WO2022014674A1 - インサート成形用ハードコートフィルムおよびインサート成形品の製造方法 - Google Patents

インサート成形用ハードコートフィルムおよびインサート成形品の製造方法 Download PDF

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Publication number
WO2022014674A1
WO2022014674A1 PCT/JP2021/026610 JP2021026610W WO2022014674A1 WO 2022014674 A1 WO2022014674 A1 WO 2022014674A1 JP 2021026610 W JP2021026610 W JP 2021026610W WO 2022014674 A1 WO2022014674 A1 WO 2022014674A1
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hard coat
film
layer
meth
acrylate
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PCT/JP2021/026610
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English (en)
French (fr)
Japanese (ja)
Inventor
亮平 富田
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東山フイルム株式会社
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Priority to CN202180061091.8A priority Critical patent/CN116348538A/zh
Priority to DE112021003817.6T priority patent/DE112021003817T5/de
Priority to KR1020227044420A priority patent/KR20230038142A/ko
Publication of WO2022014674A1 publication Critical patent/WO2022014674A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability

Definitions

  • the present invention relates to a hard coat film for insert molding and a method for manufacturing an insert molded product.
  • inserts are used to integrate a film decorated on the surface or a film having functionality.
  • the molding method is widely used.
  • an insert film provided with an uncured or semi-cured hard coat layer is molded into the shape of the surface of a molded product by a preform mold, and then the hard coat layer is irradiated with ionizing radiation.
  • a method for manufacturing an insert-molded article which is completely cured, and the cured insert film is integrated with a molding resin and injection-molded.
  • Patent Document 1 is only described as having an uncured or semi-cured hardcourt layer, and is uncured or uncured or semi-cured before being molded into the shape of the molded product surface by the preform mold. No mention is made of maintaining the smoothness of the soft hardcourt layer in the semi-cured state, and there remains a problem in terms of smoothness that does not impair the surface quality of the insert molded product.
  • the hard coat film for insert molding according to the present invention has a base film and a hard coat layer formed on the surface of the base film, and the hard coat layer is ionized.
  • radiation consists of a composition which is cured by, the hard coat layer, indentation hardness measured by nanoindentation method is a 10 ⁇ 200N / mm 2 at 30 °C, 100N / mm 2 at 0.99 ° C. It is as follows.
  • the base film is composed of a multilayer structure having a layer containing polycarbonate and a layer containing poly (meth) acrylate, and the hard coat layer is in contact with the layer containing the poly (meth) acrylate layer of the base film. It should be formed.
  • the arithmetic average surface roughness (Ra) of the surface of the pressure-sensitive adhesive layer in contact with the hard coat layer is 200 nm or less. good.
  • the method for manufacturing an insert molded product according to the present invention has the following steps (1) to (7).
  • the indentation hardness which is composed of a composition that is cured by ionizing radiation on the surface of the base film and is measured by the nanoindentation method, is 10 to 200 N / mm 2 at 30 ° C. and at 150 ° C.
  • Ra arithmetic average surface roughness
  • the hard coat film for insert molding according to the present invention has a base film and a hard coat layer formed on the surface of the base film, and the hard coat layer is cured by ionizing radiation. It is composed of a composition, and the indentation hardness of the hard coat layer measured by the nanoindentation method is 10 to 200 N / mm 2 at 30 ° C. and 100 N / mm 2 or less at 150 ° C. Therefore, it has excellent scratch resistance, suppresses indentations during storage, and has excellent surface smoothness after preformation.
  • FIG. 1 is a cross-sectional view of a hard coat film for insert molding according to an embodiment of the present invention.
  • the insert molding hard coat film 10 according to the embodiment of the present invention has a base film 12 and a hard coat layer 14 formed on the surface of the base film 12.
  • the base film 12 is not particularly limited as long as it has transparency.
  • Examples of the base film 12 include a transparent polymer film and a glass film.
  • Transparency means that the total light transmittance in the visible light wavelength region is 50% or more, and the total light transmittance is more preferably 85% or more.
  • the total light transmittance can be measured according to JIS K7361-1 (1997).
  • polymer material of the base film 12 examples include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, poly (meth) acrylate, polystyrene, polyamide, polyimide, polyacrylonitrile, and polypropylene, polyethylene, polycycloolefin, and cycloolefin copolymer.
  • polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, poly (meth) acrylate, polystyrene, polyamide, polyimide, polyacrylonitrile, and polypropylene, polyethylene, polycycloolefin, and cycloolefin copolymer.
  • polyolefins such as, polyphenylene sulfide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and the like.
  • the polymer material of the base film 12 may be composed of only one of these, or may be composed of a combination of two
  • the base film 12 may have a single-layer structure or a multi-layer structure having two or more layers.
  • the base film 12 may have a multilayer structure of two or more layers from the viewpoint of easy formability and hardness adjustment. From the viewpoint of moldability and hardness, the base film 12 having a multilayer structure of two or more layers may have a layer containing polycarbonate on one surface and a layer containing poly (meth) acrylate on the other surface. That is, the base film 12 may be composed of a multilayer structure (PC / PMMA composite film) having a layer containing polycarbonate and a layer containing poly (meth) acrylate.
  • the hard coat layer 14 may be formed in contact with the layer including the poly (meth) acrylate layer of the base film 12.
  • the layer containing polycarbonate is a layer containing polycarbonate as the main component of the polymer.
  • the layer containing poly (meth) acrylate is a layer containing poly (meth) acrylate as a polymer main component.
  • the polymer main component is the polymer component having the highest content in the layer. Preferably, it is a polymer component contained in the layer in an amount of 50% by mass or more.
  • the polymer main component may be more preferably contained in the layer in an amount of 60% by mass or more, more preferably 70% by mass or more.
  • the glass transition temperature (Tg) of the base film 12 is preferably in the range of 80 to 170 ° C., more preferably in the range of 90 to 160 ° C., and more preferably 120 to 160 ° C. from the viewpoint of durability and moldability in a high temperature and high humidity environment.
  • the ° C range is even more preferred.
  • each layer is in the range of the glass transition temperature (Tg).
  • the thickness of the base film 12 is not particularly limited, but is preferably in the range of 2 to 500 ⁇ m from the viewpoint of excellent handleability and the like. It is more preferably in the range of 30 to 450 ⁇ m, still more preferably in the range of 75 to 400 ⁇ m.
  • the term "film” generally means a film having a thickness of less than 0.25 mm, but even if the film has a thickness of 0.25 mm or more, the thickness is 0 if it can be rolled into a roll. Even if it is .25 mm or more, it shall be included in the "film".
  • the hard coat layer 14 contributes to improving the scratch resistance of the hard coat film 10 for insert molding.
  • the hard coat layer 14 preferably has a pencil hardness of H or higher, more preferably 3H or higher, and even more preferably 4H or higher in the state after curing. Pencil hardness can be measured according to JIS K5600-5-4.
  • the hard coat layer 14 is preferably composed of a composition that is cured by ionizing radiation from the viewpoint of scratch resistance, productivity and the like.
  • Ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules.
  • Examples of ionizing radiation include electromagnetic waves such as ultraviolet rays (UV), X-rays and ⁇ -rays, charged particle beams such as electron beams (EB), ⁇ -rays and ion rays. Of these, ultraviolet (UV) is particularly preferable from the viewpoint of productivity.
  • the composition cured by ionizing radiation contains at least one of a monomer, an oligomer, and a prepolymer having an ionizing radiation-reactive reactive group.
  • the ionizing radiation-reactive reactive group include a radically polymerized reactive group having an ethylenically unsaturated bond such as an acryloyl group, a methacryloyl group, an allyl group and a vinyl group, and a cationically polymerizable reactive group such as an oxetanyl group. And so on.
  • an acryloyl group, a methacryloyl group, and an oxetanyl group are more preferable, and an acryloyl group and a methacryloyl group are particularly preferable. That is, (meth) acrylate is particularly preferable.
  • (meth) acrylate means “at least one of acrylate and methacrylate”.
  • (Meta) acryloyl means “at least one of acryloyl and methacryloyl”.
  • (Meta) acrylic” means “at least one of acrylic and methacrylic”.
  • the (meth) acrylate may be composed of only a monofunctional (meth) acrylate, may be composed of only a polyfunctional (meth) acrylate, or may be composed of a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate. It may be composed of a combination of acrylates.
  • the composition cured by ionizing radiation preferably contains a polyfunctional (meth) acrylate.
  • Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, and isobutyl (meth) acrylate.
  • T-butyl (meth) acrylate pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl ( Meta) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) ) Acrylate, Isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate
  • polyfunctional (meth) acrylate examples include bifunctional (meth) acrylate, trifunctional (meth) acrylate, and tetrafunctional (meth) acrylate. More specifically, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonandiol di (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol
  • oligomers and prepolymers examples include urethane (meth) acrylate, silicone (meth) acrylate, alkyl (meth) acrylate, and aryl (meth) acrylate.
  • a polymer having an ionizing radiation-reactive reactive group and the like can also be mentioned.
  • the (meth) acrylate of the composition cured by ionizing radiation may be composed of only one kind of the above-mentioned (meth) acrylate, or may be composed of two or more kinds.
  • the composition that is cured by ionizing radiation may or may not contain a polymer that is not cured by ionizing radiation, in addition to a component that is cured by ionizing radiation and becomes a polymer. Further, the composition cured by ionizing radiation may contain a polymerization initiator. Further, if necessary, an additive or the like generally added to the curable composition may be contained. Examples of the additive include a dispersant, a leveling agent, a defoaming agent, a stiffening agent, an antifouling agent, an antibacterial agent, a flame retardant, a slip agent, an inorganic particle, a resin particle, and an anti-fingerprint agent. Further, if necessary, a solvent may be contained.
  • thermoplastic resins examples include polyester resin, polyether resin, polyolefin resin, polyamide resin, (meth) acrylic resin and the like.
  • thermosetting resin examples include unsaturated polyester resin, epoxy resin, alkyd resin, and phenol resin.
  • Examples of the polymerization initiator include a photopolymerization initiator.
  • Examples of the photopolymerization initiator include alkylphenone-based, acylphosphine oxide-based, and oxime ester-based photopolymerization initiators.
  • Examples of the alkylphenone-based photopolymerization initiator include 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-.
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethyl-pentylphosphine oxide and the like.
  • oxime ester-based photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and etanone-1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by mass based on the total amount of the composition cured by ionizing radiation. More preferably, it is in the range of 1 to 5% by mass.
  • Inorganic particles and resin particles are added to the hard coat layer 14 for the purpose of preventing blocking from the hard coat layer 14, suppressing the formation of wrinkles in insert molding, improving the surface hardness, and the like.
  • By forming fine surface irregularities on the hard coat layer 14 with the added inorganic particles and resin particles blocking in which the front surface and the back surface adhere to each other when the hard coat film 10 for insert molding is wound or stacked in a roll shape. Is easy to suppress. Further, since it has an appropriate slipperiness with the insert molding die, it is possible to suppress the occurrence of wrinkles in the insert molding hard coat film 10.
  • the anti-fingerprint agent is added to the hard coat layer 14 for the purpose of making it difficult for fingerprints to adhere to the hard coat layer 14, making it easier to wipe off fingerprints, or making the wiped marks less noticeable.
  • the anti-fingerprint agent include a fluorine-containing compound having an ultraviolet reactive group, and among them, a (meth) acrylate containing a perfluoroalkyl group is preferably used. Examples of such a compound include "KY-1203" manufactured by Shin-Etsu Chemical Co., Ltd., "Megafuck RS-75” manufactured by DIC, "Optur DAC-HP” manufactured by Daikin Industries, Ltd., and "Futergent 601AD” manufactured by Neos.
  • the content of the fluorine-containing compound having an ultraviolet reactive group is preferably in the range of 0.1 to 13% by mass with respect to 100% by mass of the solid content contained in the hard coat layer 14. It is more preferably in the range of 0.3 to 10% by mass, still more preferably in the range of 0.5 to 9% by mass.
  • the content of the fluorine-containing compound having an ultraviolet reactive group is 0.1% by mass or more, the slipperiness of the surface of the hard coat layer 14 is improved, so that excellent scratch resistance can be obtained and antifouling can be obtained. It is possible to improve the sex.
  • the content of the fluorine-containing compound having an ultraviolet reactive group is 13% by mass or less, the scratch resistance of the hard coat layer 14 is unlikely to decrease.
  • the composition cured by ionizing radiation may be diluted with a solvent.
  • the solvent include ethanol, isopropyl alcohol (IPA), n-butyl alcohol (NBA), ethylene glycol monomethyl ether (EGM), ethylene glycol monoisopropyl ether (IPG), propylene glycol monomethyl ether (PGM), diethylene glycol monobutyl ether and the like.
  • Alcohol solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, acetone, aromatic solvents such as toluene and xylene, ethyl acetate (EtAc), propyl acetate, isopropyl acetate, butyl acetate.
  • ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, acetone, aromatic solvents such as toluene and xylene, ethyl acetate (EtAc), propyl acetate, isopropyl acetate, butyl acetate.
  • EtAc ethyl acetate
  • propyl acetate isopropyl acetate
  • butyl acetate examples thereof include an ester solvent such as (BuAc) and
  • the solid content concentration (concentration of components other than the solvent) of the composition cured by ionizing radiation may be appropriately determined in consideration of coatability, film thickness, and the like. For example, it may be 1 to 90% by mass, 1.5 to 80% by mass, 2 to 70% by mass, and the like.
  • the thickness of the hard coat layer 14 is not particularly limited, but is preferably 0.5 ⁇ m or more from the viewpoint of having sufficient hardness and the like. It is more preferably 2.0 ⁇ m or more, still more preferably 3.0 ⁇ m or more. Further, it is preferably 15 ⁇ m or less from the viewpoint that curl due to the difference in heat shrinkage with the base film 12 can be easily suppressed. It is more preferably 10 ⁇ m or less, still more preferably 5.0 ⁇ m or less.
  • the thickness of the hard coat layer 14 is the thickness of a relatively smooth portion in a portion having no unevenness caused by inorganic particles or resin particles in the thickness direction.
  • indentation hardness measured by nanoindentation method is 10 ⁇ 200N / mm 2 at 30 ° C., more preferably 12 ⁇ 160N / mm 2, more preferably 15 ⁇ 130N / Mm 2 . If the indentation hardness at 30 ° C. is less than 10 N / mm 2 , there is a possibility that indentations may be generated on the hard coat layer 14 due to foreign matter contamination or external force during storage or in the decoration process. Further, when the protective film is peeled off before the preform step described later, the hard coat layer 14 may be transferred to the protective film or the peelability of the protective film may be deteriorated. On the other hand, if it is 200 N / mm 2 or more, the crosslink density cannot be made sufficient, and the hardness of the hard coat layer 14 after curing may be insufficient.
  • the indentation hardness of the hard coat layer 14 before curing is 100 N / mm 2 or less at 150 ° C. It is more preferably 98 N / mm 2 or less, still more preferably 90 N / mm 2 or less. If the indentation hardness at 150 ° C. exceeds 100 N / mm 2 , smoothing due to the fluidity when the hard coat layer 14 is heated becomes difficult, unevenness cannot be suppressed, and the appearance is deteriorated. Further, the indentation hardness at 150 ° C. is preferably 0.1 N / mm 2 or more. It is more preferably 0.5 N / mm 2 or more, and further preferably 1.0 N / mm 2 or more.
  • the indentation hardness at 150 ° C. is 0.1 N / mm 2 or more, the fluidity of the hard coat layer 14 does not become excessively high, and the hard coat layer 14 may hang down and the uniformity of the thickness may be impaired. Hateful.
  • the hard coat film 10 for insert molding can be manufactured by forming the hard coat layer 14 on one surface of the base film 12.
  • the hard coat layer 14 can be formed by applying a composition for forming the hard coat layer 14 on one surface of the base film 12 and drying the hard coat layer 14 as necessary.
  • the surface of the base film 12 may be surface-treated before coating. Examples of the surface treatment include corona treatment, plasma treatment, hot air treatment, ozone treatment, and ionizing radiation treatment.
  • Examples of the coating of the composition forming the hard coat layer 14 include a reverse gravure coat method, a direct gravure coat method, a die coat method, a bar coat method, a wire bar coat method, a roll coat method, a spin coat method, and a dip coat method.
  • Various coating methods such as spray coating method, knife coating method, and kiss coating method, and various printing methods such as inkjet method, offset printing, screen printing, and flexo printing can be used.
  • the drying step is not particularly limited as long as the solvent used in the coating liquid can be removed, but it is preferably performed at a temperature of 50 to 150 ° C. for about 10 seconds to 180 seconds. In particular, the drying temperature is preferably 50 to 120 ° C.
  • the hard coat layer 14 is not completely cured in an uncured or semi-cured state.
  • the hard coat film for insert molding is set into a uncured or semi-cured state, it is possible to prevent cracks from occurring in the hard coat layer 14 even when the hard coat film for insert molding is preformed into a deep shape.
  • the hard coat film 10 for insert molding may be provided with a decorative layer, if necessary.
  • the decorative layer is formed on the surface of the base film 12 opposite to the surface having the hard coat layer 14.
  • the decorative layer is usually formed as a print layer.
  • a resin such as a polyvinyl resin, a polyamide resin, a polyacrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, or an alkyd resin is used as a binder, which is appropriate. It is preferable to use a coloring ink containing a color pigment or dye as a coloring agent. Further, in the case of metal coloring, metal particles such as aluminum, titanium and bronze, and a pearl pigment obtained by coating mica with titanium oxide can also be used.
  • a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression.
  • the decorative layer may be made of a metal thin film layer or a combination of a printed layer and a metal thin film layer.
  • the metal thin film layer is formed by a vacuum vapor deposition method, a sputtering method, an ion plating method, a plating method, or the like.
  • a metal foil may be used. Metals such as aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead and zinc, alloys or compounds thereof are used depending on the metallic luster color to be expressed.
  • an anchor layer such as a front anchor layer or a rear anchor layer may be provided in order to improve the adhesion between the other transfer layer and the metal thin film layer.
  • the material of the anchor layer it is preferable to use a two-component curable urethane resin, a thermosetting urethane resin, a thermosetting resin such as a melamine resin or an epoxy resin, or a thermoplastic resin such as a vinyl chloride copolymer resin. ..
  • the method for forming the anchor layer include a coating method such as a gravure coating method, a roll coating method, and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.
  • the base film 12 has a base film 12 and a hard coat layer 14 formed on the surface of the base film 12, and the hard coat layer 14 has ionizing radiation.
  • the indentation hardness of the hardcourt layer 14, measured by the nanoindentation method, is 10 to 200 N / mm 2 at 30 ° C and 100 N / mm 2 or less at 150 ° C. Therefore, it has excellent scratch resistance, suppresses indentations during storage, and has excellent surface smoothness after preformation.
  • FIG. 2 is a cross-sectional view of a hard coat film for insert molding according to another embodiment.
  • the hard coat film 20 for insert molding according to another embodiment includes the base film 12, the hard coat layer 14 formed on the surface of the base film 12, and the hard coat layer 14. It has a pressure-sensitive adhesive layer 16 formed on the surface and a protective film 18 formed on the surface of the pressure-sensitive adhesive layer 16.
  • a protective film 18 is arranged on the surface of the hard coat layer 14 via the adhesive layer 16. If the protective film 18 has self-adhesiveness, the pressure-sensitive adhesive layer 16 may be omitted.
  • the insert molding hard coat film 20 has a pressure-sensitive adhesive layer 16 on the surface of the hard coat layer 14 as compared with the insert molding hard coat film 10 according to the above embodiment.
  • the difference is that the protective film 18 is arranged, and other than that, it is the same as the hard coat film 10 for insert molding according to the above embodiment, and the description thereof will be omitted for the same configuration.
  • the pressure-sensitive adhesive layer 16 is for attaching the protective film 18 on the surface of the hard coat layer 14.
  • the pressure-sensitive adhesive layer 16 is composed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer 16 may be composed of a resin composition containing a pressure-sensitive adhesive. Examples of the resin of the resin composition include polyethylene and an ethylene / vinyl acetate copolymer.
  • an acrylic pressure-sensitive adhesive is particularly preferable from the viewpoint of excellent transparency and heat resistance.
  • the acrylic pressure-sensitive adhesive is preferably formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer and a cross-linking agent.
  • the (meth) acrylic polymer is a homopolymer or copolymer of the (meth) acrylic monomer.
  • examples of the (meth) acrylic monomer include an alkyl group-containing (meth) acrylic monomer, a carboxyl group-containing (meth) acrylic monomer, and a hydroxyl group-containing (meth) acrylic monomer.
  • alkyl group-containing (meth) acrylic monomer examples include (meth) acrylic monomers having an alkyl group having 2 to 30 carbon atoms.
  • the alkyl group having 2 to 30 carbon atoms may be linear, branched chain, or cyclic. More specifically, examples of the alkyl group-containing (meth) acrylic monomer include, for example, isostearyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and (meth).
  • Decyl acrylate (meth) isononyl acrylate, (meth) nonyl acrylate, (meth) isooctyl acrylate, (meth) octyl acrylate, (meth) isobutyl acrylate, (meth) n-butyl acrylate, ( Pentyl acrylate, (meth) hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, etc. Can be mentioned.
  • Examples of the carboxyl group-containing (meth) acrylic monomer include (meth) acrylic acid, (meth) carboxyethyl acrylate, and (meth) carboxypentyl acrylate.
  • the carboxyl group may be located at the end of the alkyl chain or may be located in the middle of the alkyl chain.
  • hydroxyl group-containing (meth) acrylic monomer examples include (meth) hydroxylauryl acrylate, (meth) hydroxydecyl acrylate, (meth) hydroxyoctyl acrylate, (meth) hydroxyhexyl acrylate, and (meth) hydroxybutyl acrylate. Examples thereof include hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate.
  • the hydroxyl group may be located at the end of the alkyl chain or may be located in the middle of the alkyl chain.
  • the (meth) acrylic monomer forming the (meth) acrylic polymer may be any one of the above, or may be a combination of two or more.
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, metal alkoxide-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and melamine-based cross-linking agents. ..
  • the cross-linking agent one of these may be used alone, or two or more thereof may be used in combination.
  • the pressure-sensitive adhesive composition may contain other additives in addition to the (meth) acrylic polymer and the cross-linking agent.
  • Other additives include cross-linking accelerators, cross-linking retarders, tackifiers, antistatic agents, silane coupling agents, plasticizers, release aids, pigments, dyes, wetting agents, thickeners, etc. Examples include UV absorbers, preservatives, antioxidants, metal deactivators, alkylating agents, flame retardants and the like. These are appropriately selected and used according to the use and purpose of use of the pressure-sensitive adhesive.
  • the thickness of the pressure-sensitive adhesive layer 16 is not particularly limited, but is preferably in the range of 1 to 10 ⁇ m. More preferably, it is in the range of 2 to 7 ⁇ m.
  • the arithmetic average surface roughness (Ra) of the surface of the pressure-sensitive adhesive layer 16 (or the protective film 18 having self-adhesiveness) in contact with the hard coat layer 14 is preferably 200 nm or less. It is more preferably 150 nm or less, still more preferably 100 nm or less. If the arithmetic average surface roughness (Ra) is 200 nm or less, the hard coat layer 14 is uneven even after being bonded to the hard coat layer 14 for storage, transportation, and a decoration process performed as necessary. Can be made excellent in aesthetics with suppressed.
  • the protective film 18 can prevent the surface of the hard coat layer 14 from being scratched during continuous processing, for example, in a roll process or the like, or during handling such as a decoration step following the formation of the hard coat layer 14. ..
  • the protective film 18 is peeled off from the surface of the hard coat layer 14 together with the adhesive layer 16 after the printing process and before preform. Therefore, the adhesive layer 16 has a stronger adhesive force between the protective film 18 and the adhesive layer 16 than the adhesive force between the hard coat layer 14 and the adhesive layer 16, and the hard coat layer 14 and the adhesive layer 16 have a stronger adhesive force.
  • the adhesive strength is adjusted so that the interface can be peeled off between 16.
  • the material constituting the protective film 18 is, for example, polyester such as polyethylene terephthalate or polyethylene naphthalate, polycarbonate, poly (meth) acrylate, polystyrene, polyamide, polyimide, polyacrylonitrile, and polypropylene, polyethylene, polycycloolefin, cycloolefin copolymer. Examples thereof include polyolefins such as, polyphenylene sulfide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and the like.
  • the material constituting the protective film 18 may be composed of only one of these, or may be composed of a combination of two or more. Of these, polyethylene terephthalate, polypropylene, and polyethylene are more preferable from the viewpoint of mechanical properties and material cost.
  • the protective film 18 may be composed of a single layer composed of a layer containing one or more of the above-mentioned polymer materials, or a layer containing one or more of the above-mentioned polymer materials and this layer. It may be composed of two or more layers such as a layer containing one kind or two or more kinds of polymer materials different from the above.
  • the thickness of the protective film 18 is not particularly limited, but can be within the range of 2 to 500 ⁇ m and within the range of 2 to 200 ⁇ m.
  • the protective film 18 is attached to the surface of the hard coat layer 14 via the adhesive layer 16.
  • a laminator or the like can be used for bonding.
  • aging may be performed if necessary.
  • the hard coat film for insert molding according to the present invention is placed on the surface of a resin molded product molded by injection molding or the like to improve the scratch resistance of the resin molded product.
  • the hard coat film for insert molding according to the present invention is integrally adhered to the resin molded product by being insert-molded into the resin molded product.
  • an insert molded product provided with the hard-coated film according to the present invention can be obtained.
  • this product has a hard coat coat film 10 integrally bonded to the surface of the insert molded product 22.
  • the hard coat film 10 is adhered to the surface of the insert molded product 22 on the surface on the base film 12 side, and the hard coat layer 14 is exposed on the surface.
  • the insert-molded product provided with the hard-coated film according to the present invention is suitable as a resin-molded product used for interior parts of automobiles, panels and exterior parts of electric appliances such as mobile phones.
  • it is suitable as a resin molded product that is deeply drawn.
  • the insert-molded product provided with the hard-coated film according to the present invention can be obtained by the method for manufacturing the insert-molded product according to the present invention.
  • the method for producing an insert molded product according to the present invention has the following steps (1) to (7). Depending on the case, the step of (2) below and the step of peeling off the adhesive layer and the protective film in (3) can be omitted.
  • FIG. 5 shows a manufacturing process of an insert molded product.
  • a step of forming a hard coat layer on the surface of a base film to obtain a hard coat film (2) A step of adhering a protective film on the surface of the hard coat layer via an adhesive layer. (3) A step of peeling off the protective film together with the adhesive layer and molding the hard coat film into the shape of the surface of the molded product by a preform mold. (4) A step of irradiating a molded hardcoat film with ionizing radiation to cure the hardcoat layer. (5) A step of arranging the cured hard coat film between a movable mold and a fixed mold, which are molding dies of an injection molding machine.
  • the above (1) is a step of obtaining the above-mentioned hard coat film 10 for insert molding.
  • a hard coat layer 14 is formed on the surface of the base film 12 to obtain a hard coat film 10 for insert molding.
  • the hard coat layer 14 is composed of a composition that is cured by ionizing radiation, and the indentation hardness measured by the nanoindentation method is 10 to 200 N / mm 2 at 30 ° C. and at 150 ° C. It is 100 N / mm 2 or less.
  • the above (2) is a step of obtaining the above hard coat film 20 for insert molding.
  • the protective film 18 is attached onto the surface of the hardcoat layer 14 via the adhesive layer 16.
  • the pressure-sensitive adhesive layer 16 preferably has an arithmetic average surface roughness (Ra) of 200 nm or less on the surface in contact with the hard coat layer 14.
  • the above (3) is a preform process of the hard coat film 10 for insert molding.
  • the protective film 18 is peeled off from the insert molding hard coat film 20 together with the pressure-sensitive adhesive layer 16, and the insert molding hard coat film 10 is formed by the preform mold 24 into the shape of the surface of the molded product.
  • the desired shape is set according to the surface shape of the inserted molded product 22 to be manufactured.
  • the preform shape is set so that the surface of the hard coat film 10 on the base film 12 side is in contact with the surface of the insert molded product 22.
  • the hard coat film 10 for insert molding is molded using a preform mold 24 that matches the shape of the surface of the molded product.
  • the hard coat film 10 for insert molding is subjected to the above-mentioned decoration as necessary before the preform step.
  • the preform step is a step of heating the insert molding film 10 and shaping it by using a preform mold corresponding to the shape of the injection molding die by a method such as vacuum molding, pressure molding, vacuum pressure molding, or press molding.
  • vacuum forming for example, the insert molding film 10 is heated in advance to soften it, a vacuum is created between the preform mold 24 and the insert molding hard coat film 10, and the insert molding hard coat film 10 is placed along the preform mold. It is a vacuum forming.
  • the insert molding film 10 is heated in advance to be softened, and the insert molding film 10 is stretched by the force of compressed air to be molded along the preform mold 24.
  • the press molding for example, the insert molding film 10 is heated in advance to be softened, the insert molding film 10 is sandwiched between the preform mold 24 and the concave mold, and the insert molding film 10 is formed along the preform mold 24.
  • the temperature at which the hard coat film 10 for insert molding is heated in advance is preferably close to the glass transition temperature of the base film 12.
  • the base film 12 is a two-layer laminated film of polycarbonate and polymethyl methacrylate, it is in the range of 130 to 200 ° C, preferably in the range of 145 to 180 ° C, and more preferably in the range of 145 to 160 ° C. Is.
  • the heating temperature can be measured by detecting the surface temperature of the hard coat film 10 for insert molding using, for example, an infrared radiation thermometer.
  • the above (4) is a step of irradiating the molded hard coat film 10 for insert molding with ionizing radiation to cure the hard coat layer 14.
  • the insert forming hard coat film 10 is kept along the preform mold 24 or removed from the preform mold 24, as shown in FIG. 5 (d).
  • the hardcourt layer 14 is completely cured by irradiating the ionizing radiation from the device 26 that irradiates the ionizing radiation.
  • “completely curing” means that the degree of curing of the hardcoat layer 14 is 60% or more, preferably 70% or more, more preferably 80% or more, and the upper limit is 100%.
  • the degree of curing is attributed to the ethylenically unsaturated bond of the hard coat layer 14 immediately after being applied to the base film 12 and dried using a Fourier converted infrared spectrophotometer (for example, "IR-PRESTIGE 21" manufactured by Shimadzu Corporation).
  • the absorbance is set to 0, and after irradiating with an ultraviolet ray having an integrated light amount of 1000 mJ / cm 2 , another irradiation with an ultraviolet ray having an integrated light amount of 1000 mJ / cm 2 is performed , and the value when the absorbance attributed to the ethylenically unsaturated bond does not change is 100. It can be obtained from the magnitude of the absorbance attributed to the ethylenically unsaturated bond of the hard coat layer 14 after curing.
  • ultraviolet rays and electron beams can be used.
  • a high-pressure mercury lamp, an electrodeless (microwave method) lamp, a xenon lamp, a metal halide lamp, or any other ultraviolet irradiation device can be used.
  • Irradiation with ultraviolet rays may be carried out in an atmosphere of an inert gas such as nitrogen, if necessary.
  • UV irradiation dose but it is not limited to, preferably 50 ⁇ 500mJ / cm 2, more preferably 100 ⁇ 400mJ / cm 2.
  • electron beams emitted from various electron beam accelerators such as Cockloftwald type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. ..
  • the electron beam preferably has an energy of 50 to 1000 KeV.
  • An electron beam having an energy of 100 to 300 KeV is more preferable.
  • the above (5) to (7) are insert molding processes.
  • the insert molding method is a type of plastic injection molding technology, and among synthetic resins, it is mainly a thermoplastic resin that is melted (plasticized) by applying heat and pressure to achieve an appropriate flow state.
  • injection molding which is poured into a closed mold at high speed under high pressure (injection pressure) to be sufficiently solidified and taken out, a preformed insert molding film is inserted into the mold in advance, and the film is formed. It is a method of obtaining a resin molded product integrated with.
  • the preformed hard coat film 10 for insert molding is placed inside the molding mold (movable mold) of the injection molding machine.
  • the mold is closed, the thermoplastic resin, which is the molding resin supplied to the hopper of the injection molding machine, is weighed and kneaded by the rotation of the screw, and the molding resin melted at a high temperature is injected, and the pressure and heat at the time of molding are injected.
  • the hard coat film 10 for insert molding is integrated on the surface thereof and adhered on the base film 12 side.
  • the mold is opened, and as shown in FIG. 5 (e), the insert molded product 30 in which the hard coat film 10 for insert molding is integrated with the resin molded product 22 is taken out.
  • the molding resin used for such injection molding is not particularly limited as long as it has transparency, but (meth) acrylic resin, polycarbonate resin, polystyrene resin, ABS resin, polyethylene resin, polypropylene resin, and the like.
  • Thermoplastic resins such as fluororesins and polyamide resins and other thermocurable resins can be used.
  • composition for forming a hard coat layer ⁇ 1> An ultraviolet curable composition containing an acrylic resin (“NXD-001A” manufactured by Nippon Kako Paint Co., Ltd. “was used.
  • composition for forming a hard coat layer ⁇ 2> An ultraviolet curable composition (“Z-624-12L” manufactured by Aica Kogyo Co., Ltd.) containing a modified acrylic resin and silica particles was used.
  • composition for forming a hard coat layer ⁇ 3> A solvent is added to an ultraviolet curable composition (“Z-608-2AF (PGM)” manufactured by Aica Kogyo Co., Ltd.) containing a modified acrylic resin, diluted to a solid content concentration of 20% by mass, and used for forming a hard coat layer.
  • Z-608-2AF (PGM) manufactured by Aica Kogyo Co., Ltd.
  • the composition ⁇ 3> was obtained.
  • composition for forming a hard coat layer ⁇ 4> An ultraviolet curable composition containing a modified acrylic resin and silica particles (“Z-624-12L” manufactured by Aika Industries) and an ultraviolet curable composition containing dipentaerythritol penta / hexaacrylate (“M403” manufactured by Toagosei). ) Is mixed so that the mass ratio of the solid content is 8: 1, a solvent is added, and the mixture is diluted so that the solid content concentration becomes 30% by mass to obtain a composition for forming a hard coat layer ⁇ 4>. rice field.
  • a protective film with an adhesive layer was placed on the surface of the hard coat layer so that the adhesive layer was in contact with the hard coat layer, bonded using a hand roller, and then pressure-bonded using a laminator (nip pressure). 0.6MPa / 500mm). Then, it was cut into 294 ⁇ 210 mm, loaded with 16.2 g / cm 2 (10 kg for a 294 ⁇ 210 mm film), and allowed to stand for 48 hours. From the above, a hard coat film was produced.
  • the prepared hard coat film was cut into a size of 210 ⁇ 148 mm, the protective film with an adhesive layer was peeled off, and then the hard coat film was heated by sandwiching it from above and below using two infrared heaters.
  • the distance between the infrared heater and the hard coat film was 100 mm, the temperature of the infrared heater was 600 ° C., and the heating temperature was 7 seconds.
  • the surface temperature of the hard coat film 1 after 7 seconds of heating was 150 ° C.
  • the infrared heater on the opposite side of the hard coat layer is moved away from the hard coat film, and immediately, while creating a vacuum between the preform type (42 x 60 mm, box type with a drawing depth of 30 mm) and the hard coat film, hard
  • the surface of the coat film opposite to the hard coat layer was pressed against the film and molded along the preform mold.
  • the infrared heater on the hard coat layer side continued to heat at 600 ° C., and the temperature of the preform type was set to 90 ° C.
  • the hard-coated film was pressed against the preform mold and allowed to stand for 5 seconds, and then removed from the preform mold.
  • the hard coat layer side of the preformed hard coat film was irradiated with ultraviolet rays having a light intensity of 200 mJ / cm 2 using an ultraviolet irradiation device (high-pressure mercury lamp manufactured by Eye Graphics) to completely cure the hard coat layer. ..
  • the hard coat film from which the protective film with the adhesive layer was peeled off was cut into 15 mm ⁇ 15 mm, and using an ultra-fine indentation hardness tester (“ENT-NEXUS” manufactured by Elionix Inc.), based on ISO14577 Standard measurement, 30 In an environment of ° C and 150 ° C, a Berkovich indenter (triangular pyramid diamond indenter, interridge angle 115 °) is pushed into the measurement sample, a load-unloading test is performed, and the hard coat layer (before preform and curing) is analyzed by test data analysis. Indentation hardness was obtained. The maximum pushing load was 400 ⁇ N, the maximum load holding time was 5 seconds, and the unloading ratio used during the analysis was 200%.
  • ENT-NEXUS ultra-fine indentation hardness tester
  • the arithmetic average roughness Ra of the surface was measured using a non-contact surface / layer cross-sectional shape measurement system (“Vertcan 2.0 (model: R5300GL-LA100-AC)” manufactured by Mitsubishi Chemical Systems). Measurements were made on the surface (on the adhesive layer side) of the protective film with adhesive layer or self-adhesive protective film, as well as on the surface of the hardcourt layer (before curing) of the hardcourt film before and after preform. I went there.
  • the hard coat film for insert molding after being completely cured by irradiating with ultraviolet rays was cut into 50 mm ⁇ 100 mm, placed on a glass plate having a thickness of 2 mm, and the pencil hardness on the surface of the hard coat layer was measured. .. It was measured by the method specified in JIS K 5600-5-4 using a pencil hardness tester (manufactured by Tester Sangyo). The test load was 500 g, and repeated tests were performed while changing the hardness of the pencil, and the maximum hardness when the scratches and dents generated by the same pencil were within 1 out of 5 times was used as the evaluation value.
  • Comparative Example 1 since the indentation hardness at 30 ° C. exceeds 200 N / mm 2 , the pencil hardness of the hard coat layer (HC layer) after being completely cured is as low as HB. In Comparative Examples 2 to 4, since the indentation hardness at 30 ° C. is less than 10 N / mm 2 , indentations are likely to occur during storage and in the decorating process. Further, since the indentation hardness at 150 ° C. exceeds 100 N / mm 2 , the surface roughness after curing is large due to insufficient leveling property during heating in the preform step, and the appearance is inferior. Further, in Comparative Example 4, since the surface roughness Ra of the protective film is relatively high at 180 nm, the hard coat surface tends not to return to smooth even when heated in the preform step.
  • Examples 1 to 6 are composed of a composition in which the hard coat layer is cured by ionizing radiation, and the indentation hardness of the hard coat layer measured by the nanoindentation method is 10 at 30 ° C. Since it is ⁇ 200 N / mm 2 and 100 N / mm 2 or less at 150 ° C., the pencil hardness of the hard coat layer after complete curing is as hard as 3H or 4H, and it is excellent in scratch resistance. In addition, it can be seen that indentations during storage can be suppressed. Furthermore, it can be seen that the surface smoothness after preformation is excellent.
  • Hard coat film for insert molding 12
  • Base film 14
  • Hard coat layer 16
  • Adhesive layer 18
  • Protective film 22
  • Resin molded product 24
  • Preform type 26 Device to irradiate ionizing radiation

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