (d2) having silanol groups. The term "silanol group" refers to a hydroxy group (OH group) bonded to a silicon atom.

[0036] Examples of silica particles (d1) include silica particles, i.e., particles containing SiO2 as a main component, which have silanol groups on the surface of the particles, and these silanol groups are not surface-modified with (meth)acryloyl groups, etc. The term "main component" refers to the component with the highest content, and means, for example, a component with a content of 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.

[0037] The average particle diameter of the silica particles (d1) is preferably 10 nm or more and 8 μm or less. In this case, the light transmittance of the surface resin layer 20 can be further improved. The average particle diameter of the silica particles (d1) is more preferably 20 nm or more and 3 μm or less, and even more preferably 30 nm or more and 1 μm or less. The "average particle diameter" of the silica particles (d1) refers to the volume-based median diameter measured by laser diffraction.

[0038] For example, silica sol can be used as the silica particles (d1). "Silica sol" refers to a colloidal solution in which silica particles are uniformly dispersed in an organic solvent or other dispersing medium. Examples of dispersing mediums include methyl ethyl ketone and propylene glycol monomethyl ether acetate.

[0039] The silicate oligomer (d2) is a hydrolysis condensation product of multiple silicate esters, and refers to an oligomer having a polysiloxane structure (-Si-O-Si-) and at least one silanol group. Examples of silicate esters include tetraalkoxysilanes such as tetramethoxysilane. Examples of the silicate oligomer (d2) include compounds represented by the following formula (1):

[0040] [ka]

[0041] In the above formula (1), R 1 and R 2are each independently a hydrocarbon group or a hydrogen atom. 1 and X 2 are each independently a hydrocarbon group or a hydrogen atom, and n is an integer of 2 to 100. 1 may be the same or different, and multiple R 2 may be the same or different. 1 , R 2 , X 1 and X 2 At least one of is a hydrogen atom.

[0042] R 1 , R 2 , X 1 and X 2 Examples of the hydrocarbon group represented by R include alkyl groups such as methyl and ethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. 1 , R 2 , X 1 and X 2 As the group, an alkyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is even more preferable.

[0043] The proportion of the silicon-containing substance (d), i.e., the total proportion of the silica particles (d1) and silicate oligomer (d2), is preferably 3 to 20 parts by mass relative to 100 parts by mass of the ultraviolet-curable resin (a). In this case, the maintenance of surface hydrophilicity can be further improved. The lower limit of the proportion of the silicon-containing substance (d) is more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit of the proportion of the silicon-containing substance (d) is more preferably 17 parts by mass or less, even more preferably 15 parts by mass or less, and particularly preferably 13 parts by mass or less.

[0044] (Silane coupling agent) The silane coupling agent (e) is a silane coupling agent having a (meth)acryloyl group, and refers to a silane compound having a (meth)acryloyl group as a functional group and a hydrolyzable group. Examples of the hydrolyzable group include a trialkylsilyl group and an alkyldialkoxysilyl group. The laminate film 1 can further improve the maintenance of surface hydrophilicity by containing the silane coupling agent (e) in the resin composition (X).

[0045] Examples of the silane coupling agent (e) include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 2-(meth)acryloxypropyltrimethoxysilane, and 2-(meth)acryloxypropyltriethoxysilane.

[0046] When the resin composition (X) contains the silane coupling agent (e), the proportion of the silane coupling agent (e) is, for example, from 0.05 to 1 part by mass, preferably from 0.1 to 0.5 parts by mass, relative to 100 parts by mass of the ultraviolet-curable resin (a). In this case, the laminate film 1 can further improve the maintenance of surface hydrophilicity.

[0047] (Other ingredients) Examples of other components include a solvent, a leveling agent, a surfactant, and the like.

[0048] The solvent is not particularly limited, and known solvents can be used, such as monoalcohols such as methanol, ethanol, and isopropanol; monoetherified alkylene glycols such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; esters such as ethyl acetate and butyl acetate; and ketones such as 4-methyl-2-pentanone and methyl ethyl ketone. A volatile solvent is preferred. A volatile solvent refers to a solvent having a boiling point of, for example, 150°C or lower. By using a volatile solvent as the solvent, a dried coating film of the resin composition (X) can be more easily formed. One type of volatile solvent may be used alone, or two or more types may be mixed and used. The ratio of the solvent in the resin composition (X) is, for example, from 100 to 1,000 parts by mass, and preferably from 200 to 600 parts by mass, per 100 parts by mass of the ultraviolet-curable resin (a).

[0049] The thickness of the surface resin layer 20 is preferably 1 μm or more and 30 μm or less, and more preferably 3 μm or more and 10 μm or less. When the thickness of the surface resin layer 20 is within the above range, the laminate film 1 can further improve the maintenance of the surface hydrophilicity.

[0050] The surface resin layer 20 is formed, for example, by applying a resin composition (X) and curing the resulting coating film with ultraviolet light. The resin composition (X) is applied to the layer adjacent to which the surface resin layer 20 will be formed by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating, preferably gravure coating, so that the thickness after curing will be a predetermined thickness, and then a dried coating film (uncured resin layer) is formed. The dose of ultraviolet light can be selected appropriately depending on the type of ultraviolet-curable resin (a) used and the thickness of the surface resin layer 20 to be formed, but is usually 100 mJ / cm. 2 More than 2000mJ / cm 2 less than 300 mJ / cm 2 More than 1000mJ / cm 2 It is preferable that:

[0051] [Printing / pattern layer] The print / pattern layer 30 is a layer that imparts decorativeness to the molded article 2, and is provided as necessary in the laminate film 1, for example, between the base material layer 10 and the surface resin layer 20. The print / pattern layer 30 is formed, for example, by printing various patterns using ink and a printing machine. The pattern formed by the print / pattern layer 30 is not particularly limited, and examples include wood grain patterns, stone grain patterns, fabric patterns, tile patterns, and brickwork patterns. The print / pattern layer 30 may also be formed as a so-called solid print layer without a pattern.

[0052] [Adhesive layer] The adhesive layer 40 is a layer that is provided as needed adjacent to the surface of the base material layer 10 opposite to the surface resin layer 20, for the purpose of improving the adhesion and close contact between the laminate film 1 and the adherend 100. In three-dimensional coating molding, if the adherend 100 has an adhesive layer on its surface, the laminate film 1 does not need to have the adhesive layer 40.

[0053] The resin forming the adhesive layer 40 is not particularly limited as long as it can improve adhesiveness and adhesion, and for example, a thermoplastic resin or a thermosetting resin is used. Examples of thermoplastic resins include acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber-based resin. Examples of thermosetting resins include urethane resin and epoxy resin. Thermoplastic resins and thermosetting resins may be used alone or in combination of two or more.

[0054] [Primer layer] The primer layer can be provided, for example, between the base layer 10 and the print / pattern layer 30, or between the surface resin layer 20 and the print / pattern layer 30, in order to improve the adhesion between these layers.

[0055] Resin compositions for forming the primer layer preferably contain, as a binder resin, urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene, etc. These resins can be used alone or in combination of two or more. Among these, at least one selected from the group consisting of urethane resin, (meth)acrylic resin, and (meth)acrylic-urethane copolymer resin is preferred.

[0056] The thickness of the primer layer is not particularly limited, but is, for example, about 0.5 μm or more and 20 μm or less.

[0057] The laminated film 1 can be produced, for example, by forming a print / pattern layer 30, an adhesive layer 40, a primer layer, etc. in a predetermined order on one or both sides of a base layer 10, and then forming a surface resin layer 20 as the outermost layer.

[0058] <Molded products> The molded article 2 of this embodiment includes an adherend 100 and a laminated film 1 placed on the surface of the adherend 100. The adherend 100 is, for example, a member having three-dimensional irregularities. "Placed on the surface of the adherend" means that the surface of the adherend 100 and the laminated film 1 are directly overlapped by three-dimensional overmolding (TOM).

[0059] Three-dimensional overmolding (TOM) for producing the molded article 2 is carried out, for example, by overlapping the surface of the laminate film 1 opposite the surface resin layer 20 on the surface of the adherend 100, and then pressing the surface of the adherend 100 and the laminate film 1 together under heating and vacuum or reduced pressure conditions, and molding. The molding temperature is preferably in the range of 130°C to 180°C, and more preferably in the range of 150°C to 170°C. This allows for better adhesion and conformability between the laminate film 1 and the adherend 100.

[0060] The molded article 2 uses the above-mentioned laminated film 1, which is excellent in maintaining the surface hydrophilicity, and therefore the hydrophilicity of the surface can be maintained.

[0061] (3) Mode As is apparent from the above embodiments, the present disclosure includes the following aspects.

[0062] The laminated film (1) according to the first embodiment is a laminated film for three-dimensional coating molding, comprising a substrate layer (10) and a surface resin layer (20). The substrate layer (10) is made of a thermoplastic resin. The surface resin layer (20) is a layer formed by ultraviolet curing of a resin composition (X). The resin composition (X) contains an ultraviolet curable resin (a), a (meth)acryloyl group-containing compound (b), a photoinitiator (c), and a silicon-containing substance (d). The (meth)acryloyl group-containing compound (b) has at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and an amino group. The silicon-containing substance (d) contains at least one of silica particles (d1) having a silanol group and a silicate oligomer (d2) having a silanol group.

[0063] According to the first aspect, the laminated film (1) can be made to have excellent retention of surface hydrophilicity.

[0064] In the laminate film (1) according to the second embodiment, in the first embodiment, the resin composition (X) further contains a silane coupling agent (e) having a (meth)acryloyl group.

[0065] According to the second aspect, the laminated film (1) can further improve the maintenance of surface hydrophilicity.

[0066] In the laminated film (1) according to the third embodiment, in the first or second embodiment, the proportion of the silicon-containing substance (d) is 3 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the ultraviolet curable resin (a).

[0067] According to the third aspect, the laminated film (1) can further improve the maintenance of surface hydrophilicity.

[0068] In the laminated film (1) according to a fourth aspect, in any one of the first to third aspects, the (meth)acryloyl group-containing compound (a) contains potassium 3-sulfopropyl methacrylate.

[0069] According to the fourth aspect, the laminated film (1) can more reliably exhibit improved maintenance of surface hydrophilicity.

[0070] The molded article (2) according to the fifth aspect comprises an adherend (100) and the laminated film (1) according to any one of the first to fourth aspects placed on the surface of the adherend (100).

[0071] According to the fifth embodiment, the molded article (2) can maintain the hydrophilicity of the surface. [Example]

[0072] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples.

[0073] <Laminated film manufacturing> [Examples 1 to 12 and Comparative Examples 1 to 5] [Preparation of Resin Composition] Resin composition (X) was prepared by mixing the amounts (parts by mass) shown in Table 1 below of an acrylic resin as the ultraviolet-curable resin (a), 3-sulfopropyl potassium methacrylate (SPMA-K (potassium 3-(methacryloyloxy)propanesulfonate)) (manufactured by Tokyo Chemical Industry Co., Ltd.) as the (meth)acryloyl group-containing compound (b), "Irgacure-184" (manufactured by Ciba Specialty Chemicals) as the photoinitiator (c), and "KBM-5103" (acrylic group-containing silane coupling agent) (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silane coupling agent (e), and the following type of silicon-containing substance (d) in the solid content (parts by mass) shown in Table 1 below.

[0074] The silica particles (d1) and silicate oligomer (d2) used as the silicon-containing substance (d) are shown below. Silica particle A: "MEK-ST40" (Nissan Chemical Industries, Ltd.), OH group-containing organosilica, average particle size 12 nm. Silica particle B: "PMA-ST" (Nissan Chemical Co., Ltd.), OH-containing organosilica, average particle size 12 nm. Silica particle C: "MEK-ST-L" (Nissan Chemical Co., Ltd.), OH-containing organosilica, average particle size 45 nm. Silica particle D: "MEK-ST-ZL" (Nissan Chemical Co., Ltd.), OH-containing organosilica, average particle size 80 nm. Silica particle E: "MEK-ST-UP" (Nissan Chemical Co., Ltd.), OH group-containing chain organosilica, average particle size 12 nm. ·Silicate Oligomer X: "MS-51" (manufactured by Mitsubishi Chemical Corporation), an OH group-containing silicate oligomer. ·Silicate Oligomer Y: "MS-56" (manufactured by Mitsubishi Chemical Corporation), an OH group-containing silicate oligomer. Silica particles Z: "MEK-2140Y" (Nissan Chemical Industries, Ltd.), methacrylate group-containing organosilica, average particle size 12 nm.

[0075] (base material layer) An acrylic resin (polymethyl methacrylate resin) film ("HBS006H" manufactured by Mitsubishi Chemical Corporation, thickness 53 μm, softening temperature 90° C.) was used as the substrate layer.

[0076] (Formation of surface resin layer) The resin composition (X) prepared above was applied to one side of the substrate layer, and the coating was dried to form an uncured layer, which was then irradiated with ultraviolet light to form a surface resin layer, thereby obtaining a laminated film.

[0077] <Molded product manufacturing> An acrylic adhesive was applied to the surface of the substrate layer of the resulting laminated film opposite the surface on which the surface resin layer was formed, and the coating was heat-cured to form an adhesive layer, yielding a laminated film with an adhesive layer. The acrylic adhesive used had a weight-average molecular weight (Mw) of 220,000. The resulting laminated film with adhesive layer and a sheet-like adherend were then placed on the adherend using a TOM molding machine (NGF molding machine manufactured by Fuse Vacuum Co., Ltd.), with the adhesive layer side facing the adherend. The laminated film was then molded at a molding temperature of 150°C under conditions where the stretch ratios in the longitudinal and transverse directions of the laminated film were 100% to 400%, yielding a molded product.

[0078] <Evaluation> [Water contact angle] The water contact angle (°) of the surface of the surface resin layer of the molded article produced above was measured at room temperature (25°C) using a contact angle meter ("DCA-WM" manufactured by Kyowa Interface Science Co., Ltd.) initially and after aging. Initial: After the molded product is manufactured, the surface resin layer has not undergone the following treatment. After aging: The surface resin layer was subjected to running water for 30 seconds, then wiped with a wet cloth 10 times. The initial and aged water contact angles on the surface of the surface resin layer are shown in Table 1 below.

[0079] [Table 1]

[0080] As is clear from the results in Table 1, the laminate films of Examples 1 to 12 are superior in maintaining surface hydrophilicity compared to Comparative Examples 1 to 3, which do not contain the silicon-containing substance (d). Furthermore, the laminate films of Examples 1, 5, 8, 9, and 10 have the same proportion of silicon-containing substance (d), but are superior in maintaining surface hydrophilicity compared to Comparative Example 4, which uses silica particles Z having methacrylate groups but no silanol groups, and similarly, the laminate films of Examples 2, 3, 4, 6, 11, and 12 are superior in maintaining surface hydrophilicity compared to Comparative Example 5. [Explanation of symbols]

[0081] 1 laminated フィルム 2 Molded products 10 base material layer 20 Surface resin layer 30 printing·handle layer 40 Adhesive layer 100 Adhesive

Claims

1. A laminated film for three-dimensional coating molding comprising a substrate layer and a surface resin layer, the base layer is made of a thermoplastic resin, the surface resin layer is a layer formed by ultraviolet curing of a resin composition, the resin composition contains an ultraviolet curable resin, a (meth)acryloyl group-containing compound, a photoinitiator, and a silicon-containing substance; the (meth)acryloyl group-containing compound has at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and an amino group, The silicon-containing material contains at least one of silica particles having silanol groups and silicate oligomers having silanol groups. Laminated film.

2. The resin composition further contains a silane coupling agent having a (meth)acryloyl group. The laminated film according to claim 1 .

3. The ratio of the silicon-containing substance is 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin. The laminated film according to claim 1 .

4. 2. The laminated film according to claim 1, wherein the (meth)acryloyl group-containing compound comprises potassium 3-sulfopropyl methacrylate.

5. An adherend, and the laminated film according to any one of claims 1 to 4, which is placed on the surface of the adherend. A molded article comprising:

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