WO2009154042A1 - Film de revêtement dur pour le moulage - Google Patents

Film de revêtement dur pour le moulage Download PDF

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Publication number
WO2009154042A1
WO2009154042A1 PCT/JP2009/058041 JP2009058041W WO2009154042A1 WO 2009154042 A1 WO2009154042 A1 WO 2009154042A1 JP 2009058041 W JP2009058041 W JP 2009058041W WO 2009154042 A1 WO2009154042 A1 WO 2009154042A1
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WO
WIPO (PCT)
Prior art keywords
hard coat
molding
mass
film
ionizing radiation
Prior art date
Application number
PCT/JP2009/058041
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English (en)
Japanese (ja)
Inventor
薫 澤田
憲一 森
Original Assignee
東洋紡績株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡績株式会社 filed Critical 東洋紡績株式会社
Priority to CN200980123310.XA priority Critical patent/CN102066471B/zh
Priority to KR1020117000888A priority patent/KR101355324B1/ko
Publication of WO2009154042A1 publication Critical patent/WO2009154042A1/fr

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Classifications

    • 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
    • B32B27/28—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • the present invention relates to a hard coat film for molding which has excellent surface hardness, scratch resistance and excellent moldability.
  • a polyvinyl chloride film has been representative, and due to recent needs for environmental resistance, unstretched films made of polyester, polycarbonate and acrylic resin, which have a low environmental load, and further heat resistance and resistance.
  • unstretched films made of polyester, polycarbonate and acrylic resin, which have a low environmental load, and further heat resistance and resistance.
  • a biaxially stretched polyester film having excellent solvent properties is used. (For example, see Patent Documents 1 to 10).
  • a molding film is attached to a position where it touches the outside, such as a home appliance, a car nameplate or a building material member, in order to prevent scratches, the surface hardness of the molding film is supplemented and the scratch resistance is improved.
  • a hard coat layer is provided on the surface.
  • a method for providing a hard coat layer on a molding film As a method for providing a hard coat layer on a molding film, a method is generally employed in which a hard coat layer is laminated after being molded by a pressure forming method, a vacuum forming method, or the like, and then post-processed by a dipping method, a spray method, or the like.
  • the hard coat layer is laminated by single-wafer processing, so that there is a limit to improvement in production speed and there is a problem in stability of quality. Therefore, after a hard coat layer is provided on a film before molding by a roll-to-roll method, a molded body by a method of molding is required.
  • JP-A-9-156267 JP-A-9-187903 JP-A-10-296937 Japanese Patent Laid-Open No. 11-268215 JP 2001-129951 A Japanese Patent Laid-Open No. 2001-212868 JP 2002-249652 A Japanese Patent Laid-Open No. 2003-221606 JP 2004-075713 A JP 2005-290354 A JP 2005-305383 A JP 2007-284626 A JP 2007-313728 A International Publication No. 2008/029666 Pamphlet
  • the hard coat film proposed in Patent Documents 11 and 13 has an appropriate surface hardness
  • the hard coat film has only limited processing characteristics such as bendability and punching, and is proposed in Patent Document 12.
  • the hard coat film has extensibility, the surface hardness was not satisfactory.
  • the hard coat film proposed in Patent Document 14 attempts to achieve both surface hardness and formability, it has sufficient performance in fields where higher formability and higher surface hardness are required. In some cases, it could not be demonstrated. That is, the above-mentioned patent document does not provide a hard coat film for molding that satisfies both high surface hardness and high moldability at the same time.
  • the object of the present invention is to solve the above problems, that is, by processing and laminating a hard coat layer on a molding film before molding, it contributes to improving productivity and stability of quality.
  • Another object of the present invention is to provide a molding hard coat film having both surface hardness, scratch resistance, and moldability capable of following deformation during molding.
  • the present invention is as follows.
  • a first invention is a molding hard coat film having a hard coat layer formed by applying and curing a coating liquid on at least one surface of a base film, wherein the coating liquid has three or more functional groups. Containing at least a radiation curable compound and a monofunctional and / or bifunctional ionizing radiation curable compound, and the inclusion of the monofunctional and / or bifunctional ionizing radiation curable compound in the ionizing radiation curable compound contained in the coating solution It is a hard coat film for molding whose amount is 5% by mass or more and 95% by mass or less. 2nd invention is the said hard coat film for shaping
  • 3rd invention is the said hard coating film for shaping
  • 4th invention contains the particle
  • the said hard coat for molding It is a film.
  • 5th invention contains an ionizing radiation-curable silicone resin in the said hard-coat layer, and content in the hard-coat layer of the said ionizing radiation-curable silicone resin is 0 with respect to 100 mass parts of said ionizing radiation-curable compounds. ..
  • the hard coat film for molding that is 15 parts by mass or more and 15 parts by mass or less.
  • 6th invention is a molded object formed by shape
  • 7th invention is the said molded object whose thickness of a hard-coat layer is 0.5 micrometer or more and 50 micrometers or less.
  • the 8th invention is a manufacturing method of the hard-coat film roll for shaping
  • the coating solution contains at least an organic solvent, an ionizing radiation curable compound having three or more functional groups, and a monofunctional and / or bifunctional ionizing radiation curable compound, The content of the monofunctional and / or bifunctional ionizing radiation curable compound in the ionizing radiation curable compound contained in the coating solution is 5% by mass or more and 95% by mass or less, After applying the coating solution, the film is dried under conditions of a film tension of 50 N / m or more and 300 N / m or less and a temperature of 40 ° C. or more and 120 ° C. or less, and then hardened to provide a hard coat layer. It is a manufacturing method of a hard coat film roll.
  • the hard coat film for molding of the present invention has characteristics of both surface hardness, scratch resistance and moldability that can follow deformation during molding. Since the present invention has a high surface hardness and excellent extensibility, it can be suitably used as, for example, a nameplate member or a building material member as a preferred embodiment. Further, as a preferred embodiment of the present invention, when an ionizing radiation curable resin or / and particles having an amino group are used, both characteristics of surface hardness and moldability can be achieved at a higher level. For example, as a member such as a casing It can be preferably used.
  • the present invention does not require a hard coat process after molding, can contribute to productivity and stability of quality in the manufacturing process of the molding process, and is used as a film roll for molding as a preferred embodiment of the present invention. Is excellent in the quality stability of the molded body.
  • the base film is not particularly limited, but has a moldability.
  • moldability means that a molded body can be formed by a molding process such as mold molding, pressure molding, or vacuum molding. Specifically, it has a film stress characteristic that can form a molded body without breaking the base film even when a high stress is partially generated in a portion that is locally elongated by molding.
  • the base film examples include plastics such as polyester, acrylic, cellulose, polyethylene, polypropylene, polyolefin, polyvinyl chloride, polycarbonate, phenol, and urethane. Examples include a film or sheet and a laminate of any two or more of these. A polyester film having a good balance between heat resistance and flexibility is preferable.
  • a polyester film containing a copolymerized polyester excellent in moldability at the time of heat molding at low temperature or low pressure is preferable.
  • the copolyester include (a) a copolyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol, or (b) terephthalic acid and isophthalic acid.
  • a copolyester composed of an aromatic dicarboxylic acid component containing an acid and a glycol component containing ethylene glycol is preferred.
  • the aromatic dicarboxylic acid component is Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more. Particularly preferred is 95 mol% or more, and particularly preferred is 100 mol%.
  • the polyester film containing the copolymerized polyester includes a copolymerized polyester component as a component of the film, and specific examples thereof include the following.
  • the base film consists entirely of a copolymerized polyester, (2) the base film contains a copolymerized polyester as part of the constituent components (for example, a copolymerized polyester, polyethylene terephthalate, polyethylene naphthalate, etc. (Consisting of a resin composition mixed with another (homo) polyester), (3) a base film comprising a multilayer of a polyester layer containing a copolymerized polyester and a polyester layer not containing the copolymerized polyester.
  • the base film is particularly preferably a biaxially stretched film from the viewpoints of heat resistance and solvent resistance.
  • the stretching method include a tubular stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and the like, but a sequential biaxial stretching method is preferable in view of flatness, dimensional stability, thickness unevenness, and the like.
  • a sequential biaxial stretching method in the case of using a polyester film as a base film, the film is stretched in the longitudinal direction from 50 ° C. to 110 ° C. in the longitudinal direction and from 1.6 times to 4.0 times in the longitudinal direction. After preheating, the glass can be stretched in the width direction from 1.2 times to 5.0 times at a glass transition temperature of -40 ° C to + 65 ° C.
  • a heat setting treatment can be performed at a temperature of ⁇ 40 ° C. or more and ⁇ 10 ° C. or less of the melting point of the polyester.
  • the base film used in the present invention preferably contains particles in the film to form protrusions on the film surface in order to impart handling properties (for example, winding property after lamination).
  • particles to be included in the film inorganic particles such as silica, kaolinite, talc, calcium carbonate, zeolite, alumina, etc., heat resistant polymer particles such as acrylic, PMMA, nylon, polystyrene, polyester, benzoguanamine / formalin condensate, etc. Is mentioned.
  • the content of particles in the film is preferably small, for example, preferably 1 ppm or more and 1000 ppm or less.
  • the film may contain a light-resistant agent (ultraviolet ray inhibitor), a pigment, an antistatic agent, and the like.
  • the total light transmittance of the base film is 80% or more and the haze is 5% or less.
  • the transparency of the substrate film is inferior, the visibility when the printed layer is viewed from the hard coat layer side is lowered.
  • the base film used in the present invention may be a single layer film or a composite film of two or more layers in which a surface layer and a center layer are laminated.
  • a composite film there is an advantage that the functions of the surface layer and the center layer can be designed independently. For example, by containing particles only on the thin surface layer and forming irregularities on the surface, the handling property is maintained, but the thick central layer does not substantially contain particles, so that the composite film as a whole is transparent. Can be further improved.
  • the method for producing the composite film is not particularly limited, but considering productivity, after extruding the raw material of the surface layer and the central layer from separate extruders, leading to one die and obtaining an unstretched sheet, Lamination by a so-called coextrusion method that is oriented in at least one axial direction is preferable.
  • the thickness of the base film used in the present invention varies depending on the material, but when a polyester film is used, the lower limit is preferably 35 ⁇ m or more, more preferably 50 ⁇ m or more. On the other hand, the upper limit of the thickness is preferably 260 ⁇ m or less, more preferably 200 ⁇ m or less.
  • the thickness is small, not only the handling property becomes poor, but also when heated at the time of drying so as to reduce the residual solvent of the hard coat layer, the film tends to be wrinkled and flatness tends to be poor.
  • the thickness is large, not only is there a problem in terms of cost, but flatness due to curling tends to occur when the material is wound and stored in a roll shape.
  • the molding hard coat film of the present invention has a configuration in which a hard coat layer is laminated on one surface of a base film, and an intermediate layer may be provided for the purpose of improving the adhesion between the base film and the hard coat layer. preferable.
  • the handleability of a base film can be provided by providing the intermediate
  • the resin constituting the intermediate layer examples include polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, melamine resins, and mixed resins thereof, but adhesion to the base film and the hard coat layer. If the resin constituting the base film and the hard coat layer is acrylic, specifically, among acrylic, copolymer polyester, and polyester urethane It is preferable to select at least one kind.
  • the intermediate layer may contain a crosslinking agent for the purpose of improving adhesion and improving water resistance to form a crosslinked structure.
  • a crosslinking agent for the purpose of improving adhesion and improving water resistance to form a crosslinked structure.
  • the crosslinking agent include urea, epoxy, melamine, and isocyanate.
  • the intermediate layer may contain various particles for the purpose of improving the slipperiness by forming irregularities on the film surface before the formation of the hard coat layer.
  • the particles contained in the intermediate layer include inorganic particles such as silica, kaolinite, talc, calcium carbonate, zeolite, and alumina, and organic particles such as acrylic, PMMA, nylon, styrene, polyester, and benzoguanamine / formalin condensate. Is mentioned.
  • a coating method is preferable.
  • the coating method using a known coating method such as gravure coating method, kiss coating method, dip method, spray coating method, curtain coating method, air knife coating method, blade coating method, reverse roll coating method, etc. It can be provided by an in-line coating method in which a coating layer is provided, or an offline coating method in which a coating layer is provided after film production.
  • the in-line coating method is not only excellent in terms of cost, but by adding particles to the intermediate layer, it is not necessary to include particles in the base film, so that the transparency can be highly improved. This is preferable because it is possible.
  • the hard coat layer In the hard coat film for molding of the present invention, a hard coat layer is laminated directly or via an intermediate layer on at least one surface of the base film.
  • the hard coat layer has a coating with a hardness higher than that of the base material in order to supplement the surface hardness of the base material made of the base film and improve the scratch resistance, and also to deformation during molding.
  • the layer which has the outstanding moldability which can be followed is shown. More specifically, the hard coat film for molding of the present invention has a pencil hardness of at least H as the surface hardness, and an elongation of at least 10% according to the evaluation method described below. It can be suitably used as a member for use or for building materials.
  • the hard coat layer that can be used in the present invention needs to contain an ionizing radiation curable resin as a main component. Unlike the thermosetting resin, heat treatment at the time of curing is not required, and heat shrinkage of the base film due to heat can be reduced, which is preferable.
  • the ionizing radiation curable compound refers to a compound that polymerizes and / or reacts when irradiated with an electron beam, radiation, or ultraviolet light, and the compound reacts and / or reacts.
  • a hard coat layer is formed.
  • the ionizing radiation curable compound used in the present invention include melamine-based, acrylic and silicon-based ionizing radiation curable compounds. Among them, acrylate-based ionizing radiation curable compounds are preferable in terms of obtaining high surface hardness. .
  • the ionizing radiation curable compound includes not only monomers and precursors but also ionizing radiation curable resins obtained by polymerization and / or reaction thereof.
  • examples of the acrylate ionizing radiation curable compound include polyurethane acrylate, polyester acrylate, epoxy acrylate, polyol acrylate and the like, but are not particularly limited, and any acrylate ionizing radiation curable compound may be used. .
  • the hard coat layer in the present invention is applied to a base film with a coating solution containing at least an ionizing radiation curable compound having three or more functional groups and a monofunctional and / or bifunctional ionizing radiation curable compound, and then an electron beam. It is cured by polymerizing and / or reacting by irradiation with either radiation or ultraviolet rays.
  • the monofunctional (monofunctional) acrylate ionizing radiation curable compound in the present invention has at least one (meth) acryloyl group in the molecule. If it is a compound to contain, it will not restrict
  • acrylamide (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, di Cyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (
  • the bifunctional acrylate ionizing radiation curable compound in the present invention is a polyhydric alcohol having two or more alcoholic hydroxyl groups in one molecule.
  • a compound in which the hydroxyl group is an esterified product of two (meth) acrylic acids can be used.
  • the trifunctional or higher functional acrylate ionizing radiation curable compound in the present invention includes (a) specifically pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meta) )
  • a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound with two or more alcoholic hydroxyl group-containing compounds in advance, and further containing an alcoholic hydroxyl group.
  • examples thereof include epoxy (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule obtained by reacting acid or methacrylic acid.
  • the ionizing radiation curable compound contained in the coating solution contains one or more ionizing radiation curable compounds having three or more functional groups in addition to the one or bifunctional ionizing radiation curable compound. is important.
  • a tri- or higher functional ionizing radiation curable compound component having a high crosslinking density is used as a hard segment, and the mono- and / or bi-functional ionizing radiation curable compound reacts to form a hard segment, and 1 and A bifunctional ionizing radiation curable compound component is present as a soft segment.
  • the content of the bifunctional ionizing radiation curable compound is 5% by mass or more and 95% by mass or less.
  • the lower limit of the content is more preferably 10% by mass or more, and further preferably 20% by mass or more.
  • the content of the monofunctional and / or bifunctional ionizing radiation curable compound in the ionizing radiation curable compound is 20% by mass or more and 80% by mass or less, both the surface height and the moldability are more highly balanced. Specifically, pencil hardness of 2H or more and elongation of 20% or more can be achieved at the same time, and high hardness and high workability are required at the same time, for example, for nameplates such as automobiles and casings for portable devices. It is suitable for a molding film.
  • the present inventor has found that the use of an ionizing radiation curable compound having an amino group as the ionizing radiation curable compound can achieve both higher surface hardness and moldability. That is, it is preferable that at least one ionizing radiation curable compound contained in the coating solution has an amino group.
  • action by using the compound which has an amino group as an ionizing radiation hardening compound it thinks as follows. When the hard coat layer has a partial hardness distribution difference, local cracking is likely to occur when the hard coat layer is stretched. As a factor of such a difference in the partial hardness distribution, there is polymerization inhibition (oxygen inhibition) of the ionizing radiation curable resin by oxygen.
  • the amino group traps radical oxygen, and the influence of oxygen inhibition on the curing reaction of the surface layer portion of the hard coat layer is reduced. A uniform curing reaction proceeds. As a result, the stress applied to the hard coat layer during molding is dispersed throughout the layer, and the occurrence of cracks during molding is suppressed. Therefore, it is considered that the surface height and moldability can be achieved at a higher level.
  • the surface of the hard coat layer is hardened more than when no amino group is contained due to the effect of fast curing of the coating film due to the inclusion of amino groups as the ionizing radiation curable resin. Hardness can be improved.
  • the content of the ionizing radiation curable compound containing an amino group in the ionizing radiation curable compound contained in the coating solution is preferably 2.5% by mass or more and 95% by mass or less.
  • the lower limit of the content of the ionizing radiation curable compound containing an amino group in the ionizing radiation curable compound contained in the coating solution is more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the upper limit of the content is more preferably 92.5% by mass or less, further preferably 90% by mass or less, and further preferably 50% by mass or less.
  • the content of the ionizing radiation curable compound containing an amino group in the ionizing radiation curable compound contained in the coating solution is less than 2.5% by mass, it is difficult to uniformly cure the entire hard coat layer. It becomes difficult to obtain resistance to cracks. Further, when the ionizing radiation curable compound containing an amino group becomes high in concentration, yellowing of the hard coat layer becomes strong due to the amino group. Therefore, when the content exceeds 95% by mass, high transparency is impaired. May be.
  • the color b value of the film is preferably 2 or less. In this case, the ionizing radiation curable compound containing the amino group is 92.5% by mass or less. It is preferable that
  • the coating solution contains a monofunctional and / or bifunctional ionizing radiation curable compound and an ionizing radiation curable compound having three or more functional groups.
  • the ionizing radiation curable compound of the part may be any one containing an amino group.
  • any one of a monofunctional ionizing radiation curable compound, a bifunctional ionizing radiation curable compound, or an ionizing radiation curable compound having three or more functional groups is an ionizing radiation curable compound containing an amino group. Is also a preferred embodiment.
  • examples of the acrylate ionizing radiation curable compound having an amino group include acrylamide, 7-amino-3,7-dimethyloctyl ( (Meth) acrylate, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide
  • examples include tetrachlorophenyl (meth) acrylate and N-vinylformamide.
  • the present inventor has also found that by including particles in the hard coat layer, the moldability can be further improved and the surface hardness and the moldability can be both enhanced.
  • grains in a hard-coat layer it thinks as follows.
  • the hardness of the hard coat layer is increased, a strong stress is temporarily generated in the hard coat layer having high hardness at the time of molding, so that the hard coat layer is cracked at once.
  • the presence of particles in the hard coat layer relieves internal stress applied to the hard coat layer at the time of molding at the interface between the ionizing radiation curable compound and the particles and suppresses the generation of cracks.
  • Examples of the particles included in the hard coat layer include amorphous silica, crystalline silica, silica-alumina composite oxide, kaolinite, talc, calcium carbonate (calcite type, vaterite type), zeolite, alumina, hydroxyapatite, and the like.
  • Heat-resistant polymer particles such as inorganic particles, crosslinked acrylic particles, crosslinked PMMA particles, crosslinked polystyrene particles, nylon particles, polyester particles, benzoguanamine / formalin condensate particles, benzoguanamine / melamine / formaldehyde condensate particles, melamine / formaldehyde condensate particles, Organic / inorganic hybrid fine particles such as silica / acrylic composite compounds may be mentioned, but in the present invention, the type of particles is not particularly limited.
  • the shape of the particles examples include a spherical shape, a block shape, a plate shape, a fiber shape, and a flake shape.
  • the shape of the particles is not particularly limited. In view of the above, spherical particles are preferable.
  • the average particle diameter of the particles is preferably 10 nm or more and 300 nm or less, the lower limit is preferably 40 nm or more, and the upper limit is preferably 200 nm or less, particularly the lower limit is 50 nm or more and the upper limit is 100 nm or less. preferable.
  • the average particle diameter of the particles is smaller than 10 nm, the average particle diameter is too small, and therefore, any or all of the effects of improving the surface hardness, scratch resistance, and moldability described above may be small.
  • a hard-coat layer becomes weak and a moldability may fall.
  • the average particle diameter is an average particle diameter measured by dispersing the particles in a solvent that does not swell using a Coulter counter (manufactured by Beckman Coulter, Multisizer II type).
  • the content of the particles to be contained in the hard coat layer is preferably 5% by mass or more and 70% by mass or less as a solid component in the hard coat layer, and particularly preferably, the lower limit of the content is 15% by mass.
  • the upper limit is 50% by mass or less.
  • the content of the particles is less than 5% by mass, any of the above-described effects of improving the surface hardness, scratch resistance, and moldability due to the addition of the particles may be reduced.
  • the content of the particles exceeds 70% by mass, a large amount of the fine cracks described above are generated at the time of molding, and haze increases (whitens), thereby impairing the transparency of the molded body.
  • the inventor of the present application contains an ionizing radiation curable silicone resin in the hard coat layer, thereby imparting slipperiness, improving the scratch resistance of the surface, and further increasing the surface hardness and moldability. I found that they can be compatible. Further, according to such an embodiment, the ionizing radiation curable silicone resin itself is cross-linked by the curing reaction, and in some cases, the ionizing radiation curable resin constituting the hard coat layer is also cross-linked. When using a molded body formed by molding the hard coat film for molding of the present invention for a long period of time, it is possible to obtain a new effect that the function of the surface scratch resistance over time is not impaired. it can.
  • the ionizing radiation curable silicone resin is, for example, a radical addition type having an alkenyl group and a mercapto group, a hydrosilylation reaction type having an alkenyl group and a hydrogen atom, a cationic polymerization type having an epoxy group, and a (meth) acryl group.
  • silicone resins having an epoxy group or (meth) acryl group in the molecule include epoxypropoxypropyl-terminated polydimethylsiloxane, (epoxycyclohexylethyl) methylsiloxane-dimethylsiloxane copolymer, methacryloxypropyl-terminated polydimethylsiloxane, and acryloxy. And propyl-terminated polydimethylsiloxane.
  • silicone resin having a vinyl group in the molecule include terminal vinyl polydimethylsiloxane and vinylmethylsiloxane homopolymer.
  • the addition amount of the ionizing radiation curable silicone resin to be contained in the hard coat layer is preferably 0.15 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable compound for constituting the hard coat layer. More preferably, it is desirable to blend 0.3 to 13 parts by mass, and still more preferably 0.5 to 5 parts by mass.
  • the blending amount of the ionizing radiation curable silicone resin is less than the lower limit, the effect of improving the scratch resistance when formed into a molded product is poor, and when it exceeds the upper limit, the hard coat layer is sufficiently cured when formed. It may not be possible.
  • the ionizing radiation curable silicone resin contained in the hard coat layer may be used alone or in combination of two or more.
  • the surface hardness and moldability of the hard coat layer can be made extremely highly compatible. Specifically, the surface hardness is 2H or higher and the elongation is 20% or higher, more preferably the surface hardness is 2H or higher.
  • a molding hard coat film having an elongation of 30% or more can be obtained, and for example, it can be suitably used for applications such as a cover member for automobiles, a deep housing or container.
  • a method of polymerizing and / or reacting the coating solution a method of irradiating with an electron beam, radiation, or ultraviolet rays may be mentioned.
  • ultraviolet rays When ultraviolet rays are irradiated, a photopolymerization initiator is added to the coating solution. Is desirable.
  • the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoyl formate, p-isopropyl- ⁇ -hydroxyisobutylphenone, ⁇ -hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiura Disulfide, thioxanthone
  • photopolymerization initiated peroxide compounds such as t-butyl peroxide.
  • photopolymerization initiators may be used alone or in combination of two or more.
  • the addition amount of the photopolymerization initiator is suitably 0.01 parts by weight or more and 15 parts by weight or less per 100 parts by weight of the ionizing radiation curable compound contained in the coating solution, and the reaction is slow when the amount used is small. In addition to the poor quality, the remaining unreacted material does not provide sufficient surface hardness and scratch resistance. On the other hand, when the addition amount is large, there is a problem that the hard coat layer is yellowed by the photopolymerization initiator.
  • the coating solution contains a known thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,5-t-butyl hydroquinone in order to prevent thermal polymerization during production and dark reaction during storage. It is preferable to add.
  • the addition amount of the thermal polymerization inhibitor is preferably 0.005 parts by mass or more and 0.05 parts by mass or less per 100 parts by mass of the ionizing radiation curable compound contained in the coating solution.
  • an organic solvent can be blended in the coating solution for the purpose of improving the workability during coating and controlling the coating film thickness within a range that does not impair the purpose of the present invention.
  • the organic solvent when a base film having a low melting point is used, it may be necessary to adjust the drying temperature after coating to 150 ° C. or lower, so the boiling point of the organic solvent is 50 ° C. or higher and 150 ° C. or lower. Is preferred. Specific examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol, acetate solvents such as methyl acetate, ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene. And cyclic ether solvents such as dioxane. These solvents can be used alone or in admixture of two or more.
  • the coating liquid should have a surface tension lowered to improve the coating appearance of the hard coat layer, in particular, dents due to fine bubbles, dents due to adhesion of foreign matters, and repellency in the drying process.
  • a surfactant can be contained.
  • surfactant known cationic, anionic, and nonionic surfactants can be suitably used, but they have polar groups due to problems such as alteration of the coating solution and poor adhesion of the hard coat layer to the base film.
  • group which is not carried out is preferable, and also the silicone type surfactant or fluorine-type surfactant which is excellent in surface active ability is preferable.
  • Silicone surfactants include dimethyl silicon, amino silane, acrylic silane, vinyl benzyl silane, vinyl benzyl silyl amino silane, glycid silane, mercapto silane, dimethyl silane, polydimethyl siloxane, polyalkoxy siloxane, hydrodiene modified siloxane, vinyl modified siloxane, Vitroxy modified siloxane, amino modified siloxane, carboxyl modified siloxane, halogenated modified siloxane, epoxy modified siloxane, methacryloxy modified siloxane, mercapto modified siloxane, fluorine modified siloxane, alkyl group modified siloxane, phenyl modified siloxane, alkylene oxide modified siloxane, etc. .
  • Fluorosurfactants include ethylene tetrafluoride, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonic acid amide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfone.
  • Acid salts perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethyl ammonium salts, perfluoroalkyl amino sulfonates, perfluoroalkyl phosphate esters, perfluoroalkyl alkyl compounds, perfluoroalkyl alkyl betaines, perfluoroalkyl halides, etc. Is mentioned.
  • the content of the surfactant is preferably 0.01% by mass or more with respect to the coating solution constituting the hard coat layer.
  • the surfactant content is preferably 2.00% by mass or less.
  • the surfactant used preferably has an HLB of 2 or more and 12 or less.
  • the HLB of the surfactant is more preferably 3 or more, and particularly preferably 4 or more.
  • a surfactant having an HLB of 12 or less deterioration of slipperiness can be suppressed.
  • HLB means W. of Atlas Powder Co. in the United States.
  • C. Griffin is named Hydrophil Lyophile Balance and is a value obtained by indexing the balance between the hydrophilic group and the lipophilic group contained in the surfactant molecule as a characteristic value. It means that the lower the HLB value, the more lipophilic, while the higher the HLB value, the higher the hydrophilicity.
  • various additives can be blended as necessary.
  • examples thereof include fluorine and silicon compounds for imparting water repellency, antifoaming agents for improving coatability and appearance, and antistatic agents and coloring dyes and pigments.
  • the hard coat layer is formed by applying a coating liquid containing an ionizing radiation curable compound, particles, a photopolymerization initiator, and a surfactant in an organic solvent, followed by curing on a base film. It is preferable.
  • a method for laminating the hard coat layer a known method may be mentioned, but a method in which the coating solution is applied and dried on a substrate film and then cured is preferable.
  • a coating method there are known coating methods such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, a bar coating method, and a lip coating method.
  • a gravure coating method particularly a reverse gravure method, which can be applied by a roll-to-roll method and can be applied uniformly, is preferable.
  • a method for dissolving or dispersing the ionizing radiation curable compound, particles, photopolymerization initiator and the like contained in the coating solution in an organic solvent a method of stirring and dispersing them under heating is preferable.
  • a method of stirring and dispersing them under heating is preferable.
  • the solubility of the ionizing radiation curable compound, particles and photopolymerization initiator can be improved. Therefore, the deterioration of the coating appearance due to undissolved materials can be suppressed.
  • a known dispersing machine can be used. Specific examples include a ball mill, a sand mill, an attritor, a roll mill, an agitator, a colloid mill, an ultrasonic homogenizer, a homomixer, a pearl mill, a wet jet mill, a paint shaker, a butterfly mixer, a planetary mixer, and a Henschel mixer.
  • the solid content concentration of the ionizing radiation curable compound, particles, photopolymerization initiator, etc. contained in the coating solution is preferably 5% by mass or more and 70% by mass.
  • concentration of the solid content of the coating liquid By adjusting the concentration of the solid content of the coating liquid to 5% by mass or more, it is possible to suppress a decrease in productivity due to a long drying time after coating.
  • concentration of the solid content of the coating solution to 70% by mass or less, it is possible to prevent deterioration in leveling properties due to an increase in the viscosity of the coating solution and accompanying deterioration in coating appearance.
  • the solid content concentration of the coating liquid, the type of organic solvent, and the type of surfactant are adjusted so that the viscosity of the coating liquid is in the range of 0.5 cps to 300 cps. It is preferable.
  • the thickness of the hard coat layer after coating and curing depends on the degree of elongation during molding, but it is preferable that the thickness of the hard coat layer after molding be 0.5 ⁇ m or more and 50 ⁇ m or less.
  • the lower limit of the thickness of the hard coat layer before molding is preferably 0.6 ⁇ m or more, and more preferably 1.0 ⁇ m or more.
  • the upper limit of the thickness of the hard coat layer before molding is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, further preferably 60 ⁇ m or less, and further preferably 20 ⁇ m or less.
  • the thickness of the hard coat layer is less than 0.6 ⁇ m, it is difficult to obtain hard coat properties. Conversely, when the thickness exceeds 100 ⁇ m, the hard coat layer tends to be poorly cured or curled due to cure shrinkage.
  • pre-drying such as when an organic solvent is blended in the coating solution, known hot air drying, infrared heaters and the like can be used as a method of applying on the base film and drying, but hot air with a fast drying speed is used. Drying is preferred.
  • the drying temperature after coating is preferably 40 ° C. or higher and 120 ° C. or lower, and particularly preferably the lower limit is 45 ° C. or higher and the upper limit is 80 ° C. or lower. If it is less than 40 degreeC, the organic solvent contained in a coating liquid cannot fully be removed, and problems, such as brushing, may generate
  • the film tension during drying is preferably 50 N / m or more and 300 N / m or less, particularly preferably the lower limit is 100 N / m or more and the upper limit is 250 N / m or less.
  • the tension of the film is less than 50 N / m, the traveling film meanders and it is impossible to apply the coating solution.
  • it exceeds 300 N / m wrinkles are generated in the film, and the flatness is deteriorated and the appearance of the wound film is deteriorated.
  • the base film is a film having a low temperature and excellent moldability, the film is stretched in the traveling direction during drying and contracts in the width direction, and in the worst case, a problem arises in productivity such as breaking.
  • a hard coat layer an antistatic layer, an easy adhesion layer, an adhesive layer, an easy slip layer, an electromagnetic wave absorption layer, a dye, a pigment, etc., as long as the effect of the present invention is not impaired on the surface not provided with the hard coat layer.
  • Other functions such as a resin layer containing a dye may be added.
  • the hard coat layer is formed by irradiating the coating solution with ultraviolet rays.
  • the integrated quantity of light to be irradiated preferably 50 mJ / cm 2 or more 1000 mJ / cm 2 or less, and more preferably the lower limit is 300 mJ / cm 2 or more, the upper limit is 700 mJ / cm 2 or less. Note that it is desirable to perform irradiation in a nitrogen gas atmosphere because oxygen inhibition is reduced and scratch resistance is improved.
  • the integrated light quantity is less than 50 mJ / cm 2 , the polymerization reaction of the ionizing radiation curable compound is not promoted, and the surface hardness of the hard coat layer is significantly reduced.
  • the integrated light quantity exceeds 1000 mJ / cm 2 , the base film may be deformed due to the influence of heat.
  • the integrated light quantity can be measured by “UVR-T35” manufactured by Topcon.
  • the irradiation dose is preferably 5 kGy or more and 100 kGy or less, and more preferably the upper limit is 30 kGy or more and the lower limit is 70 kGy or less.
  • the polymerization reaction of the ionizing radiation curable compound is not promoted, and the surface hardness of the hard coat layer is significantly reduced.
  • it exceeds 100 kGy the lifetime of the electron beam irradiation tube is remarkably reduced, which is not preferable in terms of production cost.
  • the molding hard coat film of the present invention is a film having excellent surface hardness. Specifically, although it varies depending on the base film, in the case of a molding hard coat film using a biaxially oriented polyester film containing a copolymerized polyester as a base film, the measured value of pencil hardness is preferably H or more, Further, it is particularly preferably 2H or more. Here, the pencil hardness was evaluated according to JIS-K5600.
  • the content of mono- or bifunctional ionizing radiation-curable compounds in the ionizing radiation-curable compound contained in the coating solution for forming the hard coat layer and the ionizing radiation-curable compound having an amino group The content can be changed depending on the amount of particles, the amount of particles present in the hard coat layer, and the thickness of the hard coat layer.
  • the molding hard coat film of the present invention is a film having excellent scratch resistance. Specifically, in the case of a hard coat film for molding using a biaxially oriented polyester film containing a copolymerized polyester as a base film, although it varies depending on the base film, steel of # 0000 with a load of 500 gf in accordance with JIS-K5600. The surface is reciprocated 20 times with wool, and the presence or absence of scratches and the extent of the scratches are visually observed. The deep scratches are preferably a small amount of 10 or less, and more preferably no deep scratches at all.
  • the content of the monofunctional or bifunctional ionizing radiation curable compound in the ionizing radiation curable compound contained in the coating solution for forming the hard coat layer or the ionizing radiation curable type having an amino group can be changed depending on the content of the compound and the amount of particles present in the hard coat layer.
  • the hard coat film for molding of the present invention is a film having excellent moldability.
  • the elongation is 10 at both room temperature and the actual film temperature of 160 ° C. % Or more, preferably 20% or more, and particularly preferably 30% or more.
  • the elongation means that a hard coat film for molding was cut into a strip shape having a length of 10 mm and a width of 150 mm, and when the actual film temperature was pulled at 160 ° C., cracks or whitening occurred in the hard coat layer.
  • the stretching ratio at the time was defined as the degree of elongation (%).
  • the content of mono- or bifunctional ionizing radiation-curable compound in the ionizing radiation-curable compound contained in the coating solution for forming the hard coat layer or ionization having an amino group It can be changed depending on the content of the radiation curable compound and the amount of particles present in the hard coat layer.
  • the hard coat film for molding of the present invention preferably has transparency when printing is performed on the surface on which the hard coat layer is not laminated. Specifically, although it varies depending on the base film, in the case of a molding hard coat film using a biaxially oriented polyester film containing a copolymerized polyester as the base film, the haze is preferably 5% or less. The method for adjusting the haze can be changed depending on the abundance of particles in the hard coat layer.
  • the hard coat film for molding of the present invention is preferably not colored when printing is performed on the surface on which the hard coat layer is not laminated.
  • the value of the color tone b * may be 2.0 or less. preferable.
  • the color tone b * is changed depending on the content of the ionizing radiation-curable compound having an amino group in the ionizing radiation-curable compound contained in the coating solution for forming the hard coat layer and the amount of the photoinitiating polymer added. be able to.
  • the color tone b * is obtained by measuring the color tone b * value with a C light source and a viewing angle of 2 degrees using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000), and averaging the measured values of 5 times. Value.
  • the molding hard coat film roll of the present invention is obtained through a step of continuously winding a long molding hard coat film in a roll shape around a cylindrical core.
  • productivity at the time of processing can be improved, and further, it can contribute to the stability of the quality of the molded body.
  • the length of the molding hard coat film roll obtained by continuously winding the long molding hard coat film into a roll on a cylindrical core is not particularly limited depending on the application, but is preferably 50 m or more and 5000 m or less, 100 m or more and 3000 m or less is more preferable.
  • the frequency of switching the hard coat film for molding at the time of processing the printed layer in the subsequent process is increased and workability is deteriorated.
  • the molding hard coat film expands and contracts due to the external environmental temperature, and winding tightening occurs, resulting in a poor appearance of the core.
  • the width of the molding hard coat film roll varies depending on the application and is not particularly limited, but is preferably 100 mm or more and 2000 mm or less, more preferably 500 mm or more and 1500 mm or less from the viewpoint of workability.
  • the cylindrical core around which the hard coat film for molding is wound is preferably a plastic core.
  • a plastic core When a commonly used paper core is used, paper dust or the like is generated and tends to adhere to the hard coat layer and become defective.
  • the plastic core known ones can be preferably used, but a polypropylene core and an FRP core are preferable in terms of strength.
  • the size of the cylindrical core is preferably 3 to 6 inches in diameter. When a core having a small diameter is used, the winding core is wrinkled and the handling property in the subsequent process becomes poor. On the other hand, when the diameter is large, the roll diameter becomes large and the handling property becomes poor.
  • the hard coat film for molding In order to wind the hard coat film for molding around the core, it is preferable to start winding after fixing the hard coat film for molding to the core via a double-sided tape.
  • a double-sided tape When a double-sided tape is not used, winding deviation is likely to occur during winding or during transportation.
  • a well-known thing can be used as a double-sided tape, what has an adhesion layer on both surfaces of a plastic film is preferable at the point of generation
  • the thickness of the double-sided tape is preferably 5 ⁇ m or more and 50 ⁇ m or less. When it is thin, the strength is lowered and workability is deteriorated, and the fixing force of the film is lowered. On the other hand, when the thickness is thick, the flatness of the hard coat film for molding the core portion becomes poor due to a step due to the tape.
  • the present invention it is preferable to provide unevenness (embossing) on both ends in the width direction of the molding hard coat film.
  • unevenness embssing
  • the lower limit of the height of the unevenness is preferably 10 ⁇ m, more preferably 15 ⁇ m.
  • the upper limit of the height of the unevenness is preferably 40 ⁇ m, more preferably 35 ⁇ m.
  • a publicly known method can be used as a method of giving unevenness. Specifically, a method of pressing the metal roll having protrusions on the surface to give irregularities can be mentioned. In addition, it is preferable to give uneven
  • the molding hard coat film of the present invention is a molding material that is molded using a molding method such as vacuum molding, pressure molding, mold molding, press molding, laminate molding, in-mold molding, drawing molding, bending molding, and stretch molding. It is suitable as.
  • the hard coat layer follows the deformation during molding and no cracks are generated, and the surface hardness and scratch resistance can be maintained.
  • the thickness of the hard coat layer of the molded body formed by molding the above-described hard coat film for molding is preferably 0.5 ⁇ m or more and 50 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the thickness of the hard coat layer of the molded body is less than 0.5 ⁇ m, hard coat properties cannot be obtained, and when heat is applied to the molded body in terms of heat resistance, the hard film cannot follow the shrinkage of the base film. The surface of the coat layer becomes rough like a wave, and the appearance is impaired.
  • it exceeds 50 ⁇ m there is no difference in the surface hardness at the thickness of the hard coat layer beyond that, and the merit is reduced in terms of quality.
  • the molded body molded in this way has a hard coat layer to compensate for surface hardness, so it is mounted at a position where it touches the outside and is required to have scratch resistance. It can be suitably used as a molding member such as a building material, a decorative board, a decorative steel plate, and a transfer sheet.
  • Pencil Hardness The pencil hardness of the hard coat layer of the obtained molding hard coat film was measured according to JIS-K5600. The indentation (scratch) was judged visually. Here, those having a pencil hardness of H or higher were judged to have excellent surface hardness, and those having a pencil hardness of 2H or higher were judged to have particularly excellent surface hardness.
  • the scratch resistance of the hard coat layer of the obtained molding hard coat film was measured according to JIS-K5600.
  • the hard coat layer surface was reciprocated 20 times with # 0000 steel wool at a load of 500 gf, and the presence or absence of scratches and the extent of the scratches were visually observed.
  • the rank was determined according to the following criteria based on the observation results.
  • the scratch resistance rank was C or higher, and there was scratch resistance, and those of B or higher were judged to have good scratch resistance.
  • B Although a thin wound is observed, a deep wound is not observed.
  • C Narrow scratches are observed, and a small amount of deep scratches are also observed.
  • D A lot of deep scratches are observed.
  • Color tone b * The color tone b * value of the obtained hard coat film for molding was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000), and the color tone b * value was measured at a viewing angle of 2 degrees with a C light source. The measured values were averaged.
  • Pencil hardness after molding thickness of hard coat layer
  • the pencil hardness after molding was evaluated by the evaluation method (2).
  • the spectral reflectance at the center of the film sample piece (molded body) after molding is obtained from a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150 type), and the peak valley method is calculated from the waveform at a wavelength of 400 nm to 600 nm. Using this, the thickness of the hard coat layer was calculated.
  • the refractive index of the hard coat layer required at that time is that a single film of the hard coat layer is prepared from the hard coat coating solution of each example and comparative example, and an Abbe refractometer (NAR-1T SOLID, manufactured by Atago) is used. Asked.
  • Coating appearance In order to determine whether the drying temperature and film tension after application of the coating solution are appropriate, the coating appearance was evaluated. When a hard coat layer is provided by coating and curing on a base film having a width of 1000 mm and a length of 200 m, if the hard coat layer does not show any brushing, missing coating, or repellency, it is good (O), and if a defect is seen. It was determined to be defective (x).
  • Example 1 Hard coat layer after coating and curing the following coating solution A using a wire bar on a biaxially oriented polyester film (Toyobo, Soft Shine: A1532, thickness 125 ⁇ m) containing a copolyester having easy-adhesion layers on both sides
  • the film is applied to a thickness of 2 ⁇ m, dried with hot air at a temperature of 80 ° C. for 60 seconds, and passed through a high-pressure mercury lamp with an output of 120 W / cm at a speed of 8 m / min at a position of 20 cm (integrated light quantity 300 mJ / cm 2 ).
  • a hard coat film for molding was obtained.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 2 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid B.
  • Coating solution B ⁇ Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 17.18% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 2.86% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 2.86% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14%
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 3 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid C.
  • Coating liquid C Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 8.02 mass% (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 7.44% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 7.44% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14%
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 4 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid D.
  • Coating liquid D Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 21.75 mass% (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 0.58% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 0.57% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Co
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 5 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid E.
  • Coating liquid E ⁇ Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 1.15% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 0.58% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 21.17% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.1
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 6 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid F.
  • Coating fluid F Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 21.75 mass% (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 1.15% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals) ⁇ Silicone-based surfactant 0.03% by mass (Toray Dow Corning DC
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 7 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid G.
  • Coating liquid G ⁇ Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 1.15% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 21.75% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals) ⁇ Silicone-based surfactant 0.03% by mass (Toray Dow Corning DC
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 8 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid H.
  • Coating liquid H ⁇ Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 1.15% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Dimethylaminoethyl methacrylate 21.75% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals) ⁇ Silicone-based surfactant 0.03% by mass (
  • the obtained hard coat film for molding had a large amount of amine compound added, so that the coloring was noticeably not preferred, but the moldability, surface hardness, and scratch resistance were all good. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 9 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid I.
  • Coating liquid I ⁇ Methyl ethyl ketone 64.48% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Diethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DE, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 10 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid J.
  • Coating liquid J ⁇ Methyl ethyl ketone 64.48% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ N-vinylformamide 5.72% by mass (Arakawa Chemical, Beam Set 770, 1 functional group) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Irgacure 184 manufactured by Ci
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 11 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid K.
  • Hard coat coating solution K Methyl ethyl ketone 67.93 mass% -Pentaerythritol triacrylate 11.58 mass% (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.79% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.79% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 7.72% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initi
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 12 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid L.
  • Coating liquid L Methyl ethyl ketone 4.24% by mass -Pentaerythritol triacrylate 6.22 mass% (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 3.12% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 3.12% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) Silica fine particles 82.73% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 0.55% by mass (Irga
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 13 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid M.
  • Coating liquid M Methyl ethyl ketone 71.46% by mass -Pentaerythritol triacrylate 11.72% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.86% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.86% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) Silica fine particles 3.90% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.17%
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 14 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid N.
  • Coating liquid N -Pentaerythritol triacrylate 5.28% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 2.64% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 2.64% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 88.88% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 0.55% by mass (Irgacure 184 manufactured by Cib
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 15 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid O.
  • Coating solution O ⁇ Methyl ethyl ketone 58.76% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 17.17% by mass (Manufactured by Fuso Chemical Industries, PL2L-MEK, solid content ratio: 20%, average particle size: 20 nm) -Photo
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 16 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid P.
  • Coating liquid P Methyl ethyl ketone 58.76% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 17.17% by mass (Manufactured by Fuso Chemical Industries, PL30L-MEK, solid content ratio: 20%, average particle size: 297 nm) -
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 17 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid Q.
  • Coating liquid Q Methyl ethyl ketone 58.76% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 17.17% by mass (Nippon Shokubai Co., Ltd., Seahoster KE-E50, solid content ratio: 20%, average particle size: 511 nm)
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 18 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid R.
  • Coating liquid R ⁇ Methyl ethyl ketone 72.50% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Melamine / formaldehyde condensate fine particles 3.43 mass% (Nippon Shokubai, Eposter S, average particle size: 196 nm) -Photopolymerization initi
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 19 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid S.
  • Coating solution S ⁇ Methyl ethyl ketone 75.08 mass% ⁇ Pentaerythritol triacrylate 11.85% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.93 mass% (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.92% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) -Photopolymerization initiator 1.19% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals) ⁇ Silicone-based surfactant 0.03% by mass (Toray Dow Corn
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 20 In Example 1, the molding hardware was changed in the same manner as in Example 1 except that the base film was changed to a biaxially stretched polyester film (Cosmo Shine: A4300, thickness 125 ⁇ m manufactured by Toyobo Co., Ltd.) having easy-adhesion layers on both sides. A coated film was obtained.
  • a biaxially stretched polyester film Cosmo Shine: A4300, thickness 125 ⁇ m manufactured by Toyobo Co., Ltd.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 21 In Example 1, the base film was changed to an unstretched polycarbonate film (made by Teijin Chemicals, PC-2151, thickness 250 ⁇ m), and the coating liquid for forming the hard coat layer was changed to the following coating liquid T Produced a hard coat film for molding in the same manner as in Example 1.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 22 In Example 1, a hard coat film for molding was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer after application and curing was 1.1 ⁇ m.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 23 In Example 1, a hard coat film for molding was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer after coating and curing was 50 ⁇ m.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 24 In Example 1, a hard coat film for molding was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer after coating and curing was 0.5 ⁇ m.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and coloring, and was good as a hard coat film for molding.
  • the surface hardness of the molded body molded from the obtained molding hard coat film was slightly poor. This is due to the fact that the thickness of the hard coat layer is reduced to a value outside the range where the surface hardness can be maintained by molding.
  • Table 1 The obtained results are shown in Table 1.
  • Example 25 In Example 1, a hard coat film for molding was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer after coating and curing was 60 ⁇ m.
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and degree of coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 1 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid U.
  • Coating solution U ⁇ Methyl ethyl ketone 64.48% by mass -Pentaerythritol triacrylate 22.90% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Irgacure 184 made by Ciba Specialty) ⁇ Silicone-based surfactant 0.03% by mass (Toray Dow Corning DC57)
  • the obtained hard coat film for molding had good surface hardness, scratch resistance and coloring, but had poor moldability and was poor as a hard coat film for molding.
  • the obtained results are shown in Table 1.
  • Example 2 a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid V.
  • Coating fluid V ⁇ Methyl ethyl ketone 64.48% by mass ⁇ Tripropylene glycol diacrylate 11.45% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 11.45% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) -Photopolymerization initiator 1.14% by mass (Irgacure 184 made by Ciba Specialty) ⁇ Silicone-based surfactant 0.03% by mass (Toray Dow Corning DC57)
  • the obtained hard coat film for molding was good in both moldability and coloring, but had poor surface hardness and scratch resistance and was poor as a hard coat film for molding.
  • the obtained results are shown in Table 1.
  • Example 26 A film roll having a width of 1000 mm and a length of 200 m of a biaxially oriented polyester film (coating polyester manufactured by Toyobo Co., Ltd., Soft Shine: A1532, 125 ⁇ m in thickness) containing a copolyester having an easy-adhesion layer on both sides is shown below in roll-to-roll.
  • the coating liquid W was applied using a micro gravure method so that the thickness of the hard coat layer after coating and curing was 2 ⁇ m, and dried for 60 seconds with hot air at a temperature of 80 ° C. under the condition of a film tension of 180 N / m.
  • the resulting coated hard coat film had a good coating appearance and a good shrinkage in the width direction. Further, the obtained hard coat film for molding had the same moldability, surface hardness and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The obtained results are shown in Table 2.
  • Example 27 a molding hard coat film roll was prepared in the same manner as in Example 26 except that the drying temperature was changed to 40 ° C.
  • the resulting coated hard coat film had a good coating appearance and a good shrinkage in the width direction. Further, the obtained hard coat film for molding had the same moldability, surface hardness and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The obtained results are shown in Table 2.
  • Example 28 In Example 26, a molding hard coat film roll was prepared in the same manner as in Example 26 except that the drying temperature was changed to 120 ° C.
  • the resulting coated hard coat film had a good coating appearance and a good shrinkage in the width direction. Further, the obtained hard coat film for molding had the same moldability, surface hardness and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The obtained results are shown in Table 2.
  • Example 29 In Example 26, a molding hard coat film roll was prepared in the same manner as in Example 26 except that the film tension was changed to 50 N / m.
  • the resulting coated hard coat film had a good coating appearance and a good shrinkage in the width direction. Further, the obtained hard coat film for molding had the same moldability, surface hardness and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The obtained results are shown in Table 2.
  • Example 30 In Example 26, a molding hard coat film roll was prepared in the same manner as in Example 26 except that the film tension was changed to 300 N / m.
  • the resulting coated hard coat film had a good coating appearance and a good shrinkage in the width direction. Further, the obtained hard coat film for molding had the same moldability, surface hardness and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The obtained results are shown in Table 2.
  • Example 26 (Comparative Example 3) In Example 26, a molding hard coat film roll was prepared in the same manner as in Example 26 except that the drying temperature was changed to 30 ° C.
  • Example 26 (Comparative Example 4)
  • a molding hard coat film roll was prepared in the same manner as in Example 26 except that the drying temperature was changed to 140 ° C.
  • Example 26 (Comparative Example 5) In Example 26, a molding hard coat film roll was prepared in the same manner as in Example 26 except that the film tension was changed to 40 N / m.
  • Example 26 (Comparative Example 6) In Example 26, a molding hard coat film roll was prepared in the same manner as in Example 26 except that the film tension was changed to 320 N / m.
  • Example 31 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid R.
  • Coating liquid X Methyl ethyl ketone 63.62% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) ⁇ Ionizing radiation curable silicone compound poly
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 31 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid R.
  • Coating liquid Y Methyl ethyl ketone 64.42% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) ⁇ Ionizing radiation curable silicone compound poly
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • Example 32 In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following coating liquid R.
  • (Coating solution Z) ⁇ Methyl ethyl ketone 61.62% by mass ⁇ Pentaerythritol triacrylate 11.45% by mass (Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, 3 functional groups) ⁇ Tripropylene glycol diacrylate 5.73% by mass (Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups) ⁇ Dimethylaminoethyl methacrylate 5.72% by mass (Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1) ⁇ Silica fine particles 11.45% by mass (Nissan Chemical Industries, MEK-ST-L, solid content ratio: 30%, average particle size: 50 nm) ⁇ Ionizing radiation curable silicone compound polyether
  • the obtained hard coat film for molding had good moldability, surface hardness, scratch resistance, and coloring, and was good as a hard coat film for molding. Moreover, the surface hardness of the molded object molded from the obtained molding hard coat film was also good. The obtained results are shown in Table 1.
  • the molded body formed by molding the hard coat film for molding of the present invention requires scratch resistance. It is suitable as a housing for portable appliances such as home appliances, automobile nameplates or building materials, mobile phones, audio, portable players / recorders, IC recorders, car navigation systems, PDAs, and notebook PCs. Also, on the manufacturing side of the molding process, processing and laminating the hard coat layer on the base film before molding can contribute to the improvement of productivity and quality stability, and the contribution to the industry is great. .

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Abstract

L'invention porte sur un film de revêtement dur pour le moulage, qui a à la fois une dureté de surface élevée et une aptitude au moulage élevée. De façon spécifique, l'invention porte sur un film de revêtement dur pour le moulage, qui a une couche de revêtement dur sur au moins un côté d'un film de base. La couche de revêtement dur est obtenue par revêtement et durcissement d'un liquide de revêtement. Le liquide de revêtement contient au moins un composé durcissable sous l'action d'un rayonnement ionisant, ayant au moins trois groupes fonctionnels et un composé monofonctionnel et/ou bifonctionnel, durcissable sous l'action d'un rayonnement ionisant. La teneur du composé monofonctionnel et/ou bifonctionnel, durcissable sous l'action d'un rayonnement ionisant dans les composés durcissables sous l'action d'un rayonnement ionisant contenu dans le liquide de revêtement n'est pas inférieure à 5% en masse mais non supérieure à 95 % en masse.
PCT/JP2009/058041 2008-06-18 2009-04-23 Film de revêtement dur pour le moulage WO2009154042A1 (fr)

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JP2011126158A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2017226161A (ja) * 2016-06-23 2017-12-28 東洋紡株式会社 積層フィルム
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