阅读说明：本技术 成型用层叠膜 (Laminated film for molding ) 是由 铃木翔 加藤龙哉 橘和寿 于 2020-03-09 设计创作，主要内容包括：本发明提供一种成型用层叠膜等,其具有与以往同等以上的硬涂性,并且改善了作为层叠膜整体的形状追随性。本发明的成型用层叠膜至少依次具备基材膜、硬涂层和功能层,上述硬涂层至少含有树脂、和相对于上述硬涂层中所含的全部树脂成分100质量份为1～50质量份的无机氧化物粒子。(The present invention provides a laminated film for molding, which has a hard coating property equal to or higher than that of the conventional laminated film and has improved shape following property as the whole laminated film. The laminated film for molding comprises at least a base film, a hard coat layer and a functional layer in this order, wherein the hard coat layer contains at least a resin and 1-50 parts by mass of inorganic oxide particles per 100 parts by mass of the total resin components contained in the hard coat layer.)

1. A laminated film for molding, which comprises at least a base film, a hard coat layer and a functional layer in this order,

the hard coat layer contains at least a resin and 1 to 50 parts by mass of inorganic oxide particles per 100 parts by mass of the total resin components contained in the hard coat layer.

2. The laminate film for molding of claim 1, wherein the inorganic oxide particles have an average particle diameter D of 1 to 1500nm₅₀。

3. The laminate film for molding of claim 1 or 2, wherein the hard coat layer has a thickness of 0.5 μm to 5 μm.

4. The laminate film for molding of any one of claims 1 to 3, wherein the inorganic oxide particles comprise 1 kind selected from the group consisting of alumina particles and silica particles.

5. The laminate film for molding of any one of claims 1 to 4, wherein the hard coat layer has a pencil hardness of HB or more, the pencil hardness being in accordance with JIS K5600-5-4: 1999, measured under a load of 750 g.

6. The laminated film for molding of any one of claims 1 to 5, wherein the base film, the hard coat layer and the functional layer are stacked without interposing another layer therebetween.

7. The laminate film for molding of any one of claims 1 to 6, wherein the functional layer contains a resin.

8. The multilayer film for molding according to any one of claims 1 to 7, wherein the functional layer contains an inorganic oxide in an amount of 1 to 100 mass% with respect to the total components contained in the functional layer.

9. The laminate film for molding of any one of claims 1 to 8, wherein the functional layer has a thickness of 20nm to 200 nm.

10. The laminate film for molding of any one of claims 1 to 9, wherein the functional layer is at least 1 selected from an antireflection layer, an antifouling layer, an antiglare layer and a decorative layer.

11. The laminate film for molding use according to any one of claims 1 to 10, which is used for film insert molding.

Technical Field

The present invention relates to a laminated film that can be used for molding.

Background

In order to protect and decorate personal computers, mobile devices, mobile phones, electronic notebooks, display panels for vehicles, and the like, an insert molding method using a film in which a hard coat layer is laminated has been used.

As such a laminated film, patent document 1 describes a laminated film for molding, which is characterized by having a hard coat layer having a crack elongation of 5% or more and a low refractive index layer having a refractive index of 1.47 or less in this order on a base film.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2014-41244

Disclosure of Invention

Problems to be solved by the invention

In recent years, in film molding, in particular, molding is performed to form a shape having a curved surface with a small radius of curvature, and a laminate film used for the molding is required to have not only hard coating properties such as scratch resistance but also more excellent shape following properties. The shape-following property (moldability) of the laminated film can be evaluated by, for example, the elongation (hereinafter, also simply referred to as "elongation") of the laminated film until cracks occur when both ends of the laminated film are stretched.

In order to allow the laminated film to exhibit excellent shape-following properties, it is preferable that the hard coat layer, the low refractive index layer, and the like laminated on the laminated film have excellent elongation. However, it has been clarified that the hard coat layer is formed for the purpose of preventing damage to the film surface, and therefore, is made of a relatively hard and brittle material, and therefore, there is room for improvement in relation to other layers provided, in order to improve the shape followability of the entire laminated film. For example, in a laminated film in which a hard coat layer and an antireflection layer are provided on a base film, cracks may occur between the base film and the hard coat layer, between the hard coat layer and the antireflection layer, and the like, and it has been found that a high elongation cannot be exhibited as the whole laminated film.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a laminate film for molding, etc., which has a hard coat property equal to or higher than that of the conventional one and which has improved shape-following properties as a whole laminate film.

Means for solving the problems

The present inventors have conducted intensive studies on the formulation and various physical properties of a hard coat layer in order to solve the above problems, and as a result, have found that by providing a functional layer on a predetermined hard coat layer, excellent pencil hardness and scratch resistance, and excellent elongation of the entire laminated film can be simultaneously achieved, and have completed the present invention.

That is, the present invention provides various specific embodiments shown below.

(1) A multilayer film for molding, which comprises at least a base film, a hard coat layer and a functional layer in this order, wherein the hard coat layer contains at least a resin and 1-50 parts by mass of inorganic oxide particles per 100 parts by mass of the total resin components contained in the hard coat layer.

(2) The multilayer film for molding of (1), wherein the inorganic oxide particles have an average particle diameter D of 1 to 1500nm₅₀。

(3) The multilayer film for molding of (1) or (2), wherein the hard coat layer has a thickness of 0.5 to 5 μm.

(4) The multilayer film for molding according to any one of the above (1) to (3), wherein the inorganic oxide particles include 1 kind selected from alumina particles and silica particles.

(5) The multilayer film for molding of any one of the above (1) to (4), wherein the hard coat layer has a pencil hardness of HB or more (load of 750g in accordance with JIS K5600-5-4: 1999).

(6) The multilayer film for molding use according to any one of the above (1) to (5), wherein the base film, the hard coat layer, and the functional layer are stacked without interposing another layer therebetween.

(7) The multilayer film for molding according to any one of the above (1) to (6), wherein the functional layer contains a resin.

(8) The multilayer film for molding according to any one of the above (1) to (7), wherein the functional layer contains 1 to 100 mass% of an inorganic oxide with respect to the entire components contained in the functional layer.

(9) The multilayer film for molding according to any one of the above (1) to (8), wherein the functional layer has a thickness of 20 to 200 nm.

(10) The multilayer film for molding of any one of the above (1) to (9), wherein the functional layer is at least 1 selected from an antireflection layer, an antifouling layer, an antiglare layer and a decorative layer.

(11) The laminated film for molding according to any one of the above (1) to (10), which is used for film insert molding.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a laminate film for molding and the like having a hard coat property equal to or higher than that of the conventional one and improved in shape-following property as a whole laminate film can be provided.

Drawings

Fig. 1 is a cross-sectional view schematically showing a molding laminated film 101 according to an embodiment.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The positional relationship such as up, down, left, right, and the like is based on the positional relationship shown in the drawings unless otherwise specified. The dimensional ratios in the drawings are not limited to the illustrated ratios. However, the following embodiments are illustrative of the present invention, and the present invention is not limited to these embodiments, and can be implemented by being arbitrarily modified within a range not departing from the gist thereof. In the present specification, for example, the expression of a numerical range of "1 to 100" includes both the lower limit value "1" and the upper limit value "100". The same applies to other numerical ranges.

Fig. 1 is a schematic cross-sectional view showing a main part of a laminate film 101 for molding according to the present embodiment. The multilayer film 101 for molding of the present embodiment includes a base film 11, a hard coat layer 21 provided on one surface 11a side of the base film 11, and a functional layer 31 provided on one surface 21a side of the hard coat layer 21. That is, the molding laminated film 101 has a laminated structure (3-layer structure) in which at least the functional layer 31, the hard coat layer 21, and the base film 11 are arranged in this order. On the back surface side of the molding laminated film 101 (the other surface 11b side of the base film 11), any layer such as a printing layer, an adhesive layer, and an undercoat layer may be provided as necessary. Each constituent element of the molding laminated film 101 will be described in detail below.

< substrate film >

The type of the substrate film 11 is not particularly limited as long as it can support the hard coat layer 21 and the functional layer 31. From the viewpoints of dimensional stability, mechanical strength, weight reduction, and the like, a synthetic resin film is preferably used as the base film 11. Examples of the synthetic resin film include films formed of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, cyclic olefin polymers, polystyrene, triacetyl cellulose, (meth) acrylic acid esters, polyvinyl chloride, fluorine-based resins, and the like. These can be used alone in 1 or a combination of 2 or more. Further, a laminate film using any combination of these may also be preferably used. In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid. Among these base films 11, polyester films, polyimide films, polycarbonate films, (meth) acrylic films, and laminated films obtained by combining any of these films are preferable, and polycarbonate films are more preferable.

The appearance of the substrate film 11 may be any of transparent, translucent, colorless, and colored, and is not particularly limited, and a substrate film having high light transmittance is preferable. Specifically, it is preferably measured according to JIS K7361-1: 1997, the total light transmittance of the transparent resin film is 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more. The substrate film 11 may be subjected to plasma treatment, corona discharge treatment, far ultraviolet irradiation treatment, anchor treatment, or the like as necessary. The substrate film 11 may contain an ultraviolet absorber or a light stabilizer.

Refractive index n of base film 11₀Preferably 1.45 to 1.75, and more preferably 1.50 to 1.75.

The thickness of the base film 11 is not particularly limited, and may be suitably set in accordance with the required performance and use, and is usually 10 to 500. mu.m, preferably 100 to 400. mu.m, and more preferably 150 to 300. mu.m.

< hard coating layer >

The hard coat layer 21 is a coating film provided to increase the surface hardness of the base film 11 and prevent the surface from being damaged. In addition, the surface smoothness of the base film 11 may be improved. The hard coat layer 21 of the present embodiment may be a hard coat film containing at least a resin and inorganic oxide particles dispersed in the resin in order to have shape-following properties as the entire laminate film. In the present embodiment, the hard coat layer 21 is provided only on one surface 11a of the base material film 11, but the hard coat layer 21 may be provided on the other surface 11b (lower surface in the drawing) side of the base material film 11.

(resin)

As a material constituting the hard coat layer 21, a known material can be used, and the kind thereof is not particularly limited. In general, the curable resin composition may be a cured product obtained by curing a curable resin composition containing at least inorganic oxide particles and a known resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin.

Examples of the thermoplastic resin and the thermosetting resin include, but are not particularly limited to, saturated or unsaturated polyester resins, (meth) acrylic urethane resins, (meth) polyester acrylate resins, urethane (meth) acrylate resins, epoxy (meth) acrylate resins, urethane resins, epoxy resins, vinyl resins, polycarbonate resins, cellulose resins, acetal resins, polyethylene resins, polystyrene resins, polyamide resins, polyimide resins, melamine resins, phenol resins, silicone resins, and the like. These can be used alone in 1 or a combination of 2 or more.

As the ionizing radiation curable resin, for example, a photopolymerizable prepolymer that is cured by irradiation of ionizing radiation (ultraviolet rays or electron beams) can be used. The photopolymerizable prepolymer may be used alone, but from the viewpoint of imparting or improving various properties such as improvement in crosslinking curability and adjustment of curing shrinkage, it is preferable to use a photopolymerizable monomer in combination, and if necessary, an auxiliary agent such as a photopolymerization initiator, a photopolymerization accelerator, and a sensitizer (e.g., an ultraviolet sensitizer) may be used.

Photopolymerizable prepolymers are generally classified into cationic polymerization type and radical polymerization type. Examples of the cationically polymerizable photopolymerizable prepolymer include epoxy resins and vinyl ether resins. Examples of the epoxy resin include a bisphenol epoxy resin, a novolac epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin. Examples of the radical polymerizable photopolymerizable prepolymer include (meth) acrylic prepolymers (hard prepolymers). These photopolymerizable prepolymers may be used alone in 1 kind or in combination in 2 or more kinds. Among them, from the viewpoint of hard coatability, a (meth) acrylic prepolymer (hard prepolymer) having 2 or more (meth) acryloyl groups in 1 molecule and having a three-dimensional network structure formed by crosslinking and curing is preferable.

Examples of the (meth) acrylic prepolymer include, but are not particularly limited to, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, polyfluoroalkyl (meth) acrylate, and silicone (meth) acrylate. These (meth) acrylic prepolymers may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the urethane (meth) acrylate prepolymer include, but are not particularly limited to, prepolymers obtained by esterifying a urethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate by reacting with (meth) acrylic acid. These urethane (meth) acrylate prepolymers may be used alone in 1 kind or in combination in 2 or more kinds.

Examples of the polyester (meth) acrylate prepolymer include, but are not particularly limited to, a prepolymer obtained by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends thereof obtained by condensation of a polycarboxylic acid and a polyhydric alcohol with (meth) acrylic acid, a prepolymer obtained by esterifying the hydroxyl groups at the ends of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth) acrylic acid, and the like. These polyester (meth) acrylate prepolymers may be used alone in 1 kind or in combination in 2 or more kinds.

Examples of the epoxy (meth) acrylate prepolymer include, but are not particularly limited to, bisphenol epoxy resins having a relatively low molecular weight, and prepolymers obtained by esterification of the ethylene oxide ring of a novolac epoxy resin with (meth) acrylic acid. These epoxy (meth) acrylate prepolymers may be used alone in 1 kind or in combination in 2 or more kinds.

Examples of the photopolymerizable monomer include monofunctional (meth) acrylic monomers (e.g., 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butoxyethyl (meth) acrylate, etc.), 2-functional (meth) acrylic monomers (e.g., 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate, neopentyl glycol di (meth) acrylate, etc.), and (meth) acrylic monomers having 3 or more functional groups (for example, dipentaerythritol hexa (meth) acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like), but are not particularly limited thereto. These photopolymerizable monomers may be used alone in 1 kind or in combination in 2 or more kinds. In the present specification, "(meth) acrylate" is a concept including both acrylate and methacrylate.

Among them, polyester (meth) acrylate prepolymers or urethane (meth) acrylates are preferable. The commercially available polyester (meth) acrylate prepolymer or urethane (meth) acrylate is not particularly limited, and examples thereof include AT-600, UA-1011, UA-306H, UA-306T, UA-3061, UF-8001, UF-8003, UV7550B, UV 7600B, UV-1700B, UV-6300B, UV-7605B, UV-7640B, UV-7650B, U-4HA, U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, U-2PPA, UA-NDP, Ebecryl-284, and Daicel-UCB, manufactured by Kyowa Kagaku K, Co., Ltd, Ebecryl-264, Ebecryl-9260, Ebecryl-1290K, Ebecryl-5129, UN-3220HA, UN-3220HB, UN-3220HC, UN-3220HS, RQ series manufactured by Mitsubishi corporation, and BEAMSET series manufactured by Mitsuwa chemical industry.

The content of the polyester (meth) acrylate prepolymer or the urethane (meth) acrylate is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, based on 100% by mass of the total solid content of the curable resin composition for forming the hard coat layer 21.

The content of the monomer having 4 or more polymerizable functional groups in the molecule (excluding the polyester (meth) acrylate prepolymer or the urethane (meth) acrylate) is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less, based on 100% by mass of the total solid content of the curable composition for forming the hard coat layer 21.

The polymerizable functional group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, and allyl group.

The monomer having 4 or more polymerizable functional groups in the molecule is not particularly limited, and examples thereof include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol hexa (meth) acrylate.

In addition to the polyester (meth) acrylate prepolymer or the urethane (meth) acrylate, a monomer or oligomer containing 1 to 3 polymerizable functional groups in the molecule is preferably contained.

The monomer or oligomer having 1 to 3 polymerizable functional groups in the molecule is not particularly limited, examples thereof include methyl (meth) acrylate, lauryl (meth) acrylate, ethoxydiglycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate.

The content of the monomer or oligomer having 1 to 3 polymerizable functional groups in the molecule is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass, based on 100% by mass of the total solid content of the curable composition for forming the hard coat layer 21.

When a photopolymerizable prepolymer and a photopolymerizable monomer are used for forming the hard coat layer 21, a photopolymerization initiator is preferably used. Examples of the photopolymerization initiator include, but are not particularly limited to, radical polymerizable photopolymerizable prepolymers and photopolymerizable monomers, such as acetophenone, benzophenone, michler's ketone, benzoin, benzyl methyl ketal, benzoyl benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propane, α -acyloxime ester, and thioxanthones. Examples of the photopolymerization initiator for the cationically polymerizable photopolymerizable prepolymer include compounds composed of onium such as aromatic sulfonium ion, aromatic oxysulfonium ion, and aromatic iodonium ion, and anion such as tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and hexafluoroarsenate, but are not particularly limited thereto. These can be used alone in 1 or a combination of 2 or more.

The amount of the photopolymerization initiator to be blended is not particularly limited, and may be appropriately set within a range of 0.2 to 10 parts by mass per 100 parts by mass of the total of the photopolymerizable prepolymer and the photopolymerizable monomer. In the present specification, the amount of the photopolymerization initiator is added as a part of the total resin components contained in the hard coat layer 21.

Examples of the photopolymerization accelerator include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate. Examples of the ultraviolet sensitizer include, but are not particularly limited to, n-butylamine, triethylamine, and tri-n-butylphosphine. These can be used alone in 1 or a combination of 2 or more.

The blending amount of the photopolymerization accelerator assistant and the ultraviolet sensitizer is not particularly limited, and may be appropriately set within a range of 0.2 to 10 parts by mass per 100 parts by mass of the total of the photopolymerizable prepolymer and the photopolymerizable monomer.

(inorganic oxide particles)

The hard coat layer 21 in the present embodiment contains at least 1 to 50 parts by mass of inorganic oxide particles per 100 parts by mass of the total resin components contained in the hard coat layer 21. By containing the inorganic oxide particles, excellent elongation of the entire laminated film can be obtained.

Examples of the inorganic oxide particles include, but are not particularly limited to, alumina particles, silica particles, titania particles, zirconia particles, antimony oxide particles, tin oxide particles, tantalum oxide particles, zinc oxide particles, cerium oxide particles, lead oxide particles, and indium oxide particles. These can be used alone in 1 or a combination of 2 or more. Among them, at least 1 kind selected from alumina particles and silica particles is preferable, and alumina particles are more preferable.

Average particle diameter D of inorganic oxide particles₅₀The particle size is not particularly limited, but is preferably 1 to 1500nm, more preferably 10 to 1000nm, further preferably 15 to 300nm, particularly preferably 20 to 150nm, and most preferably 30 to 100 nm. By using the average particle diameter D having such a range₅₀The inorganic oxide particles according to (1), wherein the laminated film tends to exhibit excellent elongation as a whole of the laminated film.

In the present specification, the average particle diameter D is₅₀The median particle diameter (D) is measured by a laser diffraction particle size distribution measuring apparatus (for example, SALD-7000, manufactured by Shimadzu corporation)₅₀). Further, the median diameter (D)₅₀) Refers to the amount of particles in the particle distributionThe particle size at 50 vol% cumulatively calculated from the small particle size side.

The content of the inorganic oxide particles is preferably 1 to 50 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass, based on 100 parts by mass of the total resin components contained in the hard coat layer 21. By using the inorganic oxide particles in the content within this range, the laminated film tends to exhibit excellent elongation and excellent hard coating properties.

The hard coat layer 21 may contain various additives as long as the effects of the present invention are not excessively inhibited. Examples of the various additives include, but are not particularly limited to, surface conditioners, lubricants, colorants, pigments, dyes, fluorescent brighteners, flame retardants, antibacterial agents, mildewcides, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, plasticizers, leveling agents, flow control agents, antifoaming agents, dispersants, storage stabilizers, crosslinking agents, silane coupling agents, and the like.

The surface hardness of the hard coat layer 21 is not particularly limited, but is preferably HB or more, more preferably F or more, and further preferably H or more. The value of the surface hardness was determined by using a hardness in accordance with JIS K5600-5-4: 1999, the pencil scratch value (pencil hardness) measured under a load of 750 g.

Refractive index n of hard coat layer 21₂The amount of the surfactant is not particularly limited, and is preferably 1.35 to 1.70, more preferably 1.45 to 1.70.

The thickness of the hard coat layer 21 is not particularly limited, and is preferably 0.5 to 5 μm, more preferably 1 to 4 μm, and still more preferably 2 to 4 μm.

< functional layer >

The functional layer 31 will be explained. The functional layer 31 is a layer provided to improve the functionality of the multilayer film 101 for molding, for example, to improve surface smoothness, surface hardness, scratch resistance, stain resistance, optical characteristics, and the like. The functional layer 31 may be a known functional layer used for a laminated film. Specifically, there may be mentioned, but not limited to, an antireflection layer, an antifouling layer, an antiglare layer, a decorative layer, an anti-fingerprint adhesion layer, an anti-blocking layer, an ultraviolet absorbing layer, and a newton ring inhibition layer. The functional layer 31 may be a single layer having any of these functions, may be a single layer in which a plurality of these functions are combined, or may be a composite in which a plurality of layers are laminated. Among these functional layers 31, at least 1 selected from an antireflection layer, an antifouling layer, an antiglare layer, and a decorative layer is preferable, and an antireflection layer is more preferable.

The functional layer 31 preferably contains a resin. As the resin, the resins listed in the description of the hard coat layer 21 may be used, and a fluorine-based resin or a silicon-based resin may be used.

The functional layer 31 preferably contains 1 to 100 mass% of an inorganic oxide with respect to all components contained in the functional layer 31. Examples of the inorganic oxide include, but are not particularly limited to, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, antimony oxide, tin oxide, tantalum oxide, zinc oxide, cerium oxide, lead oxide, and indium oxide. Among these, silicon oxide or aluminum oxide is preferable, and silicon oxide is more preferable.

The content of the inorganic oxide is preferably 1 to 100% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 60% by mass. When the content of the inorganic oxide is in this range, the molding laminated film 101 tends to exhibit a significantly more excellent elongation of the entire laminated film.

(anti-reflection layer)

The antireflection layer is provided to reduce reflection on the surface of the hard coat layer 21 and to improve the total light transmittance of the entire molding laminated film 101. In order to prevent reflection of the surface portion, it is also considered to design the refractive index of the hard coat layer 21 to be small. However, if the hard coat layer 21 is designed so that the refractive index becomes small, the hard coatability of the hard coat layer 21 may decrease. Therefore, in the present embodiment, in order to prevent reflection of the surface portion without lowering the hard coating property of the hard coating layer 21, an antireflection layer having a refractive index lower than the refractive index of the hard coating layer 21 is formed on the surface of the hard coating layer 21. The antireflection layer in the present embodiment preferably has a refractive index lower than that of the hard coat layer 21.

The antireflection layer contains, for example, a resin or an inorganic oxide. The resin exemplified in the description of the hard coat layer 21 may be used, but when the stain-proofing property and the refractive index need to be adjusted, the resin preferably contains a fluorine-based resin or a silicone-based resin. When the antireflection layer contains a resin, it preferably further contains inorganic oxide particles. When the antireflection layer contains an inorganic oxide, the antireflection layer may further contain different types of inorganic oxide particles. The inorganic oxide particles may be the inorganic oxide particles described above.

Examples of the fluorine-containing resin include a fluorine-containing monomer, a fluorine-containing oligomer, and a fluorine-containing polymer compound. Here, the fluorine-containing monomer and the fluorine-containing oligomer are monomers and oligomers having an ethylenically unsaturated group and a fluorine atom in a molecule.

Examples of the fluorine-containing monomer and fluorine-containing oligomer include fluorine-containing (meth) acrylates (e.g., 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3, 3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, β - (perfluorooctyl) ethyl (meth) acrylate, etc.), fluoroalkyl di- (. alpha. -fluoroacrylic acid) esters (e.g., di- (. alpha. -fluoroacrylic acid) -2, 2, 2-trifluoroethylene glycol, di- (. alpha. -fluoroacrylic acid) -2, 2, 3, 3, 3-pentafluoropropylglycol, di- (α -fluoroacrylic) -2, 2, 3, 3, 4, 4-hexafluorobutylglycol, di- (α -fluoroacrylic) -2, 2, 3, 3, 4, 4, 5, 5, 5-nonafluoropentylglycol, di- (α -fluoroacrylic) -2, 2, 3, 3, 4, 4, 5, 5, 6, 6-undecafluorohexylglycol, di- (α -fluoroacrylic) -2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7-tridecafluorohexylglycol, di- (α -fluoroacrylic) -2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-pentadecafluorooctanediol, Di- (α -fluoroacrylic acid) -3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl glycol, di- (α -fluoroacrylic acid) -2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 9-heptadecafluorononyl glycol, etc.), and the like.

Examples of the fluorine-containing polymer compound include a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as a constituent unit. Specific examples of the fluorine-containing monomer unit include fluoroolefins (e.g., vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2, 2-dimethyl-1, 3-dioxole, etc.), partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (e.g., "Viscoat 6 FM" (manufactured by Osaka organic chemical Co., Ltd.), "M-2020" (manufactured by Osaka industries, Ltd.)), fully or partially fluorinated vinyl ethers, and the like. Examples of the monomer for imparting a crosslinkable group include (meth) acrylate monomers having a crosslinkable functional group in advance in the molecule, such as glycidyl methacrylate, and (meth) acrylate monomers having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, and the like (for example, (meth) acrylic acid, hydroxymethyl (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, and the like).

In the antireflective layer, if the content of the fluorine-based resin is 1% by mass or more based on 100% by mass of the total resin solid content of the composition, the effect can be exhibited.

Examples of the silicone resin include polymers of polysiloxane compounds having an ethylenically unsaturated group. Specifically, 2-or more-functional silicone compounds having an ethylenically unsaturated group at both ends of the silicone main chain in the molecule are preferable, and particularly, 3-or more-functional silicone compounds having 1 or more ethylenically unsaturated groups at both ends and in the side chain of the silicone main chain are more preferable. Examples of the ethylenically unsaturated group include a vinyl group, an acryloyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group.

Commercially available silicone compounds having an ethylenically unsaturated group include, for example, Silaplane FM-0711, Silaplane FM-0721, Silaplane FM-0725, X-24-8201, X-22-174DX, X-22-1602, X22-1603, X-22-2426, X-22-2404, X-22-164A, X-22-164C, X-22-2458, X-22-2459, X-22-2445, X-22-2457, BY16-152D, BY16-152, BY16-152C, BYK-UV3570, available from BYK Japan K corporation, and the like, available from Chisso corporation.

The content of the silicon-based resin in the antireflection layer is preferably 1.5 mass% or more and less than 10 mass% with respect to 100 mass% of the total solid content of the low refractive index layer.

As the inorganic oxide contained in the antireflection layer, an inorganic oxide sol can be used. Examples of the inorganic oxide sol include a silica sol and an alumina sol. Among these inorganic oxide sols, silica sols are preferably used from the viewpoint of refractive index, fluidity, and cost. The inorganic oxide sol is a material in which the tyndall phenomenon cannot be observed due to the presence of an inorganic oxide, and is a so-called homogeneous solution. For example, even if a material generally called a colloidal silica sol is used, if the tyndall phenomenon is observed, it is not included in the inorganic oxide sol in this embodiment.

Such an inorganic oxide sol can be prepared by hydrolyzing inorganic alkoxides such as tetraethoxysilane, methyltrimethoxysilane, zirconia propanol, aluminum isopropoxide, titanium butoxide, and titanium isopropoxide. Examples of the solvent of the inorganic oxide sol include methanol, ethanol, isopropanol, butanol, acetone, 1, 4-dioxane, and the like.

The inorganic oxide particles are preferably particles obtained by pulverizing the inorganic oxide fine powder, and examples thereof include silica particles and alumina particles. Among these, silica particles are preferably used from the viewpoint of refractive index, fluidity, and cost. The shape of the inorganic oxide particles is not particularly limited, and porous or hollow inorganic oxide particles having a low refractive index are preferably used.

The thickness of the antireflection layer preferably satisfies the following formula in terms of the light antireflection theory.

d＝(a+1)λ/4n₃

Where d is the thickness of the anti-reflection layer (unit is "nm"), a is 0 or a positive even number, λ is the central wavelength of light to be prevented from being reflected, and n is the central wavelength of light to be prevented from being reflected₃Is the refractive index of the anti-reflection layer. Specifically, d is, for example, preferably about 2000nm or less, more preferably 1000nm or less, still more preferably 800nm or less, particularly preferably 500nm or less, and most preferably 300nm or less. Since the central wavelength of light whose reflection is to be prevented is in the visible light range, λ is 550nm, which is the central wavelength of a wavelength generally called the visible light range, and when silicon oxide is used as the inorganic thin film, the refractive index n is about 1.40, and therefore the thickness d of the antireflection layer is about 100 nm.

If the thickness of the antireflection layer is increased, interference unevenness due to the thickness unevenness is less likely to occur, and the hard coating property of the hard coat layer 21 provided on the lower surface is less likely to be exhibited. In this embodiment, in order to prevent a decrease in the hard coating property of the hard coat layer 21 and a decrease in the antireflection effect due to light interference, an antireflection layer is thinly formed on the surface of the hard coat layer 21.

Refractive index n of the anti-reflection layer₃Preferably 1.20 to 1.47, and more preferably 1.20 to 1.45. The refractive index n of the antireflection layer of the multilayer film 101 for molding of the present embodiment is preferably set to be equal to₃Refractive index n smaller than that of hard coat layer 21₂More preferably, the refractive index n of the hard coat layer 21₂Smaller by more than 0.1.

The laminated film 101 for molding described in detail above can be obtained by, for example, forming the hard coat layer 21 on the one surface 11a side of the base film 11 and then laminating the functional layer 31 on the surface 21a side of the hard coat layer 21. The method for forming these layers may be carried out by a conventional method, and is not particularly limited. Examples of a preferable method for producing the hard coat layer 21 and the functional layer 31 include conventionally known coating methods such as blade coating, dip coating, roll coating, bar coating, die coating, blade coating, air knife coating, kiss coating, spray coating, and spin coating. As the solvent of the coating liquid used herein, for example, water; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; ether solvents such as methyl cellosolve and ethyl cellosolve; and alcohol solvents such as methanol, ethanol, and isopropanol, and mixed solvents thereof. The hard coat layer 21 and the functional layer 31 can be formed by subjecting the coating film thus coated to ionizing radiation treatment, heat treatment, pressure treatment, and/or the like as necessary. As a pretreatment before lamination of each layer, an anchor treatment, a corona treatment, or the like may be performed as necessary.

The light source used for the ionizing radiation irradiation is not particularly limited. For example, an ultra-high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, an electron beam accelerator, or the like may be used. The dose of the ultraviolet light at this time may be appropriately set depending on the kind of the light source used, the output performance, etc., and is not particularly limited, and the dose of the ultraviolet light is usually 100 to 6000mJ/cm in cumulative amount²The left and right are standard.

The heat source used for the heat treatment is not particularly limited. Either of contact and noncontact can be suitably used. For example, a far infrared heater, a short wavelength infrared heater, a medium wavelength infrared heater, a carbon heater, an oven, a heating roller, or the like can be used. The treatment temperature in the heat treatment is not particularly limited, but is usually 80 to 200 ℃ and preferably 100 to 150 ℃.

< Properties of laminated film for Molding >

The total light transmittance of the multilayer film 101 for molding of the present embodiment is preferably 80% or more, more preferably 85 to 99%, and further preferably 90 to 98%. The total light transmittance may be measured by a method according to JIS K7361-1: 1997.

For example, if the application requires antiglare properties, the haze of the multilayer film 101 for molding of the present embodiment is preferably 6% or more. On the other hand, in the case of an application requiring transparency, the haze is preferably 5% or less, more preferably 0.01 to 3%, and still more preferably 0.1 to 1%. The haze can be measured by a method according to JIS K7136: 2000, respectively.

The arithmetic average roughness (Ra) of the outermost surface of the multilayer film 101 for molding of the present embodiment is preferably 120nm or less, more preferably 0.1 to 50nm, still more preferably 0.1 to 10nm, and still more preferably 0.1 to 5 nm. The arithmetic average roughness (Ra) can be determined by a method in accordance with JIS B0601: 2001 were measured by the method of the above publication.

The molding laminated film 101 of the present embodiment can be used for, for example, decoration molding, in-mold molding, and film insert molding. The molding laminate film 101 of the present embodiment exhibits excellent elongation of the entire laminate film, and therefore is less likely to crack even in a 90 ° bending test with a small radius of curvature (for example, about 1 mm), and is particularly superior to the prior art in terms of excellent shape-following properties of the entire laminate film.

The elongation of the multilayer film 101 for molding of the present embodiment is preferably 5% or more, more preferably 10 to 200%, further preferably 30 to 150%, and particularly preferably 40 to 100%. The laminate film 101 for molding satisfying the above range tends to exhibit excellent elongation and excellent hard coating properties. The use for molding is preferably an application requiring the above elongation.

The elongation can be determined by the following method in accordance with JIS K7127: 1999, more specifically, it can be measured by the method described in examples. When the elongation of the multilayer film 101 for molding in which the hard coat layer 21 and the like are laminated on the base film 11 is measured, if the measurement is performed under a temperature condition substantially lower than the glass transition temperature of the base film 11, the base film 11 may be broken. In such a case, by heating the molding laminated film 101 to a temperature near the glass transition temperature of the base film 11, preferably ± 5 ℃, the elongation can be measured accurately.

The molding laminate film 101 of the present embodiment is suitably used as an exterior film for a case of an electric device such as a mobile phone or a notebook computer, an icon sheet of a mobile phone, and a protective film for a display panel mounted on a vehicle. In particular, the film is particularly useful as a protective film for a display device such as a Cathode Ray Tube (CRT), a Plasma Display Panel (PDP), a Liquid Crystal Display (LCD), or an electroluminescent display (OELD or IELD).

Examples

The present invention will be described in detail below based on experiments, but the present invention is not limited to these experiments. Various conditions may be adopted in the present invention as long as the object of the present invention is achieved without departing from the gist of the present invention. In the following description, "part" means "part by mass" unless otherwise specified.

[ measurement method ]

< Total light transmittance and haze >

The following were used according to JIS K7361-1: 1997 total light transmittance (Tt) was measured by the measurement method according to JIS K7136: 2000 the Haze (Haze) was measured by a Haze meter "NDH 2000" (trade name, manufactured by japan electrochrome industries, ltd.), using the surface of each of the molding laminated films opposite to the substrate as a light incident surface, and the total light transmittance (Tt) and the Haze (Haze) were measured.

< arithmetic average roughness (Ra) >

Using a specimen according to JIS B0601: 2001, the arithmetic mean roughness (Ra) of each multilayer film for molding was determined by using an atomic force microscope "Nanocute System" (trade name, manufactured by Hitachi High-Tech Science, probe: Si single crystal probe, measurement mode: DFM mode, image processing: flattening (XY)1 time).

[ evaluation method ]

< elongation >

As for the evaluation of the shape-following property, the following properties were evaluated in accordance with JIS K7127: 1999 tensile test was carried out to measure the elongation of each film. The sample was cut into a short shape of 100mm in length by 25mm in width. Next, in an apparatus in which the samples were marked at intervals of 50mm in length near the center of the sample except for both ends, and a temperature adjustment mechanism was provided in a tensile tester "AGS-1 kNX" (trade name, manufactured by shimadzu corporation), the samples were set without holding the marked portion by a chuck, a tensile test was performed at a distance of 50mm between chucks and a tensile speed of 200mm/min with the glass transition temperature of the substrate being within ± 5 ℃, the length between marks at the time when a crack occurred in the sample was measured, and the elongation (%) was calculated by dividing the length by the length of the initial mark, that is, 50 mm. The presence or absence of cracks was visually confirmed.

< Pencil hardness >

As the evaluation of hard coating properties, the coating composition was evaluated in accordance with JIS K5600-5-4: 1999, the pencil hardness was measured by using a pencil scratch hardness tester "No. 553-m" (trade name, manufactured by Anthras Seisakusho K.K.). The measurement conditions were a load of 750g and a scratch speed of 0.5 mm/sec, 3 lines of pencil of a predetermined hardness were drawn on the outermost surface (surface on the opposite side to the base material film) of the molding laminated film, scratches were confirmed, and the maximum hardness (B, HB, F, H) of 1 or less at which scratches occurred was evaluated. The pencil hardness tests in tables 2 and 3 were performed after the formation of the hard coat layer, before the formation of the functional layer, and after the formation of the functional layer. The evaluation after the formation of the hard coat layer and before the formation of the functional layer is referred to as "HC-only layer" in the table, and the evaluation after the formation of the functional layer is expressed as the entire laminated film.

< chemical resistance >

The outermost surface (the surface opposite to the base film) of the laminate film for molding was coated with 0.3g of sunscreen cream "SPF 100 +" (trade name, Neutrogena corporation), aged at 80 ℃ for 6 hours, and then washed out with water to visually confirm the change in appearance.

5: no change in appearance was observed at all.

4: depending on the angle of the irradiated light, a change in appearance was slightly observed.

3: a slight change in appearance was observed.

2: a change in appearance was observed.

1: a change in appearance was clearly observed.

< scratch resistance >

For the evaluation of hard coat properties, the scratch resistance was evaluated using a melamine sponge "Shajijun" (trade name, melamine foam manufactured by LEC corporation). Here, the area of the device is 7cm²The outermost surface (surface on the opposite side to the base film) of the laminated film for molding was rubbed 30 times with a load of 200g, and then, no damage was visually observed.

5: without change

4: 1-2 thin scars appear

3: 3-10 thin scars appear

2: 10 or more thin scars were observed

1: generating sharp scars on the whole surface of the friction surface

[ production of multilayer film for Molding ]

Example 1 laminate film for Molding E1

A hard coat layer (hereinafter, also referred to as "HC layer") having a thickness of 3 μm and a refractive index of 1.52 was formed by applying a hard coat layer coating solution of the following formulation containing the inorganic oxide particles shown in Table 1 to one surface of a polycarbonate film having a thickness of 250 μm and a glass transition temperature of 150 ℃ and drying the coating solution, and then irradiating the coating solution with ultraviolet light to cure the coating solution. Then, a functional layer coating liquid of the following formulation was applied on the hard coat layer and dried, and then irradiated with ultraviolet rays to be cured, thereby forming an antireflection layer having a thickness of 100nm and a refractive index of 1.37 as a functional layer, and obtaining a molding laminate film E1. The obtained molding laminated film E1 was evaluated for elongation, pencil hardness, chemical resistance, and scratch resistance, and the results are shown in table 1.

Comparative example 1 multilayer film for Molding CE1

A multilayer film CE1 for molding was obtained by forming a hard coat layer and an antireflection layer in the same manner as in example 1, except that the blending of the inorganic oxide particles was omitted in the formation of the hard coat layer. The obtained multilayer film for molding CE1 was evaluated for elongation, pencil hardness, chemical resistance, and scratch resistance, and the results are shown in table 1.

(reference examples 1 to 3: multilayer films for Molding R1 to R3)

A hard coat layer was formed in the same manner as in example 1 except that the content of the inorganic oxide particles at the time of forming the hard coat layer was changed as shown in table 1 without forming the functional layer, to obtain a laminated film for molding. The elongation, pencil hardness, chemical resistance, and scratch resistance of each of the multilayer films for molding were evaluated, and the results are shown in table 1.

< hard coating layer coating solution >

Acrylic ultraviolet-curable resin: 167 parts by mass (solid component amount 100 parts by mass)

(trade name: BEAMSET 1200, manufactured by Mitsubishi chemical industries, Ltd., solid content: 60% by mass)

Inorganic oxide particles A-1: the amounts are given in the tables (parts by mass)

(alumina particles, average particle diameter D)₅₀: 80nm, solid content 100% by mass)

Inorganic oxide particles A-2: the amounts are given in the tables (parts by mass)

(alumina particles, average particle diameter D)₅₀: 900nm, solid content 100% by mass)

Inorganic oxide particles B: the amounts are given in the tables (parts by mass)

(silica particles, average particle diameter D)₅₀: 250nm, solid content 100% by mass)

Leveling agent: 2 parts by mass

(trade name: M-ADDITIVE, manufactured by DOW CORNING TORAY Co., Ltd., solid content 10% by mass)

Solvent: the content of the solid content was adjusted to 20% by mass

(methyl ethyl ketone (MEK))

< functional layer coating solution >

Ionizing radiation curable resin: 50 parts by mass

(trade name: BEAMSET 575, manufactured by Mitsuwa chemical industry Co., Ltd., solid content: 100% by mass)

Multifunctional acrylates: 50 parts by mass

(trimethylolpropane triacrylate (TMPTA), 100% by mass of solid content)

Photoinitiator (2): 3 parts by mass

(trade name: Omnirad 127, manufactured by IGM Resins Co., Ltd., solid content 100% by mass)

Porous silica fine particles: 100 parts by mass

(average particle diameter D)₅₀: 55nm, solid content 100% by mass)

Additive: 3 parts by mass

(trade name: MEGAFACE RS-75, manufactured by DIC corporation, solid content: 40% by mass)

Solvent: the solid content of the functional layer coating liquid was adjusted to 6 mass%

(methyl ethyl ketone (MEK))

[ Table 1]

First, as is clear from the comparison of reference examples 1 to 3, in the multilayer film for molding in which the antireflection layer is not laminated, if the inorganic oxide particles are contained in the hard coat layer, the elongation of the whole multilayer film for molding becomes smaller as the content thereof increases. On the other hand, from a comparison between comparative example 1 and example 1, it is found that, in the laminated film for molding having the antireflection layer and the hard coat layer, if the hard coat layer contains the inorganic oxide particles, the elongation of the whole laminated film for molding is improved, contrary to the results of reference examples 1 to 3 described above. Meanwhile, it is shown from the comparison between comparative example 1 and example 1 that the scratch resistance of the multilayer film for molding can be improved by containing the inorganic oxide particles in the hard coat layer.

(examples 2 to 6: laminated films E2 to E6)

A hard coat layer having a thickness of 3 μm and a refractive index of 1.52 was formed by applying the hard coat layer coating solution of the above formulation containing the inorganic oxide particles shown in Table 2 on one surface of a polycarbonate film having a thickness of 250 μm and a glass transition temperature of 150 ℃ and drying the coating solution, and then irradiating the resultant coating solution with ultraviolet rays to cure the coating solution. Then, the antireflection layer coating liquid of the above formulation was applied on the hard coat layer and dried, and then cured by irradiation with ultraviolet rays to form an antireflection layer having a thickness of 100nm and a refractive index of 1.37, thereby obtaining multilayer films E2 to E6 for molding.

The obtained multilayer films for molding E2 to E6 were evaluated for elongation, pencil hardness, chemical resistance, and scratch resistance, and the results are shown in table 2. For reference, the results of the laminated films for molding E1 and CE1 shown in example 1 and comparative example 1 are also shown in table 2.

[ Table 2]

As described above, the comparison results of examples 1 to 6 and comparative example 1 show that a laminated film having excellent properties in any of elongation, pencil hardness, chemical resistance, and scratch resistance can be realized by containing inorganic oxide particles in the hard coat layer.

(examples 11 to 15 and comparative example 2: Molding multilayer films E11 to E15, CE2)

A hard coat layer having a refractive index of 1.52 and a thickness of 3 μm was formed by applying the hard coat layer coating solution of the above formulation containing the inorganic oxide particles shown in Table 3 on one surface of a polycarbonate film having a thickness of 250 μm and a glass transition temperature of 150 ℃ and drying the coating solution, and then irradiating the resultant coating solution with ultraviolet rays to cure the coating solution. Then, the antireflection layer coating liquid of the above formulation was applied on the hard coat layer and dried, and then cured by irradiation with ultraviolet rays to form an antireflection layer having a thickness of 100nm and a refractive index of 1.37, thereby obtaining multilayer films E11 to E15 for molding.

On the other hand, as comparative example 2, a multilayer film CE2 for molding was obtained by forming a hard coat layer and an antireflection layer in the same manner as in example 11, except that the blending of the inorganic oxide particles was omitted in the formation of the hard coat layer.

The obtained multilayer films for molding E11 to E15 and CE2 were evaluated for elongation, pencil hardness, chemical resistance and scratch resistance, and the results are shown in table 3.

[ Table 3]

From comparison between comparative example 2 and examples 11 to 15, it is found that, in the laminated film for molding having an antireflection layer and a hard coat layer, if the hard coat layer contains the average particle diameter D as in the results of Table 1 and Table 2₅₀The inorganic oxide particles having a particle size of 900nm improve the elongation of the entire multilayer film for molding.

On the other hand, the comparison between examples 1 to 6 and examples 11 to 15 shows that when the content of the inorganic oxide particles is large, the average particle diameter D of the inorganic oxide particles is large₅₀If a smaller average particle diameter D is used, the influence of the difference in (A) is more likely to be large₅₀The inorganic oxide particles of (2) tend to further increase the elongation of the entire laminated film. In addition, the comparison between examples 1 to 6 and examples 11 to 15 shows that if a smaller average particle diameter D is used₅₀The inorganic oxide particles of (3) can suppress an increase in haze of the laminate film.

Examples 21 to 22 laminate films E21 to E22 for Molding

Laminated films E21 and E22 for molding of examples 21 to 22 were obtained by the same formulation and production method as in example 1 except that the kind and the blending amount of the inorganic oxide particles were changed as described in table 4. The obtained laminate films for molding E21 and E22 were evaluated, and the results are shown in table 4.

[ Table 4]

1 blending amount per 100 parts by mass of all resin components contained in the HC layer

Shows that: even when silica particles are used as the inorganic oxide particles, a laminated film for molding having excellent performance equivalent to that of a laminated film for molding using alumina particles in any of elongation, pencil hardness, chemical resistance and scratch resistance can be realized.

Industrial applicability

The present invention is suitably used as a film for exterior packaging of a case of an electric device such as a mobile phone or a notebook computer, an icon sheet of a mobile phone, and a protective film of a display panel for a vehicle. In particular, the film is particularly useful as a protective film for a display device such as a Cathode Ray Tube (CRT), a Plasma Display Panel (PDP), a Liquid Crystal Display (LCD), or an electroluminescent display (OELD or IELD).

Description of the reference numerals

101 … laminated film for molding, 11 … base material film, 21 … hard coating layer and 31 … functional layer