WO2016199847A1 - Film à couches - Google Patents

Film à couches Download PDF

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Publication number
WO2016199847A1
WO2016199847A1 PCT/JP2016/067204 JP2016067204W WO2016199847A1 WO 2016199847 A1 WO2016199847 A1 WO 2016199847A1 JP 2016067204 W JP2016067204 W JP 2016067204W WO 2016199847 A1 WO2016199847 A1 WO 2016199847A1
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WO
WIPO (PCT)
Prior art keywords
laminated film
resin
film
urethane acrylate
acrylic
Prior art date
Application number
PCT/JP2016/067204
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English (en)
Japanese (ja)
Inventor
博志 神山
Original Assignee
株式会社カネカ
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 株式会社カネカ filed Critical 株式会社カネカ
Priority to JP2017523692A priority Critical patent/JPWO2016199847A1/ja
Publication of WO2016199847A1 publication Critical patent/WO2016199847A1/fr

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Classifications

    • 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
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a laminated film.
  • these films include ⁇ Transparency that prints and patterns on the surface of the substrate are clearly visible, ⁇ Thermoformability that can be applied to various molding methods such as thermal lamination, compressed air molding that shapes the film according to the surface shape of the substrate, vacuum molding, hot press molding, insert / in-mold molding, and three-dimensional laminate molding , ⁇ Folding crack resistance, Various characteristics such as are required.
  • N, N-diethyl-3-methylbenzamide (abbreviated as DEET, Diet, etc.), which is widely used as an active ingredient of so-called insect repellents, has a solubility in materials such as plastics and leather. It is very strong and is known as a drug that can easily damage automobile interiors.
  • a method of forming a hard coat layer such as a crosslinked layer or a cured layer on the surface of the film is known.
  • the hard coat layer provided on the surface of the acrylic resin film is generally insufficient in heat deformability.
  • the method of providing a hard coat layer is characterized by thermoformability (for example, 150% to 200% or more during shape forming such as pressure forming or vacuum forming), which is a feature of acrylic resin films. Resulting in cracking of the film or hard coat layer during lamination on the surface of the molded body, peeling from the edge of the laminated body, etc. There is a problem of ease.
  • the present invention is excellent in transparency, surface hardness, bending crack resistance, folding whitening resistance, and thermoformability, and is not significantly inferior in chemical resistance and stain resistance to various chemicals, It aims at providing the laminated film which can be used for decoration and surface protection, such as a member for vehicles, furniture, and an electronic / electric equipment housing
  • the present inventors have included a unit having a specific glass transition temperature and derived from a specific urethane acrylate resin in the acrylic resin film, and further, in the urethane acrylate resin.
  • a cured resin layer in which the average number of urethane bonds contained in the derived unit is 40/1 unit the present inventors have found that the above-mentioned problems can be solved and have completed the present invention.
  • the urethane acrylate resin has a structure containing a functional group selected from an acryloyl group or a (meth) acryloyl group at the end of the polyurethane resin, and these are collectively referred to as “urethane acrylate resin” in the present text.
  • urethane acrylate resin a structure containing a functional group selected from an acryloyl group or a (meth) acryloyl group at the end of the polyurethane resin, and these are collectively referred to as “urethane acrylate resin” in the present text.
  • a laminated film comprising a cured resin layer on an acrylic resin film,
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher
  • the cured resin layer is made of a resin containing a unit derived from a urethane acrylate resin,
  • the laminated film whose average of the content number of the urethane bond in the unit derived from a urethane acrylate resin is 40/1 unit or more.
  • a laminated film comprising a cured resin layer on an acrylic resin film,
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher
  • the urethane acrylate resin is an addition reaction product of a polyvalent isocyanate containing a bifunctional isocyanate compound having a cyclic structure, a diol compound, and a hydroxyl group-containing compound containing an acryloyl group and / or a methacryloyl group.
  • the hydroxyl group-containing compound contains a compound containing two or more acryloyl groups and / or methacryloyl groups in the molecule and one hydroxyl group, (4) or (5) Such a laminated film.
  • the value obtained by dividing the average number of urethane bonds per molecule of the urethane acrylate resin by the total number of acryloyl groups and / or methacryloyl groups per molecule is in the range of 7 to 21, (4) to ( A laminated film according to any one of 7).
  • a laminated film comprising a cured resin layer on an acrylic resin film,
  • the amount of change in the haze value of the laminated film after dropping a mixed organic solvent containing 25% N, N-diethyl-3-methylbenzamide onto the cured resin layer in the laminated film and heat-treating at 80 ° C. for 24 hours is 0. .2% or less
  • a laminate comprising the laminated film according to any one of (1) to (13) on the surface of a molded product made of a thermoplastic resin or a thermosetting resin.
  • a method for producing a laminated film comprising forming a cured resin layer comprising a resin containing a unit derived from a urethane acrylate resin on an acrylic resin film,
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher
  • the manufacturing method of a laminated film whose average number of urethane bonds per molecule of urethane acrylate resin is 40 or more.
  • (16) including forming a resin layer containing a urethane acrylate resin on an acrylic resin film by a wet coating method; The method for producing a laminated film according to (15), wherein the cured resin layer is formed by curing the resin layer with active energy rays.
  • the average number of urethane bonds per molecule of the urethane acrylate resin divided by the total number of acryloyl groups and methacryloyl groups per molecule is in the range of 7 to 21 (15) or (16 The manufacturing method of the laminated
  • the laminated film of the present invention is excellent in transparency, surface hardness, folding crack resistance, folding whitening resistance, and thermoformability, and is resistant to chemicals such as printing ink, DOP, sebum, sunscreen and insect repellent. Chemical properties and stain resistance are not significantly inferior.
  • the laminated film according to the above (1) is referred to as a first laminated film.
  • the first laminated film includes a cured resin layer on the acrylic resin film.
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher.
  • a cured resin layer consists of resin containing the unit derived from urethane acrylate resin.
  • the average number of urethane bonds in the unit derived from the urethane acrylate resin is 40/1 unit or more.
  • the thickness of the laminated film is preferably 20 to 300 ⁇ m, more preferably 40 to 200 ⁇ m.
  • the thickness of the laminated film is 20 ⁇ m or more, the film has good moldability and is not easily wrinkled during film winding.
  • the thickness of the laminated film is 300 ⁇ m or less, the production cost can be easily suppressed and the film can be easily wound into a roll.
  • an arbitrary surface shape such as a hairline, a prism, a concavo-convex shape, or a matte surface may be imparted to one side or both sides according to applications.
  • Such surface shape can be imparted by a known method. For example, there is a method of transferring the surface shape of the roll by sandwiching both surfaces of the laminated film fed from the feeding device between two rolls or belts having a surface shape on at least one surface. Examples of a method for imparting such a surface shape include a method described in JP 2010-82872 A. At this time, the application of the surface irregularity shape may be performed on the acrylic resin film side or may be performed on the cured resin layer side.
  • the haze of the laminated film is preferably 2.0 or less, more preferably 1.5 or less, particularly preferably 1.0 or less, and 0.8 or less. Is more preferable.
  • the haze here is a measured value at a thickness of 75 ⁇ m under the conditions of a temperature of 23 ° C. ⁇ 2 ° C. and a humidity of 50% ⁇ 5% in accordance with JIS K6714.
  • the pencil hardness of the laminated film is preferably in the range of 2B to H. More preferably, the pencil hardness is HB to H. When the pencil hardness of the laminated film is within the above range, the laminated film is less likely to be scratched or cracked during bending, and the handleability of the laminated film is good.
  • the pencil hardness is preferably the hardness on the cured resin layer side.
  • a cured resin layer consists of resin containing the unit derived from urethane acrylate resin. Such a cured resin layer can be formed by curing a mixture of monomers including a urethane acrylate resin.
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher, preferably 108 ° C. or higher, and more preferably 112 ° C. or higher.
  • a cured resin layer exhibiting such a glass transition temperature on an acrylic resin film a laminated film excellent in surface hardness, bending crack resistance, folding whitening resistance, chemical resistance, and stain resistance is obtained.
  • Cheap From the viewpoint of thermoformability, the glass transition temperature of the cured resin layer is equal to or lower than the thermoforming temperature such as pressure forming, vacuum forming, hot press forming, insert forming, in-mold forming, and three-dimensional laminate forming.
  • the upper limit of the glass transition temperature of the cured resin layer is preferably 220 ° C. or less, more preferably 200 ° C. or less, from the viewpoint of inhibiting thermal decomposition of the acrylic resin.
  • the material of the cured resin layer such as urethane acrylate resin and the method of forming the cured resin layer will be described.
  • the urethane acrylate resin can form a cured resin layer exhibiting a desired glass transition temperature, and is not particularly limited as long as the average content of urethane bonds in units derived from the urethane acrylate resin is 40/1 units or more.
  • the urethane acrylate resin is produced by reacting a polyhydric alcohol, a polyvalent isocyanate, a hydroxyl group-containing acrylate and / or a hydroxyl group-containing (meth) acrylate, and generating a urethane bond by a reaction between the isocyanate group and the hydroxyl group.
  • (meth) acrylate refers to both acrylate and methacrylate.
  • the various properties of the urethane acrylate resin include the structure of the polyhydric alcohol, the type of polyisocyanate, and the acryloyl group and methacryloyl group (CH 2 ⁇ CH—CO—, CH 2 ⁇ of the hydroxyl group-containing acrylate or hydroxyl group-containing methacrylate). It can be adjusted by the number of C (CH 3 ) —CO—).
  • CH 2 ⁇ CH—CO— CH 2 ⁇ of the hydroxyl group-containing acrylate or hydroxyl group-containing methacrylate. It can be adjusted by the number of C (CH 3 ) —CO—).
  • Polyhydric alcohol The number of hydroxyl groups that the polyhydric alcohol used as a raw material has is not particularly limited. Preferred polyhydric alcohols include linear or branched diol compounds having 2 to 10 carbon atoms.
  • diol compound examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexane Examples include dimethanol, polytetramethylene glycol, and hydroquinone. Two or more of these may be used in combination.
  • the molecular weight of the diol compound is preferably 100 or less, more preferably 80 or less.
  • the polyhydric alcohol demonstrated above may use one type of compound independently, and may use 2 or more types together.
  • polyvalent isocyanate Although there is no restriction
  • diisocyanate compound examples include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), methylcyclohexane-2, 4 (or 2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, Butylene diisocyanate, propylene Diisocyanate, octadecylene diisocyanate,
  • polyvalent isocyanate examples include triphenylmethane-4,4 ′, 4 ′′ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene.
  • diisocyanate compounds are preferred from the viewpoint of controlling the weight average molecular weight of the urethane acrylate resin.
  • numerator is preferable from a viewpoint of control of a glass transition temperature. From these two viewpoints, it is more preferable that the polyvalent isocyanate contains a bifunctional isocyanate compound having a cyclic structure.
  • the content of the polyvalent isocyanate having a cyclic structure in the polyvalent isocyanate is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.
  • the polyvalent isocyanate has a alicyclic structure in the molecule, particularly It is more preferable to include a dicyanate compound having an alicyclic structure.
  • diisocyanate compound having such an alicyclic structure examples include isophorone diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), cyclohexylene diisocyanate, cyclohexane dimethylene diisocyanate, bis (isocyanate methyl) benzene, and bis (isocyanate methyl). And cyclohexane.
  • isophorone diisocyanate is particularly preferable.
  • polyvalent isocyanate As the polyvalent isocyanate described above, one kind of compound may be used alone, or two or more kinds may be used in combination.
  • hydroxyl group-containing (meth) acrylate examples include those having one or more hydroxyl groups in one molecule. Specifically, hydroxyethyl acrylate, trimethylolpropane diacrylate, trimethylolpropane monoacrylate, tetramethylolmethane triacrylate, tetramethylolmethane diacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, glycerin diacrylate, glycerin monoacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, hydroxyethyl methacrylate, trimethylolpropane dimethacrylate, tetramethylol methane trimethacrylate, pentaerythr
  • (meth) acrylates having a small number of hydroxyl groups are preferred, and (meth) acrylates having one hydroxyl group are more preferred.
  • the number of hydroxyl groups is one in the molecule, an undesired molecular weight extension reaction is prevented, and the relationship between the number of acryloyl groups and the total number of methacryloyl groups in the urethane acrylate resin and the weight average molecular weight can be easily controlled.
  • acrylate is more reactive than methacrylate.
  • preferable hydroxyl group-containing (meth) acrylate compounds in terms of reactivity include divalent to pentavalent hydroxyl group-containing acrylates such as pentaerythritol triacrylate, glycerol diacrylate, and dipentaerythritol pentaacrylate.
  • the average number of urethane bonds in units derived from the urethane acrylate resin is 40/1 units or more.
  • a urethane acrylate resin having an average number of urethane bonds per molecule of 40 or more is used as the urethane acrylate resin.
  • the average content of urethane bonds per molecule of the urethane acrylate resin is preferably 42 or more.
  • the upper limit of the average number of urethane bonds per molecule of the urethane acrylate resin is preferably 70 or less, more preferably 60 or less, particularly preferably 55 or less, from the viewpoint of easily forming a cured resin layer having a preferable degree of crosslinking. The following is more preferable.
  • the value obtained by dividing the weight average molecular weight by the number of acryloyl groups and the total number of methacryloyl groups per molecule is preferably in the range of 1000 or more and 3000 or less.
  • the lower limit of such a value is preferably 1000 or more, more preferably 1200 or more, and even more preferably 1300 or more.
  • 3000 or less are preferable and 2000 or less are more preferable.
  • the crosslinking density of the cured resin layer is within an appropriate range. It is easy to obtain a laminate having both chemical properties and stain resistance and excellent elongation at the time of hot stretching. Specifically, the stretching at 120 ° C. can be stretched to 150% or more, and can be stretched 2.5 times or more. From the viewpoint of easily forming a cured resin layer having a preferred degree of crosslinking, the total number of acryloyl groups and methacryloyl groups per molecule of urethane acrylate resin is preferably 6 or more.
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher.
  • the glass transition temperature of the urethane acrylate resin is preferably 60 ° C. or more, more preferably 70 ° C. or more, and particularly preferably 80 ° C. or more from the viewpoint of easily forming a cured resin layer exhibiting a glass transition temperature within a desired range. preferable.
  • the glass transition temperature of the urethane acrylate resin is less than 60 ° C., it is difficult to form a cured resin layer exhibiting a sufficiently high glass transition temperature, and as a result, chemical resistance and stain resistance may be insufficient. .
  • the value obtained by dividing the average number of urethane bonds per molecule by the total number of acryloyl groups and methacryloyl groups per molecule is preferably within the range of 7 to 21 and within the range of 7 to 15 A range of 7 or more and 10 or less is more preferable.
  • the stretch at 120 ° C. molding is 150% or more. However, it is easy to obtain a laminated film having excellent chemical resistance and stain resistance.
  • the weight average molecular weight of the urethane acrylate resin indicates a value determined on the basis of standard polystyrene by GPC (gel permeation gas chromatography) method.
  • GPC gel permeation gas chromatography
  • the weight average molecular weight of the urethane acrylate resin is preferably 6200 or more, more preferably 7000 or more, and further preferably 8000 or more.
  • stretching at 120 ° C. can be made 150% or more, and the viscosity of the urethane acrylate resin is within a range that can be handled well.
  • the urethane acrylate resin having an average number of urethane bonds per molecule of 40 or more is a urethane acrylate resin having an average number of urethane bonds per molecule of less than 40 within a range not impairing the effects of the present invention. May be used in combination.
  • a urethane acrylate resin having an average content of urethane bonds per molecule of 40 or more is a main component.
  • the content of urethane acrylate resin having an average number of urethane bonds per molecule of 40 or more in 100% by weight of all urethane acrylate resin components is preferably 70 to 100% by weight, and 80 to 100%. % By weight is more preferable, and 90 to 100% by weight is more preferable.
  • the cured resin layer may be formed by copolymerizing another polymerizable monomer together with the urethane acrylate resin.
  • polymerizable monomers conventionally known monomers having various non-conjugated double bonds can be used as long as the object of the present invention is not impaired.
  • polysynthetic monomers include, for example, monomers that give other structural units other than methyl methacrylate, which are used as raw materials for acrylic resins described later, and manufacture of acrylic ester-based crosslinked elastic bodies described later. The polyfunctional monomer used for is mentioned.
  • the amount of the urethane acrylate resin with respect to the total amount of the urethane acrylate resin and the other polymerizable monomer is preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and 100% by weight. Most preferred.
  • the urethane acrylate resin is applied on the acrylic resin film as a paint containing the urethane acrylate resin. Thereafter, a cured resin layer is formed by reaction-curing acryloyl groups and / or methacryloyl groups in the formed coating film. A laminated film is obtained through such a method.
  • a method for curing a coating film containing a urethane acrylate resin known techniques can be widely used. Among these, it is particularly preferable to use a method of irradiating active energy rays typified by ultraviolet rays.
  • a photopolymerization initiator to a paint containing a urethane acrylate resin.
  • the photopolymerization initiator include acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2- Phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Compound etc. are mentioned. Of these, 1-hydroxy-cyclohexyl-phenyl-ketone, which is excellent
  • the paint containing a urethane acrylate resin used to form the cured resin layer may contain various known leveling agents for the purpose of improving the coating property to the acrylic resin film.
  • the leveling agent for example, a fluorine leveling agent, an acrylic leveling agent, a silicone leveling agent, and an adduct or a mixture thereof can be used.
  • a leveling agent having an acryloyl group and / or a methacryloyl group is preferable in that bleeding out to the surface of the cured resin layer hardly occurs.
  • the addition amount of the leveling agent is preferably in the range of 0 to 6.0 parts by weight with respect to 100 parts by weight of the monomer containing the urethane acrylate resin.
  • the coating material containing a urethane acrylate resin contains an organic solvent.
  • the boiling point of the organic solvent is preferably 50 to 150 ° C. from the viewpoint of workability during coating and drying.
  • the type of the organic solvent is not particularly limited as long as a paint can be prepared and coating and drying operations are possible.
  • organic solvent examples include alcohols such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol; esters such as methyl acetate, ethyl acetate, and butyl acetate; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones; aromatic solvents such as toluene and xylene; monoethers of glycols such as methyl cellosolve and ethyl cellosolve. These organic solvents can be used alone or in combination of several kinds as appropriate. Moreover, you may mix
  • a paint containing a urethane acrylate resin is applied onto the acrylic resin film. That is, a coating film that is a resin layer containing a urethane acrylate resin is formed on the acrylic resin film by a wet coating method. Any known coating method can be used as the coating method. Examples of preferable coating methods include reverse coating, gravure coating, bar coating, die coating, spray coating, kiss coating, wire bar coating, and curtain coating. These methods may be used alone or in combination.
  • the coating film containing the urethane acrylate resin described above is applied onto the acrylic resin film substrate to form a coating film.
  • the coating film is irradiated with active energy rays. By performing, a cured resin layer is formed.
  • the drying temperature is preferably 80 ° C. or higher and 120 ° C. or lower. By drying at a temperature in such a range, the solvent can be sufficiently removed and the acrylic resin film can be easily prevented from being deformed by heat.
  • ultraviolet rays can be used as the active energy rays irradiated after the drying.
  • the wavelength of the ultraviolet light is preferably in the range of 200 to 400 nm.
  • Preferable ultraviolet irradiation conditions are, for example, an illuminance of 80 to 240 mW / cm 2 and an irradiation amount of 70 to 500 mJ / cm 2 .
  • active energy rays ionizing radiation such as electron beams, ⁇ rays, ⁇ rays, and ⁇ rays can be used in addition to ultraviolet rays.
  • Specific energy sources or irradiation devices include, for example, germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, electrodeless lamps, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, excimer lamps, and other lamp light sources, argon It is possible to use an irradiation device equipped with a pulse such as an ion laser or a helium neon laser, a continuous laser light source, or an electron beam using a scanning type or curtain type electron beam accelerator.
  • a pulse such as an ion laser or a helium neon laser, a continuous laser light source, or an electron beam using a scanning type or curtain type electron beam accelerator.
  • ⁇ Acrylic resin film> An acrylic resin film is used as the base film in the laminated film. By using an acrylic resin film for the base film, it is easy to obtain a laminated film having excellent transparency, weather resistance, surface hardness, and adhesion to a decorative substrate.
  • polycarbonate resin acrylic resin, ASA resin, ABS resin, AS resin and other styrene resins, saturated or unsaturated polyester resin, vinyl ester resin, epoxy resin, polyamide resin, polyphenylene sulfide resin, Thermoplastic resins such as polyphenylene oxide resins, polyacetal resins, polylactic acid resins, cellulose acylate resins, olefin- (meth) acrylic acid derivative copolymer resins, and fibers / fillers using these resins Examples include reinforced composite materials.
  • the acrylic resin film the acrylic resin, other thermoplastic resins, rubber components, other components, and a method for producing the acrylic resin film will be described.
  • acrylic resin A conventionally well-known thing can be used as an acrylic resin which is the material of an acrylic resin film.
  • the acrylic resin include 20 to 100 parts by weight of a thermoplastic acrylic polymer composed of 50 to 100% by weight of methyl methacrylate units and 0 to 50% by weight of other structural units from the viewpoint of hardness and moldability.
  • the containing resin is preferred.
  • examples of other monomers that give structural units include methyl acrylate, butyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and ⁇ -hydroxyethyl acrylate.
  • Acrylic acid and its derivatives such as phenoxyethyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylic acid, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid t-butyl, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate Methacrylic acid and its derivatives such as adamantyl methacrylate and methacrylic acid, vinyl cyanide such as acrylonitrile and methacrylonitrile, aromatic vinyl derivatives such as styrene, vinyltoluene and ⁇ -methylstyrene,
  • the method for producing the acrylic resin is not particularly limited, and known polymerization methods such as a known suspension polymerization method, bulk polymerization method, solution polymerization method, emulsion polymerization method, and dispersion polymerization method can be applied.
  • a unit having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, modification or the like.
  • specific structures include: A glutarimide structure (see, for example, JP-A-62-89705, JP-A-02-178310, and WO2005 / 54311), A lactone ring structure (see, for example, JP-A No. 2004-168882 and JP-A No. 2006-171464), A (meth) acrylic acid unit or a glutaric anhydride structure obtained by thermal condensation cyclization of the unit (see, for example, JP-A No.
  • a maleic anhydride unit see, for example, JP-A-5-119217
  • an N-substituted or unsubstituted maleimide unit see, for example, WO2009 / 84541
  • Etc By introducing these structures into an acrylic resin, the molecular chain becomes rigid, and effects such as improved heat resistance, improved surface hardness, reduced heat shrinkage, improved chemical resistance and stain resistance can be expected.
  • thermoplastic resin that is at least partially compatible with the acrylic resin may be used in combination with the acrylic resin as long as the object of the present invention is not impaired or reinforced.
  • thermoplastic resins include styrene-acrylonitrile resins, styrene- (meth) acrylic acid resins, styrene-maleic anhydride resins, styrene-N substituted or unsubstituted maleimide resins, styrene-acrylonitrile-butadiene resins, styrene.
  • -Styrenic resins such as acrylonitrile-acrylic ester resin, polyvinyl chloride resin, polycarbonate resin, amorphous saturated polyester resin, polyamide resin, phenoxy resin, polyarylate resin, olefin- (meth) acrylic acid derivative resin, cellulose
  • cellulose derivatives such as acylate, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polylactic acid resin, and PHBH resin.
  • styrene resins and polycarbonate resins have excellent compatibility with acrylic resins, and can improve the bending resistance, solvent resistance, low moisture absorption, etc. of acrylic resin films. preferable.
  • the acrylic resin film is more preferably an acrylic film using an acrylic resin composition containing a rubber component.
  • the rubber component contains a soft / elastic resin component.
  • a known rubber component such as a crosslinked or non-crosslinked polymer, a block copolymer, or a graft copolymer can be used.
  • a core shell having a hard outer layer portion obtained by polymerizing vinyl polymerizable units in the presence of particles of an acrylate-based cross-linked elastic body [cross-linked elastic body made of a polymer mainly composed of an acrylate ester]. It is preferable to use a type graft copolymer.
  • an acrylic elastic graft copolymer using acrylic ester-based crosslinked elastic particles having a specific particle diameter and crosslinking density For example, an acrylic elastic graft having a hard-soft-hard multilayer structure containing hard crosslinked acrylic particles inside the crosslinked rubber particles, as disclosed in Japanese Patent Publication No. 55-27576 and Japanese Patent No. 3563166 An acrylic resin composition containing a copolymer is used.
  • an acrylic resin composition containing such an acrylic elastic graft copolymer By using an acrylic resin composition containing such an acrylic elastic graft copolymer, transparency, heat resistance, surface hardness, bending crack resistance, bending whitening resistance, and stretching during thermoforming It is easy to obtain an acrylic resin film excellent in the balance of physical properties such as properties and thermoformability.
  • acrylic resin composition it is possible to use an acrylic resin graft copolymer produced by the same reactor, and then an acrylic resin produced continuously.
  • acrylic elastomer graft copolymer in the presence of acrylate ester crosslinked elastomer particles having a layer structure of one layer or two or more layers containing one or more acrylate ester crosslinked elastomer layers.
  • a copolymer obtained by copolymerizing a monomer mixture (b) comprising 50 to 100% by weight of a methacrylic acid ester and 0 to 50% by weight of another copolymerizable vinyl monomer is preferred.
  • the acrylic ester-based crosslinked elastic particles having a layer structure of two or more layers the acrylic ester-based crosslinked elastic layer may be present in any layer. It is more preferable that the outermost layer is an acrylate-based crosslinked elastic body layer in order to improve the bending cracking resistance of the laminated film.
  • the acrylic ester-based crosslinked elastic body has an acrylic ester, other vinyl monomers copolymerizable as necessary, and two or more non-conjugated double bonds per copolymerizable molecule.
  • a polymer of a monomer mixture (a) composed of a polyfunctional monomer is preferred.
  • Monomers and polyfunctional monomers may all be mixed (one-stage polymerization) and used more than once (two-stage polymerization) by changing the composition of the monomer and polyfunctional monomer. Polymerization may be performed separately in polymerization or higher).
  • an alkyl acrylate ester is preferable from the viewpoint of polymerizability and cost, and an alkyl group having 1 to 12 carbon atoms is preferable.
  • preferable monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, acrylic acid Examples include cyclohexyl. These may be used alone or in combination of two or more.
  • the amount of the acrylic ester used as the monomer of the acrylic ester-based crosslinked elastic body is preferably 50 to 99.9% by weight, and 70 to 99.9% by weight in 100% by weight of the monomer mixture (a). Is more preferable, and 80 to 99.9 wt% is most preferable. If the amount of acrylate ester is 50 to 99.9% by weight, it is easy to obtain a laminated film that has good impact resistance and elongation at the time of tensile break, and is less likely to crack during secondary molding.
  • Examples of other copolymerizable vinyl monomers in the acrylic ester-based crosslinked elastomer include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-methacrylic acid t- Methacrylic acid esters such as butyl, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate and dicyclopentenyl methacrylate, vinyl halides such as vinyl chloride and vinyl bromide, acrylonitrile, methacrylo Vinyl cyanides such as nitriles, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, aromatic vinyl derivatives such as styrene, vinyltoluene and ⁇ -methylstyrene, vinylidene
  • the amount of the other copolymerizable vinyl monomer in the acrylic ester-based crosslinked elastic body is preferably 0 to 49.9% by weight, and 0 to 30% by weight in 100% by weight of the monomer mixture (a). More preferred is 0 to 20% by weight.
  • the amount of the other vinyl monomer is 49.9% by weight or less, it is easy to obtain a laminated film having excellent impact resistance and elongation at the time of tensile break, and suppressing the occurrence of cracks during secondary molding of the laminated film. It's easy to do.
  • polyfunctional monomer having two or more non-conjugated double bonds per copolymerizable molecule used for the production of an acrylic ester-based crosslinked elastic body it is usually used as a crosslinking agent and / or a graft crossing agent. It may be used.
  • Preferred examples of the polyfunctional monomer include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinyl benzene, ethylene glycol dimethacrylate, propylene glycol.
  • Examples include dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetromethylolmethane tetramethacrylate, and dipropylene glycol dimethacrylate. These polyfunctional monomers may be used alone or in combination of two or more.
  • the amount of the polyfunctional monomer having two or more non-conjugated double bonds per molecule that can be used for the production of the acrylate-based crosslinked elastomer is an average of the acrylate-based crosslinked elastomer. Along with the particle diameter, it greatly affects stress whitening, elongation at the time of tensile fracture, or transparency.
  • the amount of the polyfunctional monomer used in the production of the acrylic ester-based crosslinked elastic body is preferably 0.1 to 10% by weight, preferably 1.0 to 4% by weight in 100% by weight of the monomer mixture (a). Is more preferable.
  • the amount of the polyfunctional monomer used is 0.1 to 10% by weight, it is preferable from the viewpoint of bending cracking resistance, bending whitening resistance, and resin flowability during molding.
  • the amount of the polyfunctional monomer used is too small, the bending whitening resistance and transparency are likely to be impaired.
  • the amount of the polyfunctional monomer used is excessive, bending resistance, impact resistance, transparency of the film and the like are easily impaired.
  • acrylic elastomer graft copolymer in the presence of acrylate ester crosslinked elastomer particles, 50 to 100% by weight of methacrylic acid ester and 0 to 50% by weight of other copolymerizable vinyl monomers can be used.
  • a copolymer obtained by graft copolymerization of the monomer mixture (b) is preferable. More preferably, in the presence of 5 to 90 parts by weight of acrylic ester-based crosslinked elastic particles, it consists of 50 to 100% by weight of an alkyl methacrylate and 0 to 50% by weight of another copolymerizable vinyl monomer.
  • the total amount of the acrylic ester-based crosslinked elastic particles and the monomer mixture (b) shall satisfy 100 parts by weight.
  • the amount of the methacrylic acid alkyl ester in the monomer mixture (b) is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 80% by weight or more in terms of hardness and rigidity.
  • copolymerizable vinyl monomers those used in the above-mentioned acrylic ester-based crosslinked elastic bodies and alkyl alkyl esters having an alkyl group with 1 to 12 carbon atoms can be used.
  • monomers may be used independently and may use 2 or more types together.
  • the graft copolymerization of the monomer mixture (b) in the presence of the acrylic ester crosslinked elastomer particles is performed on the acrylic ester crosslinked elastomer particles.
  • a polymer component (free polymer) which is not graft-bonded is produced.
  • Such a free polymer can be used as part or all of the acrylic resin constituting the matrix phase of the acrylic resin composition and acrylic film of the present invention.
  • a chain transfer agent may be added to the monomer mixture (b) for the purpose of controlling the molecular weight of the polymer and the amount of the above free polymer produced.
  • the chain transfer agent may be selected from those usually used for radical polymerization. For example, alkyl mercaptan having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride or a mixture thereof is preferable.
  • the chain transfer agent is used in an amount of 0 to 2 parts by weight, preferably 0 to 0.5 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture (b).
  • the graft ratio of the monomer mixture (b) to the acrylic ester-based crosslinked elastic particles is preferably 5 to 250%, more preferably 10 to 230%, and still more preferably 20 to 220%.
  • the graft ratio is preferably increased.
  • acrylic ester-based crosslinked elastic resistant particles having a graft ratio within the above range are used, it is easy to obtain an acrylic resin film excellent in bending whitening resistance, transparency, elongation at tensile fracture, and moldability.
  • the graft ratio is too low, the bending whitening resistance, transparency, and elongation at the time of tensile breakage tend to be lowered.
  • the average particle diameter d of the acrylic elastic body graft copolymer is preferably 50 nm to 400 nm, more preferably 50 nm to 350 nm, and further preferably 50 nm to 300 nm.
  • the acrylic resin film contains an acrylic elastic graft copolymer having an average particle diameter within such a range, it is easy to balance impact resistance and bending cracking resistance with transparency and whitening. If the average particle size of the acrylic elastic graft copolymer is too small, impact resistance and bending cracking resistance are likely to be impaired. If the average particle size of the acrylic elastic graft copolymer is excessive, the transparency is likely to be impaired, and bending whitening is likely to occur.
  • the average particle diameter d (nm) of the acrylate-based crosslinked elastic particles in the acrylic resin film and the amount w (% by weight) of the polyfunctional monomer used in the acrylate-based crosslinked elastic body are: In order to greatly affect the stress whitening of the film, elongation at the time of tensile break, or transparency, it is preferable that the relational expression: 0.02d ⁇ w ⁇ 0.06d is satisfied, and 0.02d ⁇ w ⁇ 0.05d. It is more preferable to satisfy the above.
  • the amount of the polyfunctional monomer is within the range of the above relational expression, the elongation at the time of secondary molding of the acrylic resin film is less likely to decrease, and cracks are less likely to occur during molding and cutting, and transparency. And has the advantage that stress whitening hardly occurs during bending or tensile deformation.
  • the acrylic ester-based crosslinked elastic particles in the acrylic resin film are averaged after the amount of the polyfunctional monomer satisfies the above relational expression.
  • the particle diameter d is preferably 50 to 250 nm, more preferably 50 to 200 nm, still more preferably 50 to 150 nm, and particularly preferably 60 to 120 nm.
  • the average particle diameter d of the acrylic ester-based crosslinked elastic particles is 50 nm or more, a decrease in elongation at the time of secondary molding and generation of cracks at the time of molding or cutting are unlikely to occur. If the average particle diameter is 250 nm or less, stress whitening is less likely to occur, and transparency, particularly after vacuum molding or in-mold molding, can ensure transparency after insert molding (transparency retention before and after heating). preferable.
  • the average particle diameter of the acrylic elastic graft copolymer is a value measured using a light scattering method in a latex state using a Microtrac particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd.
  • the method for producing the acrylic elastic graft copolymer is not particularly limited, and a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method or dispersion polymerization method can be applied.
  • the emulsion polymerization method is particularly preferable from the viewpoint that the adjustment range of the resin structure is large.
  • initiators such as known organic peroxides, inorganic peroxides, and azo compounds can be used.
  • organic peroxides 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroperoxide, benzoylperoxide
  • organic peroxides such as oxide and lauroyl peroxide
  • inorganic peroxides such as potassium persulfate and sodium persulfate
  • azo compounds such as azobisisobutyronitrile are also used. These may be used alone or in combination of two or more.
  • initiators may be used as thermal decomposition type radical polymerization initiators, or alternatively sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, ferrous sulfate, sulfuric acid It may be used as a normal redox type polymerization initiator in combination with a reducing agent such as a complex of ferrous iron and ethylenediaminetetraacetic acid-2-sodium.
  • a reducing agent such as a complex of ferrous iron and ethylenediaminetetraacetic acid-2-sodium.
  • inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate are used from the viewpoint of polymerization stability and particle size control, or t-butyl hydroperoxide, cumene hydroperoxide, etc. It is more preferable to use redox initiators in which organic process oxides of the above are combined with inorganic reducing agents such as divalent iron salts and / or organic reducing agents such as sodium formaldehyde sulfoxylate, reducing sugar, ascorbic acid, etc. preferable.
  • the above-mentioned inorganic peroxide or organic peroxide is added by a known addition method such as a method of adding to a polymerization system as it is, a method of adding by mixing with a monomer, a method of adding by dispersing in an emulsifier aqueous solution, or the like. can do. From the viewpoint of the transparency of the resulting acrylic elastic graft copolymer, a method of adding to a monomer or a method of adding by dispersing in an aqueous emulsifier solution is preferred.
  • surfactant used for the emulsion polymerization of the acrylic elastic graft copolymer there is no particular limitation on the surfactant used for the emulsion polymerization of the acrylic elastic graft copolymer, and a wide variety of known surfactants can be used.
  • anionic surfactants such as sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium dioctyl sulfosuccinate, sodium alkyl sulfate, fatty acid sodium, sodium alkyl phosphate, sodium alkyl ether phosphate, sodium alkyl phenyl ether phosphate
  • nonionic surfactants such as alkylphenols, reaction products of aliphatic alcohols with propylene oxide, and ethylene oxide.
  • These surfactants may be used alone or in combination of two or more.
  • a cationic surfactant such as an alkylamine salt may be used.
  • the acrylic elastic graft copolymer can be separated and recovered from the latex of the acrylic elastic graft copolymer obtained by emulsion polymerization by a known method. For example, after adding a water-soluble electrolyte to the latex and coagulating it, the acrylic elastomer graft copolymer is separated and recovered by washing and drying the solids, or by treatment such as spray drying or freeze drying of the latex. be able to.
  • the acrylic elastic graft copolymer is previously obtained prior to the separation and recovery of the acrylic elastic graft copolymer. It is preferable to filter the latex with a filter or mesh to remove substances that cause foreign matter defects such as environmental foreign matter and polymerization scale. As such a filter or mesh, for example, it is sufficient that the mesh is 2 times or more larger than the average particle diameter of the acrylic elastic graft copolymer, and known ones used for filtration of liquid media can be used. It is.
  • the content of the acrylic ester-based crosslinked elastic body in the acrylic resin film used in the present invention is preferably 5 to 70% by weight, more preferably 5 to 45% by weight, and further preferably 10 to 30% by weight.
  • the total amount of the acrylic resin composition comprising the acrylic elastic graft copolymer and the acrylic resin is 100% by weight. If the content of the acrylic ester-based crosslinked elastic body is 5% by weight or more, the elongation at the time of tensile break of the obtained film is difficult to decrease, cracks are hardly generated when the film is cut, and stress whitening occurs. Tend to be difficult. Moreover, if it is 70 weight% or less, the melt processing at the time of manufacturing an acrylic resin film is easy.
  • additives used for acrylic resin films can be added to the acrylic resin composition constituting the acrylic resin film within a range that does not impair the effects of the present invention.
  • additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusing agents, matting agents, lubricants, coloring agents such as pigments and dyes, antiblocking agents composed of organic or inorganic particles, metals and Examples include, but are not limited to, infrared reflectors, plasticizers, and antistatic agents made of metal oxides.
  • These additives do not interfere with the features of the acrylic resin film, and do not interfere with the adhesion between the acrylic resin film and the cured resin layer for imparting chemical resistance and stain resistance. Any amount can be used as long as it does not contaminate the outer appearance or interfere with the purpose of surface decoration or surface protection.
  • a well-known processing method can be used for manufacture of an acrylic resin film.
  • an inflation method, a T-die extrusion method, a calendar molding method, a press molding method, or an acrylic resin composition used in the present invention is dissolved and dispersed in a solvent, and then a film-like material is formed on a belt-like substrate.
  • a solvent casting method in which a film is formed by casting and volatilizing the solvent.
  • a melt processing method that does not use a solvent, particularly a T-die extrusion method is preferable. According to the melt processing method, a film having excellent surface properties can be produced with high productivity, and the burden on the global environment and working environment due to production costs and solvents can be reduced.
  • a filter or a mesh is used to cause an appearance defect or an internal foreign matter of the acrylic resin film. Filter and remove environmental foreign substances, polymerization scale, and deteriorated resin. Thereby, the appearance quality of the acrylic resin film is improved.
  • a filtration step may be performed, for example, at the stage of blending and pelletizing an acrylic resin and an acrylic elastic graft copolymer and other blends at the time of melt processing. You may perform before the film forming process by die
  • the solvent casting method it may be carried out after the solution mixing of the acrylic resin and the acrylic elastic graft copolymer and before cast film formation.
  • Known filters and meshes can be widely used. In particular, when producing a high-quality acrylic resin film by melt processing, it is preferable to use a leaf disk type filter in terms of filtration efficiency and productivity.
  • a film having excellent surface properties can be obtained by simultaneously contacting (sandwiching) both sides of a molten film with a cooling roll or a metal belt when the film is molded as required.
  • a film having a superior surface property can be obtained by simultaneously contacting a roll or metal belt maintained at a glass transition temperature of ⁇ 50 ° C. or less, preferably a glass transition temperature of ⁇ 30 ° C. or less.
  • a roll for performing such sandwiching at least one of them is a metal roll having elasticity as disclosed in, for example, Japanese Patent Laid-Open No. 2000-153547 and Japanese Patent Laid-Open No. 11-235747.
  • a roll mirror surface can be transferred using a low pinching pressure, and a film having excellent smoothness and less internal strain can be obtained.
  • Uniaxial or biaxial stretching can be carried out using a known stretching apparatus. Biaxial stretching is performed using known methods and methods as appropriate, such as sequential biaxial stretching, simultaneous biaxial stretching, and longitudinal stretching, followed by transverse stretching while relaxing the longitudinal direction to reduce film bowing. It is possible to implement.
  • Such surface shape can be imparted by a known method. For example, by sandwiching both sides of a melted film immediately after extrusion or a formed film fed out from a feeding device with two rolls or belts having a surface shape on at least one surface, the surface shape of the roll is changed. There is a method of transferring.
  • the thickness of the cured resin layer in the laminated film of the present invention is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 3 to 15 ⁇ m.
  • the thickness of the cured resin layer is 1 ⁇ m or more, it is easy to obtain a laminated film having excellent chemical resistance and stain resistance.
  • the thickness of the cured resin layer is 30 ⁇ m or less, it is easy to produce a laminated film without excessive costs, and molding processing using the laminated film is easy.
  • an adhesive suitable for lamination or an adhesive layer made of an adhesive resin may be provided between the cured resin layer and the acrylic resin film within a range not impairing the effects of the present invention.
  • multilayer film may contain the fluororesin layer in the range which does not impair the effect of this invention.
  • Adhesive layer A well-known thing can be used as an adhesive agent and adhesive resin which are the materials of an adhesive bond layer.
  • Adhesives and adhesive resins include (meth) acrylic acid alkyl ester resins, or their copolymers, styrene-butadiene copolymers, polyisoprene rubber, polyisobutylene rubber and other rubbers, and polyvinyl ether resins. , Silicone-based, maleimide-based, cyanoacrylate-based resins, vinylidene halide resins such as vinylidene chloride and vinylidene fluoride, and mixtures thereof with urethane acrylate resins and (meth) acrylic acid alkyl ester-based resins.
  • (meth) acrylic acid alkyl ester resins which are copolymers mainly composed of (meth) acrylic acid alkyl ester monomers, preferable. These may be used alone, or may be used as an adhesive composition by blending a crosslinking agent and a tackifier.
  • the (meth) acrylic acid alkyl ester resin is an alkyl ester of acrylic acid or methacrylic acid, and is not particularly limited.
  • the method for forming the cured resin layer of the urethane acrylate resin can be used in the same manner.
  • the laminated film may include a fluororesin layer.
  • a fluororesin layer By providing the fluororesin layer, it is easy to impart liquid repellency such as water repellency and lactic acid resistance to the laminated film.
  • the fluororesin layer is preferably provided on one or both outermost phases of the laminated film, and more preferably provided on the curable resin layer.
  • the fluororesin is not particularly limited as long as it can form a fluororesin layer, and a known fluororesin is used.
  • a fluoroacrylic resin is preferable.
  • a fluorine-type acrylic resin is a polymer containing the unit derived from the (meth) acrylate containing a fluoroalkyl group.
  • the fluorinated acrylic resin is preferably an acrylic resin obtained by copolymerizing a fluorine-containing vinyl monomer and other copolymerizable vinyl monomers.
  • the monomer represented by these is preferable. This is because the fluorine-based acrylic resin containing a unit derived from the monomer represented by the formula (1) is excellent in adhesion to the cured resin layer and the acrylic resin film.
  • the monomer represented by the above formula (1) known compounds can be used. Specific examples of the monomer represented by the formula (1) include trifluoromethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 3,3,3-trifluoropropyl methacrylate, tri 4,4,4 -Fluorobutyl methacrylate, 6,6,6-trifluorohexyl methacrylate, 8,8,8-trifluorooctyl methacrylate, 1,1,1,3,3,3-hexafluoropropan-2-yl methacrylate, 2- (Trifluoromethyl) ethyl methacrylate, trifluoromethyl acrylate, 2,2,2-trifluoroethyl acrylate, 3,3,3-trifluoropropyl acrylate, 4,4,4-trifluorobutyl acrylate, 6,6, 6-trifluorohexyl acrylate, 8,8,8-trifluoro Octyl acrylate, 1,1,1,3,
  • trifluoromethyl methacrylate having a terminal trifluoromethyl group in terms of transparency when formed into a film, adhesion to a cured resin layer or an acrylic resin film, chemical resistance, and contamination resistance, And 2,2,2-trifluoroethyl methacrylate are preferred.
  • copolymerized vinyl monomers that can be copolymerized with fluorine-containing vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate.
  • alkyl methacrylate is preferable from the viewpoint of transparency and adhesion to the cured resin layer and the acrylic resin film.
  • alkyl methacrylate C 1 -C 4 alkyl methacrylate is preferable.
  • C 1 -C 4 alkyl methacrylates methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, and t-Butyl methacrylate is preferred.
  • the fluorinated acrylic resin is represented by the formula (1). It is preferably a polymer of a mixture of monomers composed of 50 to 100 parts by weight of the represented monomer and 0 to 50 parts by weight of other copolymerized vinyl monomers. More preferred is a polymer of a mixture of monomers composed of 70 to 99 parts by weight of the monomer represented by the formula (1) and 1 to 30 parts by weight of other copolymerized vinyl monomers.
  • the fluorine-based acrylic resin is preferably a copolymer of a monomer represented by the formula (1) and a methacrylate-based monomer from the viewpoint of heat resistance and water repellency at high temperatures.
  • a copolymer when the total of the monomer represented by the formula (1) and the methacrylate monomer is 100 parts by weight, the monomer represented by the formula (1) is 50 parts by weight or more.
  • a polymer of a mixture of monomers consisting of less than 100 parts by weight and more than 0 parts by weight and 50 parts by weight or less of methacrylate monomers is preferred. More preferred is a polymer of a mixture of monomers composed of 70 to 99 parts by weight of the monomer represented by the formula (1) and 1 to 30 parts by weight of a methacrylate monomer.
  • the monomer mixture used for the preparation of the above preferred copolymer preferably contains more than 0 part by weight and 50 parts by weight or less of C 1 -C 4 alkyl methacrylate with respect to 100 parts by weight of the monomer mixture. It is preferable to contain 1 part by weight or more and 30 parts by weight or less.
  • the obtained fluorinated acrylic resin has a high glass transition temperature, excellent water repellency at high temperatures, and excellent lactic acid resistance.
  • the number average molecular weight of the fluororesin is not particularly limited, but is preferably 3000 to 1000000, more preferably 5000 to 500000, and particularly preferably 8000 to 300000.
  • a fluororesin having a number average molecular weight within such a range combines excellent chemical resistance with a viscosity within a range that can be easily processed.
  • the fluororesin layer may contain other resins together with the fluoroacrylic resin described above.
  • other resins include fluorine resins such as vinylidene fluoride resin (PVDF) and vinyl fluoride resin (PVF), and acrylic resins.
  • the resin constituting the fluororesin layer may or may not have three-dimensional crosslinking, and preferably does not have three-dimensional crosslinking. Since the resin has substantially no three-dimensional cross-linking, the molding process near the softening temperature of the resin is easy.
  • the fact that the resin does not substantially have a three-dimensional crosslinking means that the molecular chain structure of the resin is a chain structure having almost no network structure due to crosslinking.
  • the glass transition temperature of the resin constituting the fluororesin layer is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 80 ° C. or higher.
  • the glass transition temperature of the resin is within such a range, the laminated film can easily be imparted with contamination resistance at high temperatures.
  • the thickness of the fluororesin layer is preferably 1 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, and particularly preferably 2 to 6 ⁇ m.
  • a method for forming the fluororesin layer is not particularly limited, but a wet coating method using an organic solvent solution of a resin constituting the fluororesin layer as a coating liquid is preferable. The coating liquid is applied to the surface on which the fluororesin layer is to be formed, and the organic solvent is removed from the coating film, whereby the fluororesin layer is formed.
  • the thickness of the fluororesin layer can be adjusted by adjusting the resin concentration in the coating liquid and the thickness of the coating film made of the coating liquid.
  • the laminated film according to the above (2) is referred to as a second laminated film.
  • the second laminated film includes a cured resin layer on the acrylic resin film.
  • the glass transition temperature of the cured resin layer is 105 ° C. or higher, like the first laminated film.
  • the material of the cured resin layer is not particularly limited, but the cured resin layer is formed by polymerizing a monomer having a non-conjugated double bond.
  • the cured resin layer is preferably formed using the same material as that described for the first laminated film.
  • the acrylic resin film is the same as the first laminated film.
  • the method for adjusting the glass transition temperature of the cured resin layer within a predetermined range is not particularly limited.
  • the glass transition temperature of the cured resin layer can be increased by increasing the degree of crosslinking of the cured resin layer or by increasing the glass transition temperature of the monomer that is the raw material of the cured resin layer.
  • the second laminated film has an elongation rate of 150% or more until yield fracture under conditions of a size of 10 ⁇ 100 mm, a chuck interval of 50 mm, a pulling speed of 200 mm / min, and a tensile thermostatic bath temperature of 120 ° C.
  • the elongation is preferably 200% or more.
  • the method for adjusting the elongation of the laminated film under the above conditions is not particularly limited.
  • the elongation percentage can be adjusted by appropriately adjusting the degree of crosslinking after curing in the cured resin layer.
  • the elongation percentage can also be adjusted by adjusting the average number of urethane bonds per molecule of the urethane acrylate resin.
  • the average number of urethane bonds is not particularly limited, but a preferable range for obtaining a laminated film exhibiting a desired elongation at 120 ° C. is as described above for the first laminated film.
  • the elongation percentage can also be adjusted by adjusting the weight average molecular weight of the urethane acrylate resin.
  • the weight average molecular weight of the urethane acrylate resin is not particularly limited, but a preferable range for obtaining a laminated film exhibiting a desired elongation at 120 ° C. is as described above for the first laminated film.
  • the second laminated film may include other layers in addition to the cured resin layer and the acrylic resin film.
  • the thickness of the second laminated film, the thickness of the cured resin layer, and the thickness of the acrylic resin film are the same as those of the first laminated film.
  • the haze is the same as that of the first laminated film.
  • the second laminated film may be given any surface shape such as a hairline, a prism, an uneven shape, or a matte surface on one side or both sides depending on the application. Good.
  • the laminated film according to the above (12) is referred to as a third laminated film.
  • the third laminated film includes a cured resin layer on the acrylic resin film.
  • a mixed organic solvent containing 25% of N, N-diethyl-3-methylbenzamide was dropped on the cured resin layer in the laminated film and the haze value after heat treatment at 80 ° C. for 24 hours was obtained. The amount of change is 0.2% or less.
  • the third laminated film has the above characteristics with respect to the haze value, since the cured resin layer is sufficiently crosslinked, the third laminated film is excellent in surface hardness, chemical resistance, and stain resistance.
  • the material of the cured resin layer is not particularly limited, but the cured resin layer is formed by polymerizing a monomer having a non-conjugated double bond. Typically, the cured resin layer is preferably formed using the same material as that described for the first laminated film.
  • the amount of change in haze can be increased by increasing the degree of crosslinking of the cured resin layer or by increasing the glass transition temperature of the monomer that is the raw material of the cured resin layer.
  • the third laminated film has an elongation rate of 200% or more until it yields and breaks under conditions of a size of 10 ⁇ 100 mm, a gap between chucks of 50 mm, a pulling speed of 200 mm / min, and a tensile thermostatic bath temperature of 120 ° C.
  • the laminated film includes the cured resin layer exhibiting the glass transition temperature and the acrylic resin film and is configured to exhibit the above-described elongation, a laminated film having desired performance can be obtained.
  • the method for adjusting the elongation of the laminated film under the above conditions is not particularly limited.
  • the elongation percentage of the laminated film under the above conditions is adjusted, for example, by the same method as the elongation adjusting method described for the second laminated film.
  • the third laminated film may include other layers in addition to the cured resin layer and the acrylic resin film.
  • the thickness of the second laminated film, the thickness of the cured resin layer, and the thickness of the acrylic resin film are the same as those of the first laminated film.
  • the haze value is the same as that of the first laminated film.
  • the third laminated film may be given any surface shape such as a hairline, a prism, a concavo-convex shape, or a matte surface on one or both sides depending on the application. Good.
  • ⁇ Use of laminated film As the use of the laminated film, surface protection and decorative use for a molded article or member having a three-dimensional shape or a three-dimensional design, such as a vehicle interior material, a building material, and a housing of an electric / electronic device, are particularly preferable.
  • the use of the laminated film is not limited to these, and can be used for surface protection and decoration of a wide range of articles.
  • automotive interior applications such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, and dashboards; weatherstrips, bumpers, bumper guards, side mudguards, body panels , Spoilers, front rills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, automotive exterior applications such as windows, headlamp covers, tail lamp covers, and windshield parts; smartphones, mobile phones Applications such as housings, display windows, and buttons for portable electronic devices such as tablet terminals; TVs, DVD players, stereos Equipment, rice cookers, washing machines, refrigerators, air conditioners, humidifiers, dehumidifiers, fans, other household electronic appliances, furniture products, etc., such as housings, front panels, buttons, emblems, and cosmetics Applications: Furniture exterior materials; Wall interiors, ceilings, floors, bathtubs, toilet seats, and other architectural interior materials; Siding exterior walls, fences, roofs, gates, and
  • the surface of the member after lamination is the cured resin layer side
  • the contact surface or adhesion surface with the member is the acrylic resin film side. From the viewpoints of water resistance and stain resistance.
  • the method for laminating the laminated film on the molded body or the decorative substrate is not limited, and a known method can be used.
  • a method of surface decoration or surface protection for forming a layer comprising the laminated film of the present invention on the surface of a molded article having a three-dimensional shape for example, Japanese Patent Publication No. 63-6339 and Japanese Patent Publication No. 4-9647 are disclosed.
  • a film-in-mold molding method or a film insert molding method, or Japanese Patent No. 3733564 A three-dimensional laminate molding method similar to the method described in Japanese Patent Publication No. 3924760 can be preferably used.
  • the film-in-mold molding method or the film insert molding method is laminated with a print decoration layer or a backer sheet as necessary, and a shape is given in advance by vacuum forming, pressure forming, hot press forming, or the like.
  • the film is laminated and integrated on the surface of the injection-molded body by injection-molding the base resin into the mold cavity with the film inserted into the injection-molding mold.
  • the above three-dimensional laminate molding method is similarly used in the case where a printing decoration layer or a backer sheet is laminated as necessary, and after laminating the adhesive layer, the film with the adhesive layer softened by heat is applied in a vacuum state or a compressed air state. This is a molding method to be applied to the surface of the molded body.
  • the resin temperature, molding conditions or the formation of a three-dimensional design such as a printed layer, a decorative layer, a vapor deposition layer, an embossed shape on the laminated film of the present invention or the presence or absence of a backer sheet is not particularly limited. It can be set appropriately in consideration of the type and use of the base resin.
  • the backer sheet include known styrene resins such as ABS resin, polyolefin resins, vinyl chloride resins, polycarbonate resins, polyester resins, and acrylic resins, as described in, for example, JP-A-2000-238070.
  • a sheet of material can be widely used.
  • Parts and “%” in the following production examples, examples and comparative examples represent “parts by weight” and “% by weight”, respectively.
  • the transparency (haze, haze value) of the obtained laminated film is 23 ° C. ⁇ 2 using a light transmittance measuring device (Nippon Denshoku Industries haze meter; NDH-2000 type) according to JIS K6714. The measurement was performed at a temperature of 50 ° C. and a humidity of 50%.
  • the change in the portion of the dried laminated film or acrylic resin film where the sunscreen agent was applied was evaluated visually and touched according to the following criteria.
  • ⁇ Test without weight As with the test with weight, after extending the sunscreen to a range of 1 cm ⁇ 1 cm, leave it at 80 ° C. for 24 hours without gauze and weight, or 24 hours at 90 ° C. After leaving, the dripped sunscreen was wiped off with gauze. After the laminated film or acrylic resin film was washed with water, the change in the portion of the dried laminated film or acrylic resin film to which sunscreen was applied was evaluated in the same manner as in the test with weight.
  • the laminated films of Examples 1 to 5 and Comparative Examples 1 to 4 were contacted with a sunscreen agent on the cured resin layer, and the film of Comparative Example 5 was acrylic.
  • a sunscreen agent was brought into contact with the base resin film, and in the laminated films of Example 6 and Comparative Example 6, the sunscreen agent was brought into contact with the fluororesin layer.
  • C The unevenness
  • the mixed solution was brought into contact with the cured resin layer.
  • the mixed solution was brought into contact with the resin film, and in the laminated films of Example 6 and Comparative Example 6, the mixed solution was brought into contact with the fluororesin layer.
  • ⁇ Lactic acid resistance> One drop (0.01 g) of lactic acid water (10% lactic acid aqueous solution) is dropped on the obtained laminated film or acrylic resin film (Comparative Example 5), and left for 24 hours at 80 ° C., then laminated film or acrylic The resin film was washed with water, and the change in the application part of the dried laminated film or acrylic resin film was evaluated visually and touched according to the following criteria.
  • lactic acid water was brought into contact with the cured resin layer
  • lactic acid water was brought into contact with the acrylic resin film.
  • lactic acid water was brought into contact with the fluororesin layer.
  • A No change is observed.
  • the surface hardness of the obtained laminated film or acrylic resin film was evaluated by measuring the pencil hardness under a load of 500 g in accordance with JIS K5600-5-4.
  • the hardness on the cured resin layer side was measured, and in the film of Comparative Example 5, the hardness of the acrylic resin film surface was measured, and the laminated film of Comparative Example 6 was measured. Then, the hardness of the surface on the fluororesin layer side was measured.
  • Total number of acryloyl and methacryloyl groups of urethane acrylate resin The total number of acryloyl groups and methacryloyl groups of the hydroxyl group-containing (meth) acrylate added to the end of the urethane resin. For example, since the urethane resin ends of ethylene glycol and isophorone diisocyanate are at two locations (both ends), the number of acryloyl groups becomes 6 when three pentaerythritol trimethacrylates having acryloyl groups are added. When using 2 or more types of hydroxyl-containing (meth) acrylate, it adds at each molar ratio.
  • Glass transition temperature of urethane acrylate resin and cured resin layer The glass transition temperature of the urethane acrylate resin and the cured resin layer was measured according to the method defined in JIS K7121. However, the solution product was measured using a solvent degassed and dried. Further, the glass transition temperature of the cured resin layer was measured using a sample obtained by scraping off a part of the cured resin layer in the laminated film.
  • the average number of urethane bonds in the urethane acrylate resin is calculated from the weight average molecular weight and the number of components of the diol compound, diisocyanate compound, and hydroxyl group-containing (meth) acrylate compound.
  • weight average molecular weight 7411 ethylene glycol (molecular weight 62), isophorone diisocyanate (molecular weight 222) and pentaerythritol triacrylate (molecular weight 298)
  • both ends are pentaerythritol triacrylate and the inner side is isophorone diisocyanate / ethylene.
  • the average number of urethane bonds per molecule of the urethane acrylate resin having the above configuration is 4.
  • units of ethylene glycol and isophorone diisocyanate are added and the number of urethane bonds increases by two.
  • the molecular weight 1102 (298 ⁇ 2 + 222 ⁇ 2 + 62) of the first component is subtracted from the weight average molecular weight 7411 to be 6309, and this value is divided by the unit molecular weight 284 (62 + 222) of ethylene glycol isophorone diisocyanate.
  • the average number of urethane bonds of this urethane acrylate resin is 48 (4 + 22 ⁇ 2).
  • the obtained urethane acrylate resin (A-1) has a glass transition temperature of 120 ° C., a weight average molecular weight of 7411, a number of acryloyl groups per molecule of 6, and a weight average molecular weight of acryloyl groups and methacryloyl groups per molecule.
  • the value divided by the total number was 1235.
  • the average number of urethane bonds per molecule was 48, and the value obtained by dividing the average number of urethane bonds per molecule by the total number of acryloyl groups and methacryloyl groups per molecule was 8.
  • the obtained urethane acrylate resin (A-3) had a value obtained by dividing the weight average molecular weight by the total number of acryloyl groups and (meth) acryloyl groups per molecule.
  • the number of urethane bonds per molecule was 47, and the value obtained by dividing the number of urethane bonds per molecule by the total number of acryloyl groups and (meth) acryloyl groups per molecule was 8.
  • the obtained urethane acrylate resin (A-4) has a glass transition temperature of 98 ° C., a weight average molecular weight of 6200, the number of functional groups per molecule of 2, and a weight average molecular weight of acryloyl groups and methacryloyl groups per molecule.
  • the value divided by the total number was 3100.
  • the average number of urethane bonds per molecule was 42, and the value obtained by dividing the average number of urethane bonds per molecule by the total number of acryloyl groups and methacryloyl groups per molecule was 21.
  • the obtained urethane acrylate resin (A-6) has no glass transition temperature observed at 40 ° C. or higher, the weight average molecular weight is 6800, the total number of acryloyl groups and methacryloyl groups per molecule is 6, and the weight average molecular weight
  • the value obtained by dividing by the number of functional groups per molecule was 1133.
  • the average number of urethane bonds per molecule was 12, and the value obtained by dividing the average number of urethane bonds per molecule by the total number of acryloyl groups and methacryloyl groups per molecule was 2.
  • Monomer mixture (c1-1a): -Vinyl monomer mixture (butyl acrylate (BA) 90% and methyl methacrylate (MMA) 10%) 100 parts-allyl methacrylate (AlMA) 1 part-cumene hydroperoxide (CHP) 0.2 part then dioctyl After 0.05 part of sodium sulfosuccinate was charged, the internal temperature was adjusted to 60 ° C., 100 parts of a vinyl monomer mixture (BA 10% and MMA 90%), 0.5 part of tarlead decyl mercaptan (t-DM) and 70 parts of a monomer mixture (c1-1b) consisting of 0.5 part of CHP was continuously added at a rate of 10 parts / hour, and the polymerization was continued for another hour, whereby an acrylic elastic graft copolymer (c1- 1) (average particle size 90 nm) was obtained. The polymerization conversion rate was 98.2%. The obtained latex was salted out with calcium chloride, coagul
  • a 90 mm ⁇ L / D 36 vented single screw extruder adjusted to a temperature of 220 ° C., melt kneading at a screw rotation speed of 90 rpm and a discharge rate of 190 kg / hr, taken into a strand shape, cooled in a water bath, Cutting with a pelletizer gave resin pellets of acrylic resin (C-1).
  • the obtained laminated film was stretched 150% (2.5 times) using a biaxial stretching machine at 120 ° C. so that the total film thickness was 32 ⁇ m, and a 150% stretched product was obtained.
  • the obtained stretched product was evaluated for chemical resistance and stain resistance. The results are shown in Table 2.
  • Example 2 Except for using the urethane acrylate resin (A-2) obtained in Production Example 2, the cured resin layer obtained by curing the urethane acrylate resin was 5 ⁇ m in total thickness by the same operation as in Example 1. Obtained a laminated film of 80 ⁇ m. Table 2 shows the evaluation results regarding the obtained laminated film. Further, in the same manner as in Example 1, a 150% stretched product of the obtained laminated film was obtained. Table 2 shows the evaluation results regarding the obtained stretched product.
  • Example 3 Except for using the urethane acrylate resin (A-3) obtained in Production Example 3, the cured resin layer obtained by curing the urethane acrylate resin was 5 ⁇ m in total thickness by the same operation as in Example 1. Obtained a laminated film of 80 ⁇ m. Table 2 shows the evaluation results regarding the obtained laminated film. Further, in the same manner as in Example 1, a 150% stretched product of the obtained laminated film was obtained. Table 2 shows the evaluation results regarding the obtained stretched product.
  • Example 4 Except for using the urethane acrylate resin (A-4) obtained in Production Example 4, the cured resin layer obtained by curing the urethane acrylate resin in the same operation as in Example 1 had a total film thickness of 5 ⁇ m. Obtained a laminated film of 80 ⁇ m. Table 2 shows the evaluation results regarding the obtained laminated film. Further, in the same manner as in Example 1, a 150% stretched product of the obtained laminated film was obtained. Table 2 shows the evaluation results regarding the obtained stretched product.
  • the solvent was evaporated by leaving it in a dryer at 80 ° C. for 1 minute, and then a 20% solution of the fluorine acrylic resin obtained in Production Example 8 After coating, the film is dried for 2 minutes in an 80 ° C. dryer, irradiated with ultraviolet rays of 400 mJ / cm 2 , and the cured resin layer obtained by curing the urethane acrylate resin has a film thickness of 5 ⁇ m and a fluorine-based acrylic resin film thickness of 4 ⁇ m. A laminated film having a total film thickness of 84 ⁇ m was obtained. Further, in the same manner as in Example 1, a 150% stretched product of the obtained laminated film was obtained. Table 2 shows the evaluation results regarding the obtained laminated film and the stretched product.
  • Example 3 Except for using urethane acrylate resin (A-7) (manufactured by Nippon Synthetic Chemical Co., Ltd., UV3520EA), the cured resin layer obtained by curing the urethane acrylate resin was 5 ⁇ m in total thickness by the same operation as in Example 1. A laminated film having a thickness of 80 ⁇ m was obtained. Table 2 shows the evaluation results regarding the obtained laminated film.
  • the urethane acrylate resin (A-7) has a glass transition temperature of 46 ° C., a weight average molecular weight of 14,000, and a value obtained by dividing the weight average molecular weight by the total number of acryloyl groups and methacryloyl groups per molecule is 7000. Further, in the same manner as in Example 1, a 150% stretched product of the obtained laminated film was obtained. Table 2 shows the evaluation results regarding the obtained stretched product.
  • the weight average molecular weight is 352 and the value obtained by dividing the weight average molecular weight by the number of functional groups per molecule is 88.
  • multilayer film of the comparative example 4 the 150% stretched product of the laminated
  • Example 5 Table 2 shows the evaluation results regarding only the acrylic film (thickness 75 ⁇ m) obtained in Example 1. Moreover, it carried out similarly to Example 1, and obtained the 150% stretched product of the obtained film. Table 2 shows the evaluation results regarding the obtained stretched product.
  • Example 2 shows the evaluation results regarding the obtained laminated film and the stretched product.
  • Table 1 shows information regarding the material, film thickness, raw materials, and the like regarding the cured resin layers formed in each of the examples and comparative examples. In Comparative Examples 5 and 6, the cured resin layer was not formed.
  • Table 2 shows the evaluation results of the laminated films obtained in each of the examples and comparative examples and the stretched products thereof. In Table 1, “ ⁇ 40” means less than 40. In Table 2, “1.0 ⁇ ” means more than 1.0.
  • a cured resin layer having a glass transition temperature of 105 ° C. or higher is provided on an acrylic resin film, and the cured resin layer is made of a resin containing a unit derived from a urethane acrylate resin, and
  • the laminated film of the Example formed using the urethane acrylate resin whose number of urethane bonds per molecule is 40 or more has chemical resistance against chemicals such as printing ink, DOP, sunscreen agent, insect repellent and the like. In practice, it is difficult to cause problems regarding chemical resistance and stain resistance without being significantly inferior in contamination. About the laminated film of Example 3 and 4, when test conditions are severe, sunscreen resistance and insect repellent resistance may be inferior.
  • any evaluation of sunscreen resistance and insect repellent resistance is good under the conditions of 23 ° C., 24 hours, with gauze. That is, the laminated films of Examples 3 and 4 have no problem with respect to sunscreen resistance and insect repellent resistance in a normal environment where sunscreen and insect repellent are used. Furthermore, the laminated films of the examples have excellent transparency, surface hardness, resistance to bending cracking, and resistance to bending whitening, similar to acrylic resin films, and high stretch at a high temperature of 120 ° C. Is possible. For this reason, the laminated film of an Example is optimal for the decoration or protective film used for insert molding, in-mold molding, three-dimensional laminate molding, etc. which are used for an automotive interior / exterior member.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention vise à procurer un film à couches ayant une excellente transparence, une excellente dureté de surface, une excellente résistance à la fissuration par flexion, une excellente résistance au blanchissement par courbure, et une excellente aptitude au thermoformage, et une remarquable résistance chimique ou une une remarquable résistance aux taches vis-à-vis de divers produits chimiques, et qui peut être utilisé pour la protection de surface ou la décoration de meubles ou de matériaux de véhicule, de boîtiers de dispositifs électroniques/électriques, et analogues. La présente invention porte sur une couche de résine durcie ayant une température de transition vitreuse spécifique et comprenant des unités dérivées d'une résine d'acrylate d'uréthane spécifique, le nombre moyen de liaisons uréthane contenues dans les unités dérivées à partir d'une résine d'acrylate d'uréthane étant de 40 par unité, est formée sur un film de résine acrylique.
PCT/JP2016/067204 2015-06-12 2016-06-09 Film à couches WO2016199847A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018111793A (ja) * 2017-01-11 2018-07-19 アイカ工業株式会社 紫外線硬化型樹脂組成物及びハードコートフィルム
JP2020082729A (ja) * 2018-11-19 2020-06-04 株式会社カネカ 積層フィルム、成形体、及び車載ディスプレイ用前面板
JP2021066874A (ja) * 2019-10-23 2021-04-30 アイカ工業株式会社 光硬化性樹脂組成物及びハードコートフィルム
CN113661191A (zh) * 2019-05-30 2021-11-16 中国涂料株式会社 紫外线固化型氨基甲酸酯丙烯酸酯树脂、及含有其的紫外线固化型树脂组合物
JP7293518B1 (ja) 2022-07-11 2023-06-19 アイカ工業株式会社 自動車外装の成形用フィルム用ハードコート樹脂組成物
JP7385784B1 (ja) 2023-06-13 2023-11-22 アイカ工業株式会社 光硬化性樹脂組成物、成形用ハードコートフィルム及びそれを用いた成形品
JP7445457B2 (ja) 2020-02-21 2024-03-07 中国塗料株式会社 光硬化性塗料組成物、硬化塗膜およびそれを備える塗膜付き基材

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002293851A (ja) * 2001-03-29 2002-10-09 Kansai Paint Co Ltd 光硬化性樹脂組成物
JP2006070112A (ja) * 2004-08-31 2006-03-16 Hitachi Chem Co Ltd 光硬化性樹脂組成物
JP2010131901A (ja) * 2008-12-05 2010-06-17 Three M Innovative Properties Co 積層シート、それを貼り付けた部品およびその製造方法
JP2011157497A (ja) * 2010-02-02 2011-08-18 Daicel-Cytec Co Ltd 活性エネルギー線硬化性組成物
WO2015011804A1 (fr) * 2013-07-24 2015-01-29 ハリマ化成株式会社 Matériau de revêtement et composition de revêtement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002293851A (ja) * 2001-03-29 2002-10-09 Kansai Paint Co Ltd 光硬化性樹脂組成物
JP2006070112A (ja) * 2004-08-31 2006-03-16 Hitachi Chem Co Ltd 光硬化性樹脂組成物
JP2010131901A (ja) * 2008-12-05 2010-06-17 Three M Innovative Properties Co 積層シート、それを貼り付けた部品およびその製造方法
JP2011157497A (ja) * 2010-02-02 2011-08-18 Daicel-Cytec Co Ltd 活性エネルギー線硬化性組成物
WO2015011804A1 (fr) * 2013-07-24 2015-01-29 ハリマ化成株式会社 Matériau de revêtement et composition de revêtement

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018111793A (ja) * 2017-01-11 2018-07-19 アイカ工業株式会社 紫外線硬化型樹脂組成物及びハードコートフィルム
JP2020082729A (ja) * 2018-11-19 2020-06-04 株式会社カネカ 積層フィルム、成形体、及び車載ディスプレイ用前面板
JP7477281B2 (ja) 2018-11-19 2024-05-01 株式会社カネカ 積層フィルム、成形体、及び車載ディスプレイ用前面板
CN113661191A (zh) * 2019-05-30 2021-11-16 中国涂料株式会社 紫外线固化型氨基甲酸酯丙烯酸酯树脂、及含有其的紫外线固化型树脂组合物
JP2021066874A (ja) * 2019-10-23 2021-04-30 アイカ工業株式会社 光硬化性樹脂組成物及びハードコートフィルム
JP7445457B2 (ja) 2020-02-21 2024-03-07 中国塗料株式会社 光硬化性塗料組成物、硬化塗膜およびそれを備える塗膜付き基材
JP7293518B1 (ja) 2022-07-11 2023-06-19 アイカ工業株式会社 自動車外装の成形用フィルム用ハードコート樹脂組成物
JP7361962B1 (ja) 2022-07-11 2023-10-16 アイカ工業株式会社 成形用ハードコートフィルム及びそれを用いた成形品、並びにインサート成形品の製造方法
WO2024014053A1 (fr) * 2022-07-11 2024-01-18 アイカ工業株式会社 Composition de résine de revêtement dur pour film de moulage extérieur automobile, film de revêtement dur pour moulage, procédé de production de produit moulé par insertion, produit moulé par insertion et produit moulé hors moule
JP2024009743A (ja) * 2022-07-11 2024-01-23 アイカ工業株式会社 自動車外装の成形用フィルム用ハードコート樹脂組成物
JP7385784B1 (ja) 2023-06-13 2023-11-22 アイカ工業株式会社 光硬化性樹脂組成物、成形用ハードコートフィルム及びそれを用いた成形品
JP7492639B1 (ja) 2023-06-13 2024-05-29 アイカ工業株式会社 光硬化性樹脂組成物、成形用ハードコートフィルム及びそれを用いた成形品

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