WO2021230370A1 - Composition de résine durcissable, film pour moulage, article moulé et procédé de moulage - Google Patents

Composition de résine durcissable, film pour moulage, article moulé et procédé de moulage Download PDF

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Publication number
WO2021230370A1
WO2021230370A1 PCT/JP2021/018491 JP2021018491W WO2021230370A1 WO 2021230370 A1 WO2021230370 A1 WO 2021230370A1 JP 2021018491 W JP2021018491 W JP 2021018491W WO 2021230370 A1 WO2021230370 A1 WO 2021230370A1
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molding
film
layer
resin
group
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PCT/JP2021/018491
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English (en)
Japanese (ja)
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拓也 北村
佑一 早田
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富士フイルム株式会社
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Priority to JP2022522224A priority Critical patent/JP7443508B2/ja
Publication of WO2021230370A1 publication Critical patent/WO2021230370A1/fr

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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F

Definitions

  • the present disclosure relates to a curable resin composition, a film for molding, a molded product, and a molding method.
  • Various performances are imparted to the surface of base materials such as paper, wood, plastic, and inorganic materials such as metal and glass.
  • the coating is applied to protect the surface, or the coating is applied for the purpose of design.
  • a coating agent is applied to the surface of the molded product after molding, or painting is performed for the purpose of design. It has been.
  • a surface protective layer or a decorative layer is prepared as a film for molding, the film for molding is placed on a mold, and the film for molding is molded into a base material or a base material.
  • a method of protecting the surface or imparting design by transferring the surface protective layer or the decorative layer to a plastic molded product or the like is adopted.
  • Patent Document 1 describes an active energy ray-curable acrylic acrylate resin having a (meth) acryloyl group on one side of a base film having a release layer and having a (meth) acryloyl group as a transfer layer that can be peeled off from the base film and does not have a urethane bonding structure.
  • a curable hard coat layer made of a hard coat agent composition containing an active energy ray-curable urethane acrylate resin, and an active energy ray-curable acrylic having a hydroxyl group and a (meth) acryloyl group so as to be in contact with the hard coat layer.
  • a curable primer layer made of a primer composition containing an acrylate resin and / or an active energy ray-curable urethane acrylate resin and a polyisocyanate compound, and an active energy ray-curable in-mold transfer sheet having an adhesive layer. Have been described. This transfer sheet for active energy ray-curable in-mold molding is obtained by curing the polyisocyanate compound of the active energy ray-curable sheet.
  • Patent Document 2 describes a carboxyl group and ( For a photocurable decorative laminated film obtained by photocuring a (meth) acrylic resin having a (meth) acryloyl group on the side chain and a urethane (meth) acrylate to which a compound having a (meth) acryloyl group is added. The resin composition is described.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2011-143719
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2011-132288
  • An object to be solved by one embodiment of the present invention is to provide a curable resin composition having excellent moldability and acid resistance after curing.
  • An object to be solved by another embodiment of the present invention is to provide a molding film having excellent molding processability and acid resistance. Further, an object to be solved by another embodiment of the present invention is to provide a molding method and a molded product using the above-mentioned molding film.
  • the means for solving the above problems include the following aspects. ⁇ 1> Curing containing a (meth) acrylic resin having a number average molecular weight of 10,000 or more and 500,000 or less having a (meth) acryloyl group or a vinyl ether group, a monomer having a (meth) acryloyl group or a vinyl ether group having a molecular weight of less than 10,000, and a polymerization initiator. Sex resin layer composition.
  • ⁇ 2> The curable resin composition according to ⁇ 1>, wherein the monomer having a (meth) acryloyl group or a vinyl ether group and having a molecular weight of less than 10,000 has a structure represented by the following formula (1).
  • R 1 , R 2 , and R 3 in the formula (1) each independently have a hydrogen atom, a hydroxy group, a halogen group, and 1 to 18 carbon atoms (which may have a substituent). It represents an alkyl group, a group having a group or vinyl ether group, having a (meth) acryloyl group, at least one of R 1, R 2, and R 3 have the (meth) acryloyl group or vinyl ether group.
  • ⁇ 3> The curable resin composition according to ⁇ 2>, wherein R 1 , R 2 , and R 3 are all groups having a (meth) acryloyl group.
  • R 1 , R 2 , and R 3 are all groups having a (meth) acryloyl group.
  • ⁇ 4> A film for molding processing having a coating layer of the curable resin composition according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 5> A film for molding having a coating layer of the curable resin composition according to any one of ⁇ 1> to ⁇ 3> and a thermoplastic resin layer.
  • ⁇ 6> The film for molding processing according to ⁇ 5>, wherein the thermoplastic resin layer contains polyvinyl alcohol.
  • ⁇ 7> A molded product obtained by molding and curing the molding film according to any one of ⁇ 4> to ⁇ 6>.
  • ⁇ 8> The molded product according to ⁇ 7>, wherein the water permeation amount when allowed to stand in water at 80 ° C. for 24 hours is 500 g / m 2 / day or less.
  • a molding method comprising the step of molding the molding film according to any one of ⁇ 4> to ⁇ 6> and the step of curing the coating layer in the molded film for molding.
  • the process and the molding method including.
  • thermoplastic resin layer A step of forming a thermoplastic resin layer by coating on a coating layer of the curable resin composition according to any one of ⁇ 1> to ⁇ 3> formed by coating on a resin substrate.
  • the molding method according to ⁇ 10> which is further possessed.
  • a curable resin composition having excellent molding processability and acid resistance after curing.
  • a molding film having excellent molding processability and acid resistance.
  • FIG. 1 is a schematic cross-sectional view showing an example of a molding film according to the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing another example of the molding film according to the present disclosure.
  • the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition when a plurality of the substances corresponding to each component are present in the composition, unless otherwise specified. Means quantity.
  • total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • solid content is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
  • the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • either or both of acrylic and methacrylic may be referred to as "(meth) acrylic".
  • (meth) acrylic acid includes both acrylic acid and methacrylic acid.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are gels using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
  • THF tetrahydrofuran
  • GPC permeation chromatography
  • the curable resin composition according to the present disclosure is a (meth) acrylic resin having a (meth) acryloyl group or a vinyl ether group and having a number average molecular weight of 10,000 or more and 500,000 or less (hereinafter, also referred to as “specific polymerizable resin” or “resin A”). ), A monomer having a (meth) acryloyl group or a vinyl ether group and having a molecular weight of less than 10,000 (hereinafter, also referred to as “specific polymerizable monomer” or “monomer B”), and a polymerization initiator.
  • the curable resin composition according to the present disclosure can be cured by a curing reaction in a specific polymerizable resin and a specific polymerizable monomer to obtain a cured product (for example, a cured layer).
  • the curable resin composition of the present disclosure exerts an excellent effect.
  • the curable resin composition contains a specific polymerizable resin having a number average molecular weight of 10,000 or more and 500,000 or less and a specific polymerizable monomer having a molecular weight of less than 10,000, the curable resin composition can be deformed at a molding temperature.
  • a dense cured product that is difficult for water to permeate can be obtained.
  • the influence of the acid component on the cured product can be suppressed.
  • the water permeation amount when the cured product is allowed to stand in water at 80 ° C. for 24 hours can be easily controlled to 500 g / m 2 / day or less, and the hardness is also excellent.
  • the invasion of water into the layer is further suppressed and the hardness of the cured product is further increased. As a result, it is possible to make the cured product more excellent in acid resistance after molding while ensuring molding processability.
  • the curable resin composition contains a (meth) acrylic resin (resin A) having a (meth) acryloyl group or a vinyl ether group and having a number average molecular weight of 10,000 or more and 500,000 or less.
  • the resin A can be appropriately selected from acrylic resins having a (meth) acryloyl group or a vinyl ether group and having a number average molecular weight of 10,000 or more and 500,000 or less.
  • Resin A has a (meth) acryloyl group or a vinyl ether group as a polymerizable group and contributes to curability.
  • the (meth) acryloyl group or the vinyl ether group polymerizes to bond the resins, so that a dense three-dimensional bond structure is formed in the cured product. .. Therefore, the cured product is difficult for moisture to permeate and has a high hardness.
  • the resin A preferably has an acryloyl group as a polymerizable group.
  • the resin A examples include (meth) acryloyloxy-modified polymethyl (meth) acrylate, vinyloxy-modified polymethyl (meth) acrylate, (meth) acryloyloxypolyurethane-modified polymethyl (meth) acrylate, and (meth) acryloyloxy-modified- (polymethyl).
  • the resin A a commercially available product on the market may be used.
  • examples of commercially available products include the Acryt series manufactured by Taisei Fine Chemical Co., Ltd. (eg, Acryt 8KX-212, 8KX-212, 8KX-078, 8BR-600 and the like.
  • the glass transition temperature (Tg) in the resin A is preferably 50 ° C. or higher and 130 ° C. or lower, and more preferably 60 ° C. or 120 ° C. or lower, from the viewpoint of molding processability and acid resistance.
  • the glass transition temperature (Tg) of the resin in the present disclosure shall be determined from the measured principal maximum peak using a differential scanning calorimeter (manufactured by PerkinElmer: DSC-7) in accordance with ASTMD3418-8.
  • the temperature correction of the detection unit of this device uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat.
  • DSC-7 differential scanning calorimeter
  • the temperature correction of the detection unit of this device (DSC-7) uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat.
  • an aluminum pan is used, and an empty pan is set as a control.
  • the temperature is raised at a heating rate of 10 ° C./min, held at 200 ° C. for 5 minutes, lowered from 200 ° C. to 20 ° C. using liquid nitrogen at -10 ° C./min, held at 20 ° C. for 5 minutes, and again 20.
  • Tg be the
  • the number average molecular weight (Mn) of the resin A is preferably 5,000 or more, more preferably 10,000 or more, and more preferably 10,000 or more, from the viewpoint of molding processability and acid resistance after curing. It is more preferably 500,000 or less, and particularly preferably 15,000 or more and 200,000 or less.
  • the resin A may contain only one type, or may contain two or more types.
  • the content of the resin A in the curable resin composition is preferably 20% by mass or more and 70% by mass or less, more preferably 25% by mass or more and 65% by mass, more preferably 30% by mass, based on the total mass of the curable resin composition. More preferably, it is by mass or more and 50% by mass.
  • the curable resin composition contains a monomer (monomer B) having a (meth) acryloyl group or a vinyl ether group and having a molecular weight of less than 10,000, from the viewpoint of curability and acid resistance of the obtained cured product.
  • Examples of the monomer B include alkyl monoacrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, lauryl acrylate, isostearyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-acryloyloxypropyl).
  • alkyl monoacrylates eg, methyl acrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, lauryl acrylate, isostearyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-acryloyloxypropyl.
  • Methacrylate alkyl diacrylate (eg 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate), alkyl acrylate having 3 or more functional groups (eg pentaerythri
  • Triacrylate pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropanetetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate), cyclic alkyl acrylates (eg cyclohexyl acrylate, isobornyl acrylate, dicyclo) Pentanyl acrylate, dicyclopentenyl acrylate, 2-methyladamantyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, benzyl acrylate, tricyclodecanedimethanol diacrylate, 1,3-adamantandiol diacrylate), alkyl methacrylate (eg) : 3,4-Epoxycyclohexylmethylmethacrylate), acrylamide (eg hydroxyethylacrylamide, diethylacrylamide), 2-acryloyloxyethyl succinate,
  • R 1 , R 2 , and R 3 are each independently an alkyl group having 1 to 18 carbon atoms, which may have a hydrogen atom, a hydroxy group, a halogen group, and a substituent (meth). ) represents a group having a group, or a vinyl ether group having an acryloyl group, at least one of R 1, R 2, and R 3 have the (meth) acryloyl group or vinyl ether group.
  • Examples of the group having a (meth) acryloyl group include an acryloyl group, a methacryloyl group, 2-acryloylethyl, 4-acryloxybutyl, 3-acryloylcyclohexyl, and the like.
  • Examples of the group having a vinyl ether group include an ethyl vinyl ether group, an n-butyl vinyl ether group, a cyclohexyl vinyl ether group and the like.
  • R 1 , R 2 , and R 3 are preferably the same group, and R 1 , R 2 , and R 3 are all groups having a (meth) acryloyl group. preferable.
  • Examples of the compound having the structure represented by the formula (1) include tris (2-acryloyloxyethyl) isocyanurate (also known as trisisocyanurate (2-acryloyloxyethyl)) and tris (2-acryloyloxybutyl). Isocyanurate, caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, and the like can be mentioned.
  • Monomer B may contain only one kind, or may contain two or more kinds.
  • the content of the monomer B in the curable resin composition is preferably 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 70% by mass, more preferably 50, based on the total mass of the curable resin composition. More preferably, it is by mass or more and 65% by mass.
  • the curable resin composition further contains an organic resin (hereinafter, also referred to as “organic resin C”) within a quantitative range that does not significantly impair the effects of the present disclosure. May be good.
  • organic resin C an organic resin
  • the organic resin C examples include acrylic resins other than resin A, polyester resins, polyurethane resins, polycarbonate resins, polyolefin resins, styrene resins, acrylonitrile-styrene-butadiene resins, acrylonitrile-styrene resins, cellulose resins, polyvinyl chloride resins, and polyimide resins. , Polyamide resin, fluoropolymer and the like.
  • the organic resin C preferably has a crosslinkable group.
  • the crosslinkable group includes a (meth) acryloyl group, a vinyl ether group and the like. Since the resin A and the monomer B have a (meth) acryloyl group or a vinyl ether group, the organic resin C preferably has a (meth) acryloyl group or a vinyl ether group as a crosslinkable group.
  • the curable resin composition contains a polymerization initiator from the viewpoints of curability, scratch resistance of the obtained cured product, and chipping resistance after curing.
  • the polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
  • a photopolymerization initiator is preferred from the viewpoint of increasing the sensitivity to exposure.
  • the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator (including a photoacid generator).
  • a radical polymerization initiator is preferable from the viewpoint that the curability can be adjusted by exposure to easily control the molding processability before curing, the scratch resistance of the obtained cured film, and the chipping resistance after curing. It is more preferably a polymerization initiator.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
  • a known photopolymerization initiator can be used.
  • the oxime-based polymerization initiator described in paragraphs 0064 to 0081 of the publication can be used.
  • photopolymerization initiator examples include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (for example, IRGACURE (registered trademark) OXE-01, manufactured by BASF).
  • a commercially available product marketed as a photopolymerization initiator may be used.
  • Examples of commercially available products are "4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate (product name: CPI-100P)” and "4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate (product name: CPI-101A)”.
  • Alkyl-substituted diphenyliodonium alkylfluorosulfone product name: IK-1 (above, manufactured by San-Apro Co., Ltd.) and the like.
  • an initiator other than the halogen-containing polymerization initiator such as a trichloromethyltriazine-based compound
  • an ⁇ -aminoalkylphenone-based compound such as an ⁇ -hydroxyalkylphenone-based compound, or an oxime.
  • Oxime-based polymerization initiators such as ester-based compounds are more preferable.
  • the ⁇ -hydroxyalkylphenone-based compound is most preferable in that the change in color of the cured product is suppressed and high sensitivity can be obtained.
  • the thermal polymerization initiator is not particularly limited, and a known thermal polymerization initiator can be used, and organic peroxides, azo compounds and the like are preferably mentioned.
  • the organic peroxide is not particularly limited, and known ones can be used. Of these, those classified into ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates are preferable.
  • ketone peroxide examples include methyl ethyl ketone peroxide, cyclohexanoperoxide and the like.
  • peroxyketal examples include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 1,1-bis (t).
  • hydroperoxide examples include p-menthane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumene hydroperoxide, and t-butylhydroperoxide.
  • dialkyl peroxide examples include ⁇ , ⁇ -bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-.
  • Butyl cumyl peroxide, t-amyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexene-3 can be mentioned.
  • peroxyester examples include Kumilperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxyneodecanoate, and t-butylperoxyneoate.
  • diacyl peroxide examples include diisobutyryl peroxide, di-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, dissuccinic acid peroxide, and dibenzoyl peroxide.
  • peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and di-2-ethylhexyl peroxydicarbonate. , T-amylperoxypropyl dicarbonate, t-amylperoxy-2-ethylhexyl dicarbonate.
  • azo-based thermal radical polymerization initiator examples include water-soluble azo-based thermal radical polymerization initiators, oil-soluble azo-based thermal radical polymerization initiators, and polymer azo-based thermal radical polymerization initiators. Can be mentioned.
  • water-soluble azo-based thermal radical polymerization initiator examples include 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate and 2,2'-azobis [N-. (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2 , 2'-azobis (1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2' -Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2- (2-imidazolin) -2-yl) Propan
  • oil-soluble azo-based thermal radical polymerization initiator examples include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and dimethyl-2,2'-azobis (2-methylpropionate).
  • 1,1'-azobis cyclohexane-1-carbonitrile
  • 2,2'-azobis N-cyclohexyl-2-methylpropionamide)
  • 2,2'-azobis (2,4-dimethylvaleronitrile 2,2'-azobis (2-methylbutyronitrile
  • 2,2'-azobis [N- (2-propenyl) -2- Methylpropionamide] 2,2'-azobis (N-butyl-2-methylpropionamide)
  • polymer azo-based thermal radical polymerization initiator examples include a polydimethylsiloxane unit-containing polymer azo-based thermal radical polymerization initiator and a polyethylene glycol unit-containing polymer azo-based thermal radical polymerization initiator.
  • the content of the polymerization initiator is preferably 0.01% by mass to 20% by mass, preferably 0.1% by mass, based on the solid content mass of the curable resin composition from the viewpoint of curability and curing sensitivity. It is more preferably% to 10% by mass, and even more preferably 0.5% by mass to 5% by mass.
  • a thermal radical polymerization initiator it is preferable to use a reducing agent in combination.
  • a reducing agent a known reducing agent that reacts with the above-mentioned polymerization initiator to generate radicals can be used.
  • Typical reducing agents include, for example, tertiary amines, thiourea derivatives, transition metal salts and the like.
  • Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine and N, N-dimethylparatoluidine.
  • Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea and the like.
  • Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate and the like. Of these, transition metal salts are preferred and vanadyl acetylacetonate is more preferred in terms of reactivity.
  • the content of the reducing agent is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the solid content mass of the curable resin composition.
  • the curable resin composition preferably contains a surfactant.
  • the surfactant include a nonionic surfactant, an anionic surfactant or a cationic surfactant which is an ionic surfactant, an amphoteric surfactant and the like.
  • nonionic surfactant examples include polyalkylene glycol monoalkyl ether, polyalkylene glycol monoalkyl ester, polyalkylene glycol monoalkyl ester and monoalkyl ether. More specifically, polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, polyethylene glycol monostearyl ester and the like can be mentioned. Of these, polyalkylene glycol monoalkyl ethers are preferable from the viewpoints of storage stability, light transmission of the obtained film, and haze.
  • anionic surfactant examples include alkyl sulfates, alkylbenzene sulfonates, alkyl phosphates and the like.
  • Examples of the cationic surfactant include hexadecylpyridinium chloride, hexadecylpyridinium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyldodecyldimethylammonium bromide, benzyldimethyltetradecylammonium chloride, and benzyloctadecyldimethylammonium chloride.
  • Preferable examples include stearyltrimethylammonium bromide, benzyldimethylhexadecylammonium chloride, dimethyldipalmitylammonium bromide, dimethyldioctadecylammonium bromide, trimethylamine hydrochloride, benzalkonium chloride, dodecyldimethylbenzylammonium chloride, benzethonium chloride, polyethyleneimine and the like. ..
  • amphoteric tenside agent examples include alkylcarboxybetaine and the like.
  • the surfactant is at least one selected from the group consisting of a fluorine-based surfactant, a silicone-based surfactant, and an acetylene-based surfactant from the viewpoint of layer formability and chipping resistance after curing. It is preferable to contain a surfactant, and it is more preferable to contain a fluorine-based surfactant.
  • the fluorine-based surfactant is a surfactant having a fluoroalkyl group, for example, Megafuck series manufactured by DIC Co., Ltd. (eg, Megafuck F-553, F-444, etc.), AGC Seimi Chemical Co., Ltd. ) (Example: Surfron S-221, etc.), Neos Co., Ltd., Futergent series (eg, Futergent 100, etc.) and the like.
  • silicone-based surfactant examples include the leveling material KP series (eg, KP-124, etc.) manufactured by Shin-Etsu Chemical Co., Ltd.
  • acetylene-based surfactant examples include the surfinol series and the olphin series (eg, surfinol 420, olphin E1004, etc.) manufactured by Nissin Chemical Industry Co., Ltd.
  • the curable resin composition may contain only one type of surfactant, or may contain two or more types of surfactant.
  • the content of the surfactant is preferably 0.005% by mass to 10% by mass with respect to the solid content mass of the curable resin composition from the viewpoint of layer formability and chipping resistance after curing. It is more preferably 0.01% by mass to 5% by mass, and particularly preferably 0.01% by mass to 1% by mass.
  • the curable resin composition may contain other components depending on the purpose, in addition to the above-mentioned components.
  • known additives can be used, and examples thereof include antistatic agents and preservatives.
  • the film for molding processing of the present disclosure has the coating layer of the curable resin composition of the present disclosure described above. Further, the film for molding processing of the present disclosure has a coating layer of the curable resin composition of the present disclosure described above and a thermoplastic resin layer.
  • the molding film of the present disclosure preferably has a resin base material, and may further have a colored layer, an adhesive layer, a cover film, and another layer, if necessary.
  • the molding film according to the present disclosure can be used for various purposes, and examples thereof are particularly preferably used for the interior / exterior of automobiles, the interior / exterior of electric products, packaging containers, and the like. Above all, it can be suitably used as a molding processing film used for the interior and exterior of an automobile, and particularly preferably used as a molding processing film used for the exterior of an automobile.
  • the molding film according to the present disclosure preferably has a resin base material.
  • the resin base material conventionally known base materials used for molding such as three-dimensional molding and insert molding can be used without particular limitation.
  • the resin base may be appropriately selected depending on the intended use of the decorative film, suitability for insert molding, and the like.
  • the shape and material of the resin base material are not particularly limited and may be appropriately selected as desired.
  • the resin base material is preferably a plate-shaped base material such as a film or a sheet from the viewpoint of ease of insert molding and chipping resistance.
  • the resin base material examples include polyester resin (eg, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, etc.), acrylic resin, urethane resin, urethane-acrylic resin, polycarbonate (PC) resin, acrylic-polycarbonate.
  • polyester resin eg, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, etc.
  • acrylic resin urethane resin
  • urethane-acrylic resin polycarbonate (PC) resin
  • acrylic-polycarbonate examples thereof include resin films containing resins such as resins, triacetyl cellulose (TAC), polyolefin resins (eg, polyethylene resins, polypropylene resins, etc.), cycloolefin polymers (COP), acrylonitrile / butadiene / styrene copolymer resins (ABS resins), etc. Be done.
  • TAC triacetyl cellulose
  • the resin base material is selected from the group consisting of PET resin, acrylic resin, urethane resin, urethane-acrylic resin, PC resin, acrylic-polycarbonate resin, and polypropylene resin from the viewpoint of moldability and strength.
  • a resin film containing at least one kind of resin is preferable, and a resin film containing at least one kind of resin selected from the group consisting of acrylic resin, PC resin, and acrylic-polycarbonate resin is more preferable.
  • the resin base material may be a laminated resin base material having two or more layers.
  • the laminated resin base material for example, an acrylic resin / polycarbonate resin laminated film is preferably mentioned.
  • the resin base material may contain additives other than the above-mentioned resin, if necessary.
  • Additives include, for example, mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, natural waxes, silicones and other lubricants; magnesium hydroxide, aluminum hydroxide and other inorganic flame retardants; halogen-based, Phosphorus-based organic flame retardants; organic or inorganic fillers such as metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, wood powder; additives (eg, antioxidants, UV inhibitors, etc.) Lubricants, dispersants, coupling agents, foaming agents, colorants, etc.); Engineering plastics other than the above-mentioned resins (eg, polyolefin resin, polyester resin, polyacetal resin, polyamide resin, polyphenylene ether resin, etc.) can be mentioned.
  • a commercially available product may be used as the resin base material.
  • Commercially available products include, for example, Technoroy (registered trademark) series (acrylic resin film or acrylic resin / polycarbonate resin laminated film, manufactured by Sumitomo Chemical Co., Ltd.); ABS film (manufactured by Okamoto Co., Ltd.); ABS sheet (Sekisui Molding Industry Co., Ltd.).
  • the thickness of the resin base material is determined according to the intended use of the molded product to be manufactured, the handleability of the sheet, etc., and is not particularly limited.
  • the thickness of the resin base material is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 20 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
  • the upper limit of the thickness is preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
  • the film for molding processing of the present disclosure has a coating layer formed by coating a curable resin composition.
  • the film for molding processing of the present disclosure preferably has a layer (coating layer) of the curable resin composition formed by coating the curable resin composition on the resin base material.
  • the coating layer is a layer containing a specific polymerizable resin (resin A), a specific polymerizable monomer (monomer B), and a polymerization initiator, and has curability.
  • the coating layer is also referred to as a “curable layer”.
  • the thickness of the coating layer is preferably in the range of 1 ⁇ m or more and 20 ⁇ m or less, and more preferably in the range of 5 ⁇ m or more and 15 ⁇ m or less, from the viewpoint of acid resistance.
  • the method for forming the curable layer is not particularly limited, and a known method can be referred to.
  • the curable layer can be formed by preparing a curable resin composition as a coating liquid for forming a curable layer, applying it to a resin substrate, for example, and drying it if necessary.
  • the details of the components contained in the curable resin composition are as described above.
  • the method for preparing the coating liquid for forming a curable layer is not particularly limited, and for example, it is produced by mixing a specific polymerizable resin (resin A), a specific polymerizable monomer (monomer B), a polymerization initiator, and an organic solvent. The method of doing this can be mentioned.
  • the coating of the coating liquid for forming a curable layer is not particularly limited, and for example, any known coating method such as spray coating, brush coating, roller coating, bar coating, and dip coating can be applied.
  • the resin substrate to which the curable layer forming coating liquid is applied is subjected to corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and ultraviolet irradiation treatment.
  • the surface treatment such as may be applied.
  • the coating liquid for forming a curable layer may be dried at room temperature (25 ° C.) or heated. Above all, the drying is preferably carried out by heating to 40 ° C. to 200 ° C. Further, from the viewpoint of suppressing thermal deformation of the resin base material, it is more preferable to heat the resin base material to 40 ° C. to 150 ° C. When heating is performed, the heating time is not particularly limited, but is preferably 1 to 30 minutes.
  • the organic solvent is not particularly limited, but a hydrophilic organic solvent is preferable.
  • the hydrophilic organic solvent include hydrophilic compounds such as alcohol compounds, glycol compounds, ether compounds and ketone compounds.
  • Examples of the hydrophilic organic solvent include methanol, ethanol, isopropanol, butanol, acetone, ethylene glycol, ethyl cellosolve and the like.
  • the hydrophilic organic solvent is preferably an alcohol compound from the viewpoint of availability and reduction of environmental load, and more preferably at least one compound selected from the group consisting of ethanol and isopropanol.
  • the coating liquid for forming a curable layer may contain water.
  • the solid content of the curable resin composition is preferably 1% by mass to 90% by mass, and more preferably 5% by mass to 80% by mass. It is particularly preferably 10% by mass to 80% by mass.
  • the molding film of the present disclosure may further have a colored layer between the resin base material and the coating layer (curable layer).
  • the film for molding processing according to the present disclosure can be suitably used as a coating substitute film or the like by having a colored layer.
  • the color of the colored layer is not particularly limited as long as it is a layer having a colorant, and from the viewpoint of visibility, a colored layer having a total light transmittance of 10% or less is preferable.
  • the colored layer can be selected from various colors such as black, gray, white, red, orange, yellow, green, blue, and purple, and may be a metallic color described later.
  • the colored layer is a paint such as a commercially available repair paint and a top coat paint (for example, nax real series, nax admira series, nax multi series (manufactured by Nippon Paint Co., Ltd.); Retan PG series (Kansai Paint Co., Ltd.). It may be formed by using (manufactured), etc.).
  • a paint such as a commercially available repair paint and a top coat paint
  • nax real series, nax admira series, nax multi series manufactured by Nippon Paint Co., Ltd.
  • Retan PG series Kansai Paint Co., Ltd.
  • the colored layer preferably contains a resin from the viewpoint of strength and scratch resistance.
  • a resin a binder resin described later is preferably mentioned.
  • the colored layer may be a layer containing a polymerizable compound and obtained by curing the polymerizable compound.
  • the colored layer may be a layer containing a polymerizable compound and a polymerization initiator.
  • Colorant Examples of the colorant contained in the colored layer include pigments and dyes, and pigments are preferable from the viewpoint of durability. Further, metal tabular particles, metal particles, or pearl pigments can also be applied to obtain a metallic tone. Further, a metallic colored layer can be provided by a method such as thin film deposition or plating.
  • the pigment various conventionally known inorganic pigments and organic pigments can be used.
  • the inorganic pigment include the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765.
  • white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, as well as carbon black, titanium black, titanium carbon, iron oxide, and graphite.
  • inorganic coloring pigments such as known chromatic pigments such as black pigments, iron oxide, barium yellow, cadmium red, and chrome yellow.
  • organic pigment examples include the organic pigment described in paragraph 0093 of JP-A-2009-256572.
  • phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green
  • azo pigments such as azo red, azo yellow and azo orange
  • quinacridone pigments such as quinacridone red, cinacridone red and cinacridone magenta
  • perylene such as perylene red and perylene maroon.
  • Pigments such as carbazole violet, anthrapyridine, flavanthron yellow, isoindrin yellow, induthron blue, dibrom anzaslon red, anthraquinone red, and diketopyrrolopyrrole.
  • Specific organic pigments include, for example, C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264 and other red pigments, C.I. I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green 7, 36, 58 and other green pigments, C.I. I. Pigment Blue 15: 6, etc. blue pigment, C.I. I. Examples include purple pigments such as Pigment Violet 23.
  • a pigment having light transmittance and light reflection may be included.
  • the glitter pigment include metal glitter pigments such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, and alloys thereof, interfering mica pigments, white mica pigments, graphite pigments, and glass flake pigments. And so on. These bright pigments may be uncolored or colored. When the bright pigment includes an exposure step described later, it is preferable to use the bright pigment within a range that does not hinder the curing by exposure.
  • the colorant may be used alone or in combination of two or more. Further, the particles of the inorganic pigment and the particles of the organic pigment may be used in combination.
  • the content of the colorant in the colored layer is 1% by mass to 50% by mass with respect to the total mass of the colored layer from the viewpoint of expressing the desired hue (for example, suppressing whitening) and molding processability. Is preferable, 5% by mass to 50% by mass is more preferable, and 10% by mass to 40% by mass is further preferable.
  • "whitening" in the present disclosure means that the colored layer changes so as to exhibit a whitish color as if a matte feeling is imparted.
  • the colored layer may contain a dispersant from the viewpoint of improving the dispersibility of the pigment contained in the colored layer.
  • a dispersant By including the dispersant, the dispersibility of the pigment in the formed colored layer is improved, and the hue can be made uniform in the obtained decorative film.
  • the dispersant can be appropriately selected and used according to the type and shape of the pigment, and is preferably a polymer dispersant.
  • the polymer dispersant include silicone polymers, acrylic polymers, polyester polymers and the like.
  • a silicone polymer such as a graft-type silicone polymer as the dispersant.
  • the weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, and even more preferably 2,500 to 3,000,000. When the weight average molecular weight is 1,000 or more, the dispersibility of the pigment is further improved.
  • dispersant a commercially available product may be used.
  • Commercially available products include EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan, Homogenol L-18 manufactured by Kao Corporation, Homogenol L-95, Homogenol L-100, and Lubrizol Japan Co., Ltd.
  • examples thereof include Solsperth 20000, Solsperth 24000, DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, DISPERBYK-182 manufactured by Big Chemie Japan Co., Ltd.
  • “homogenol”, “sol sparse”, and "DISPERBYK” are all registered trademarks.
  • the dispersant may contain only one kind or two or more kinds.
  • the content of the dispersant is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the colorant.
  • the colored layer preferably contains a binder resin from the viewpoint of proper molding process.
  • the binder resin is not particularly limited, and a known resin can be appropriately selected.
  • the binder resin is preferably a transparent resin from the viewpoint of obtaining a desired hue, and specifically, a resin having a total light transmittance of 80% or more is preferable.
  • the total light transmittance is a value measured by a spectrophotometer (for example, a spectrophotometer UV-2100 manufactured by Shimadzu Corporation).
  • binder resin examples include acrylic resin, silicone resin, polyester resin, urethane resin, and olefin resin.
  • acrylic resin, a urethane resin, or a composite resin thereof is preferable from the viewpoint of weather resistance and molding processability.
  • the "acrylic resin” which is a binder resin refers to a resin containing a structural unit derived from an acrylic monomer having a (meth) acryloyl group.
  • Acrylic resins include, for example, acrylic acid homopolymers, methacrylic acid homopolymers, acrylic acid ester homopolymers, methacrylic acid ester homopolymers, acrylic acid and other monomers copolymers, and methacrylics. Polymers of acid and other monomers, copolymers of acrylic acid esters and other monomers, copolymers of methacrylic acid esters and other monomers, urethane-modified copolymers having a urethane skeleton on the side chain Etc. are included.
  • the acrylic resin include a glycidyl methacrylate addition of a cyclohexyl methacrylate / methyl methacrylate / methacrylic acid copolymer, a random copolymer of benzyl methacrylate / methacrylic acid, a copolymer of allyl methacrylate / methacrylic acid, and a benzyl methacrylate / methacrylic acid.
  • examples thereof include a copolymer of acid / hydroxyethyl methacrylate.
  • a known silicone resin can be used.
  • a methyl-based straight silicone resin, a methylphenyl-based straight silicone resin, an acrylic resin-modified silicone resin, an ester resin-modified silicone resin, an epoxy resin-modified silicone resin, and an alkyd resin can be used.
  • examples thereof include a modified silicone resin and a rubber-based silicone resin.
  • methyl-based straight silicone resin, methylphenyl-based straight silicone resin, acrylic resin-modified silicone resin, or rubber-based silicone resin is preferable, and methyl-based straight silicone resin, methylphenyl-based straight silicone resin, or rubber-based silicone is preferable.
  • Resin is more preferred.
  • Commercially available products may be used as the silicone resin, and examples of the commercially available products include KR-300, KR-311, KR-251, X-40-2406M, and KR-282 manufactured by Shin-Etsu Chemical Co., Ltd.
  • polyester resin examples include linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
  • linear saturated polyester examples include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylene methylene terephthalate), polyethylene-2,6-naphthalate and the like.
  • the content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and 20% by mass to 60% by mass with respect to the total mass of the colored layer from the viewpoint of molding processability. % Is more preferable.
  • the colored layer may contain additives in addition to the above-mentioned components, if necessary.
  • a known additive can be used.
  • the thermal polymerization inhibitor (also referred to as a polymerization inhibitor, preferably a phenothiazine) described in paragraph 0018 of the above, and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can be mentioned.
  • the method for forming the colored layer is not particularly limited, and examples thereof include a method of forming a colored layer using a composition for forming a colored layer, a method of laminating colored films, and the like. Above all, a method of forming using a composition for forming a colored layer is preferable.
  • a method of applying the composition for forming a colored layer to form a colored layer and a method of printing the composition for forming a colored layer to form a colored layer can be mentioned. Examples of the printing method include screen printing, inkjet printing, flexographic printing, gravure printing, offset printing, and the like.
  • the composition for forming a colored layer preferably contains a colorant, and more preferably contains a colorant and an organic solvent. Further, the composition for forming a colored layer may further contain the above-mentioned other components.
  • the composition for forming a colored layer can be prepared, for example, by mixing an organic solvent and a component contained in the colored layer such as a colorant.
  • the content of the components contained in the colored layer is described as the content (% by mass) with respect to the total mass of the colored layer, but when these components are contained in the composition for forming the colored layer, the content thereof is used. ,
  • the content (% by mass) of the composition for forming a colored layer with respect to the total solid content shall be read as.
  • the composition for forming a colored layer contains a pigment as a colorant
  • a pigment dispersion liquid containing the pigment and its dispersant is prepared in advance, and the pigment dispersion liquid is used to form a composition for forming a colored layer. Is preferable from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment.
  • composition for forming a colored layer a composition prepared in advance by the above method may be used, a commercially available product or the like may be used, or a composition for forming a colored layer may be prepared immediately before coating. ..
  • organic solvent a commonly used organic solvent can be used without particular limitation. Specific examples thereof include organic solvents such as esters, ethers, ketones and aromatic hydrocarbons. In addition, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate similar to Solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073. , Or methyl lactate and the like can also be suitably used as an organic solvent in the composition for forming a colored layer.
  • organic solvents such as esters, ethers, ketones and aromatic hydrocarbons.
  • organic solvents 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, diethylene glycol monoethyl ether acetate (ethylcarbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone and the like are preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the content of the organic solvent is not particularly limited, but is preferably 5% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the composition for forming the colored layer (coating liquid). ..
  • the thickness of the colored layer may be selected according to the hue, purpose, etc., and may be 1 ⁇ m or more and 25 ⁇ m or less.
  • the molding film according to the present disclosure may have an adhesive layer from the viewpoint of adhering to another member (for example, an automobile steel plate).
  • the material of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a layer containing a known adhesive or an adhesive, and a layer containing an adhesive is preferable.
  • Adhesive examples include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives and the like. Urethane resin adhesives or silicone adhesives are preferable from the viewpoint of higher adhesive strength.
  • the pressure-sensitive adhesive examples include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. Further, as an example of the adhesive, the acrylic adhesive and the ultraviolet (UV) curable type described in "Characteristic evaluation of release paper / release film and adhesive tape and their control technology" (Information Mechanism, 2004, Chapter 2). Examples thereof include adhesives and silicone adhesives.
  • the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth) acrylic monomer ((meth) acrylic polymer). When a pressure-sensitive adhesive is contained, a pressure-sensitive adhesive may be further contained.
  • the method for forming the adhesive layer is not particularly limited, and is a method of laminating a cover film on which the adhesive layer is formed, a method of laminating the adhesive layer alone, or applying a composition containing an adhesive or an adhesive to a resin base material. How to do it, etc.
  • the laminating method or the coating method is not particularly limited, and a known method can be used.
  • the thickness of the adhesive layer is preferably 0.5 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 80 ⁇ m, and even more preferably 25 ⁇ m to 50 ⁇ m in terms of both adhesive strength and handleability.
  • the molding film according to the present disclosure preferably has a thermoplastic resin layer on the coating layer as a protective layer for protecting the coating layer (curable layer).
  • a thermoplastic resin layer By having the thermoplastic resin layer, it is possible to suppress blocking at the time of film winding and to suppress stains.
  • thermoplastic resin layer a material having flexibility and being soluble by washing with water is suitable. Further, when the cover film on which the adhesive layer is formed is laminated to form the thermoplastic resin layer, a material having good peelability of the thermoplastic resin layer at the time of laminating is preferable.
  • the thermoplastic resin layer is preferably a layer containing a resin such as polyvinyl alcohol.
  • the thickness of the thermoplastic resin layer is preferably in the range of 0.1 ⁇ m or more and 10 ⁇ m or less, and preferably in the range of 1 ⁇ m or more and 5 ⁇ m or less, from the viewpoint of exhibiting the function as a protective layer and maintaining a good curing reaction of the curable layer. ..
  • thermoplastic resin layer can be suitably formed by applying a coating liquid for forming a thermoplastic resin layer or laminating the thermoplastic resin layer.
  • the method for applying and laminating the thermoplastic resin layer is not particularly limited, and examples thereof include known methods for applying and laminating.
  • the molding film according to the present disclosure may have a layer other than the above-mentioned layer depending on its use.
  • the other layer may be a film for molding or a layer known in its use.
  • examples of other layers include a reflective layer, a self-healing layer, an antistatic layer, an antifouling layer, an electromagnetic waveproof layer, and a conductive layer.
  • the other layer can be formed by a known method. Examples of the other layer include a method in which a composition containing the components contained in the layer (layer-forming composition) is applied in a layered manner and dried.
  • the molding film according to the present disclosure may have a cover film as a protective layer of the adhesive layer.
  • a cover film By having a cover film, it is possible to prevent stains and the like.
  • a cover film a material having flexibility and good peelability from a contact layer (adhesive layer in the case of a cover film arranged on the surface of the adhesive layer) can be used without limitation, and polyolefin can be used. Examples thereof include resin films such as films (eg, polyethylene films, etc.).
  • the method of attaching the cover film is not particularly limited, and a known method may be mentioned.
  • a method of laminating the cover film on the surface of the outermost layer may be used.
  • FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the molding film according to the present disclosure.
  • the molding film 10 has a curable layer 12 which is a coating layer on the resin base material 14.
  • the film 10 for molding processing can be obtained by applying the curable resin composition of the present disclosure on a resin base material.
  • FIG. 2 is a schematic cross-sectional view showing another example of the molding processing film according to the present disclosure.
  • the molding film 100 has a curable layer 12 which is a coating layer on the resin base material 14, and a colored layer 16 is arranged between the resin base material 14 and the curable layer 12.
  • the thermoplastic resin layer 22 is arranged on the side opposite to the side where the colored layer of the curable layer 12 is arranged.
  • the adhesive layer 18 and the cover film 20 are arranged in this order on the side of the resin base material 14 opposite to the side on which the curable layer 12 is arranged.
  • the colored layer 16, the adhesive layer 18, and the cover film 20 are arbitrary layers and may not be included in the molding film 100.
  • the curable resin composition of the present disclosure is applied (formation of the curable layer 12) on a resin base material having a colored layer as shown in FIG. 2, and further coated for a thermoplastic resin layer. It can be obtained by applying a liquid (forming the thermoplastic resin layer 22). Further, by applying, for example, a coating liquid for an adhesive layer (forming an adhesive layer 18) on the side of the resin base material 14 opposite to the side having the colored layer 16, and attaching a cover film, the adhesive is adhered as shown in FIG. The layer 18 and the cover film 20 can be formed.
  • the forming film according to the present disclosure can be used, for example, as a coating substitute film for an automobile steel sheet. In this case, in the film 10 for molding in FIG.
  • the resin base material 14 is a portion in contact with the automobile steel sheet. Further, in the film 100 for molding in FIG. 2, it is preferable that the adhesive layer 18 exposed by peeling off the cover film 20 becomes a portion in contact with the automobile steel plate.
  • the molded product of the present disclosure can be obtained by a known molding method using a film for molding processing, but is preferably obtained by a molding method using the film for molding processing of the present disclosure.
  • the molded product of the present disclosure is more preferably obtained by a molding method of molding and curing the molding film of the present disclosure, and particularly preferably obtained by the following molding method of the present disclosure. That is,
  • the molding method of the present disclosure includes a step of molding the molding process film of the present disclosure (hereinafter referred to as a molding step) and a step of curing a coating layer (curable layer) in the molded film for molding processing (hereinafter referred to as a curable layer). It is a molding method including a curing step).
  • the molded product of the present disclosure preferably has a water permeation amount of 500 g / m 2 / day or less when allowed to stand in water at 80 ° C. for 24 hours, and is preferably 50 g / m 2 / day to 400 g / m 2 / day. Is more preferable, and 50 g / m 2 / day to 300 g / m 2 / day is even more preferable. When the amount of water permeation is within the above range,
  • the amount of water permeation (also referred to as the amount of water permeation) is a value measured by the following method.
  • the curable resin composition is applied to a base material, and the formed coating layer is cured by irradiating it with ultraviolet (UV) light with an integrated exposure amount of 1,000 mJ / cm 2 using an exposure device, and after curing on the base material.
  • a film having a coating layer (curing layer) of the above is obtained.
  • the opening of an aluminum container containing calcium chloride as a moisture-absorbing material is sealed by stacking butyl rubber and a film in this order to obtain a test piece.
  • the test piece is immersed in water at 80 ° C. and allowed to stand for 24 hours. After 24 hours, take it out of the water and measure the mass increase (water permeation amount, unit: g / m 2 / day) from the following formula.
  • Moisture permeation test piece mass after standing-test piece mass before standing
  • the molding method of the present disclosure includes a step of molding a film for molding processing according to the present disclosure. Since the molding film of the present disclosure has excellent molding processability and can be suitably used for manufacturing a molded product, molding is performed by at least one molding method selected from the group consisting of, for example, three-dimensional molding and insert molding. More preferably.
  • the method for producing a molded product will be described in detail by taking insert molding as an example.
  • a molded product is obtained, for example, by placing a film for molding in a mold in advance and injecting a resin into the mold.
  • a molded product in which a film for molding processing is integrated on the surface of the molded product can be obtained.
  • the method for producing a molded product is a step of arranging a molding film in a mold for injection molding and closing the mold, a step of injecting a molten resin into the mold, and a step of injecting the injected molten resin. Includes a step of solidifying and taking out.
  • the injection mold (that is, the molding mold) used for manufacturing the molded product is a mold having a convex shape (that is, a male mold) and a mold having a concave shape corresponding to the convex shape (that is, a female mold). ).
  • the molding processing film is placed on the molding surface which is the inner wall surface of the female mold, and then the mold is closed.
  • the forming process film is preformed (preformed) in advance using the forming die to form the forming process film. It is also possible to impart a three-dimensional shape to the film in advance and then apply the film for molding to the molding die.
  • the fixing pin of the male die is inserted into the alignment hole of the female die.
  • the alignment hole may be formed in advance at the end portion of the film for molding (position where the three-dimensional shape is not imparted after molding) in the female mold.
  • the fixing pin may be formed in advance at a position where it fits with the alignment hole in the male mold.
  • the following method is used to align the molding film and the molding die with the molding film inserted in the molding die. Can be used.
  • the alignment mark is recognized by using two or more diagonal alignment marks when viewed from the product portion of the injection molded product (molded article).
  • the molten resin is injected into the molding die into which the molding process film is inserted.
  • the molten resin is injected onto the resin base material side.
  • the temperature of the molten resin injected into the molding die can be set according to the physical characteristics of the resin used.
  • the temperature of the molten resin is preferably in the range of 240 ° C. or higher and 260 ° C. or lower.
  • the position of the injection port (injection port) of the male mold is adjusted to match the shape of the molding die and the type of molten resin in consideration of the heat and gas generated when the molten resin is injected into the molding die. May be set. As a result, it is possible to prevent the film for molding from being abnormally deformed.
  • the molding die is opened, and the molding process film is fixed from the molding die to the solidified molten resin.
  • the intermediate molded product a burr and a dummy portion of the molded product are integrated around the molded product that is finally a product.
  • the dummy portion there is an insertion hole formed by inserting the fixing pin in the above-mentioned positioning. Therefore, a molded product can be obtained by performing a finishing process for removing the above-mentioned burrs and dummy portions from the intermediate molded product before the finishing process.
  • three-dimensional molding is also preferably used.
  • the three-dimensional molding include thermoforming, vacuum forming, compressed air forming, and vacuum forming.
  • the method of vacuum forming is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferable.
  • the vacuum refers to a state in which the room is evacuated to a degree of vacuum of 100 Pa or less.
  • the temperature at the time of three-dimensional molding may be appropriately set according to the molding processing film (resin base material when the molding processing film has a resin base material), and is preferably in a temperature range of 60 ° C. or higher, preferably 80 ° C. or higher. The temperature range of 100 ° C.
  • the temperature at the time of three-dimensional molding refers to the temperature of the molding processing film (resin base material if the molding processing film has a resin base material) used for three-dimensional molding, and refers to the molding processing film (molding processing film).
  • the temperature at the time of three-dimensional molding refers to the temperature of the molding processing film (resin base material if the molding processing film has a resin base material) used for three-dimensional molding, and refers to the molding processing film (molding processing film).
  • the film has a resin substrate, it is measured by attaching a thermocouple to the surface of the resin substrate).
  • the above vacuum forming can be performed by using a vacuum forming technique widely known in the molding field, and for example, vacuum forming may be performed using Formech 508FS manufactured by Nippon Sekki Kogyo Co., Ltd.
  • the molding method of the present disclosure includes a step (curing step) of curing the coating layer (curable layer) in the molded film for molding processing.
  • the curing method in the curing step is not particularly limited, and the specific polymerizable resin (resin A), the specific polymerizable monomer (monomer B), the polymerization initiator, and the crosslinkability of the organic resin C contained in the curable layer are not particularly limited. It may be selected according to the basis.
  • a curing method a method of curing the coating layer (curable layer) by applying light or heat is preferable, and a method of curing the coating layer (curable layer) by light irradiation is more preferable.
  • the light irradiation in the curing step may be performed from any of the two main surfaces of the molding film, but in the case of a molding film having a resin base material, for example, the resin base material is used. It is preferable to carry out from the side having the coating layer (curable layer) of.
  • the cover film is provided as the outermost layer of the two main surfaces of the molding film on the side having the curable layer, light irradiation is performed with the cover film held (the state before the cover film is peeled off). May be good.
  • the total light transmittance of the cover film is preferably 80% or more, more preferably 90% or more. ..
  • the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used.
  • the light source for light irradiation any light source capable of irradiating light in a wavelength range capable of curing the curable layer (for example, 365 nm, 405 nm) can be appropriately selected and used.
  • Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.
  • the exposure amount is not particularly limited and may be suitably set, preferably 5mJ / cm 2 ⁇ 2,000mJ / cm 2, 10mJ / cm 2 ⁇ 1,500mJ / cm 2 is more preferable.
  • Light irradiation may be performed in an atmospheric environment.
  • the film for molding does not have a thermoplastic resin layer on the coating layer (curable layer)
  • the colored layer not only the curable layer but also the colored layer may be cured simultaneously or sequentially as needed.
  • the colored layer preferably contains a polymerizable compound and a photopolymerization initiator.
  • a cured colored layer can be obtained by irradiating the colored layer containing the polymerizable compound and the photopolymerization initiator with light.
  • the heating temperature and heating time when curing is performed by heat are not particularly limited and may be appropriately selected according to the thermal polymerization initiator and the like to be used.
  • the heating temperature is preferably 60 ° C. or higher and 200 ° C. or lower, and the heating time is preferably 5 minutes to 2 hours.
  • the heating means is not particularly limited, and known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
  • the use of the molded product obtained as described above is not particularly limited and can be used for various articles.
  • Examples of applications for the molded product include the interior / exterior of an automobile, the interior / exterior of an electric product, a packaging container, and the like. Among them, the interior and exterior of the automobile are preferable, and the exterior of the automobile is more preferable.
  • the molding method of the present disclosure may include a step of producing a molding processing film (molding processing film producing step) to be molded in the molding step.
  • the process for producing a film for molding may include a step of applying the curable resin composition of the present disclosure on a resin base material to form a coating layer.
  • the process for producing a film for molding is a step of applying the curable resin composition of the present disclosure on a resin base material to form a coating layer, and a step of forming a thermoplastic resin layer on the coating layer by coating. It may have a step (thermoplastic resin layer forming step).
  • thermoplastic resin is placed on the coating layer of the curable resin composition of the present disclosure formed by coating on the resin base material. It may have a step (thermoplastic resin layer forming step) of forming a layer by coating.
  • each layer such as the formation of the coating layer and the formation of the thermoplastic resin layer in the process of producing the film for molding is as described above.
  • the molding method of the present disclosure preferably has the following aspects. That is, The molding method of the present disclosure includes a step of molding the molding film of the present disclosure (molding step), a step of curing the coating layer in the molded molding film (curing step), and thermoplasticity after the curing. It is an embodiment having a step of removing a resin layer (hereinafter referred to as a removal step).
  • a film for molding processing having a coating layer and a thermoplastic resin layer is used, and the coating layer and the thermoplastic resin layer are molded.
  • thermoplastic resin layer is the same as the molding method described above in the case of having only a coating layer, and thus the description thereof is omitted here. Further, since the curing step is also as described above, the description thereof is omitted here. Since the step of forming the thermoplastic resin layer has been described in the section of the thermoplastic resin layer, the description thereof is omitted here.
  • the thermoplastic resin layer is removed after molding. If the thermoplastic resin layer is formed using a material that can be dissolved by washing with water, it can be removed with water.
  • the specific removal method is not particularly limited as long as the thermoplastic resin layer can be removed, and examples thereof include a method of contacting with running water to wash away, a method of immersing in water, and the like. Distilled water, purified water, or the like can be used as the water.
  • the temperature of the water used for washing with water is preferably 20 ° C. or higher and 60 ° C. or lower.
  • % and “part” mean “% by mass” and “part by mass”, respectively, unless otherwise specified.
  • Example 1 -Making a film for molding- ⁇ Formation of curable layer> The following components were mixed and stirred at 25 ° C. for 24 hours to obtain a hard coat coating liquid 1 (curable resin composition).
  • -Methyl ethyl ketone 70 parts-acrylate-modified acrylic resin A (UV curable acrylic resin; acrylic resin with a number average molecular weight of 10,000 or more and 500,000 or less (denoted as acrylic polymer in Table 1)): 12.5 parts-A9300S (molecular weight less than 10,000) Monomer): 12.5 parts ⁇ Irgacure127 ( ⁇ -hydroxyacetophenone compound, manufactured by BASF; polymerization initiator): 1.47 parts ⁇ F-553 (manufactured by DIC Co., Ltd .; fluorosurfactant): 0. 03 copies
  • the obtained hard coat coating liquid 1 is applied onto an acrylic resin base material (Technoloy S001GUBX, thickness 155 ⁇ m, manufactured by Sumika Acrylic Sales Co., Ltd.) so as to have a thickness of 10 ⁇ m, and dried at 80 ° C. for 5 minutes. , A film 1A with a hard coat layer (curable layer) was obtained.
  • an acrylic resin base material (Technoloy S001GUBX, thickness 155 ⁇ m, manufactured by Sumika Acrylic Sales Co., Ltd.)
  • thermoplastic resin layer liquid 1.
  • PVA105 polyvinyl alcohol, manufactured by Kuraray Co., Ltd.
  • thermoplastic resin layer liquid 1 is applied onto a film 1A with a hard coat layer so as to have a thickness of 1.5 ⁇ m, and dried at 80 ° C. for 10 minutes (thermoplastic resin layer forming step) to obtain thermoplasticity.
  • a film 1B film for molding having a laminated structure of a resin layer / a hard coat layer (curable layer (coating layer)) / a base material was obtained.
  • ⁇ Moldability evaluation Blocking resistance>
  • the obtained film 1B was cut into a size of 10 cm ⁇ 10 cm to prepare an evaluation sample, and the two evaluation samples were superposed so that the resin base material and the thermoplastic resin layer were in contact with each other, and a 10 kg weight was placed on the film at room temperature. It was allowed to stand at (25 ° C.) for 24 hours. After standing, the two samples were separated and evaluated according to the following criteria.
  • the film 1B was biaxially stretched using a biaxial stretching device so that the length and the horizontal length were each tripled (molding step).
  • the film after biaxial stretching is subjected to a light exposure device (nitrogen purge UV irradiator, GS Yuasa Co., Ltd., metal halide lamp, output 120 W / cm) under an atmospheric atmosphere, and the integrated exposure amount is set to 1,000 mJ / cm 2. It was cured by irradiating with ultraviolet rays (UV) (curing step) to obtain a film 1C (molded product).
  • UV ultraviolet rays
  • thermoplastic resin layer ⁇ Removal of thermoplastic resin layer> The surface of the film 1C was brought into contact with running water at a temperature of 25 ° C. and washed with water for 30 seconds to remove the thermoplastic resin layer (removal step), and a film 1D (molded product) was obtained.
  • the obtained hard coat coating liquid 1 is applied onto a saponified triacetate cellulose (TAC) substrate (thickness 125 ⁇ m) so as to have a thickness of 10 ⁇ m, and an integrated exposure of 1,000 mJ / cm 2 is carried out by the above-mentioned light exposure device. It was cured by irradiating an amount of UV light to obtain a film 1E (film for molding processing) having a laminated structure of a hard coat layer / a TAC base material.
  • TAC triacetate cellulose
  • ⁇ Acid resistance Sulfuric acid resistance> 0.1 N (mol / l) sulfuric acid was added dropwise to the surface of the hard coat layer of the obtained film 1D, and the film was left at 55 ° C. for 24 hours, and then the state of the film was visually confirmed.
  • the evaluation criteria are shown below.
  • C At least one of significant swelling, discoloration, or exfoliation is observed on the entire surface of the hard coat layer.
  • Example 2 to 11 The films 2A to 11A with the hard coat layer (curable resin composition layer) were prepared in the same manner as in Example 1 except that the hard coat coating liquid 1 (curable resin composition) was changed to the composition shown in Table 1.
  • films 2B to 11B thermoplastic resin layer / hard coat layer / film for molding processing having a laminated structure of a base material
  • films 2C to 11C molded product
  • films 2D to 11D thermoplastic resin
  • a molded product from which the layer was removed) and films 2E to 11E (a film for molding processing having a laminated structure of a hard coat layer / TAC base material) were produced.
  • the obtained film was used and evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.
  • Example 3 A film 3A-2 with a hard coat layer was obtained in the same manner as in Example 1 except that the hard coat coating liquid 1 (curable resin composition) was changed to the composition shown in Table 1, and then the film 3B was further obtained.
  • -2 thermoplastic resin layer / hard coat layer / film for molding processing having a laminated structure of a base material
  • film 3C-2 molded product
  • film 3D-2 molded product from which the thermoplastic resin layer is removed
  • Film 3E-2 (a film for molding processing having a laminated structure of a hard coat layer / a TAC base material) was produced.
  • the obtained film was used and evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.
  • Example 12 to 14 -Making a film for molding-
  • a hard coat coating liquid (curable resin composition) having the composition shown in Table 1 was prepared and placed on an acrylic resin base material (Technoloy S001GUBX, thickness 155 ⁇ m, manufactured by Sumika Acrylic Sales Co., Ltd.) so as to have a thickness of 10 ⁇ m.
  • the film was applied and dried at 80 ° C. for 5 minutes to obtain films 12A to 14A with a hard coat layer (curable resin composition layer).
  • films 12B to 14B films for molding having a laminated structure of a thermoplastic resin layer / hard coat layer / base material
  • films 12C to 14C molded products
  • films 12D to 14D films 12D to 14D.
  • films 1B-2 and 2B-2 (a film for molding processing having a laminated structure of a thermoplastic resin layer / a hard coat layer / a base material), films 1C-2 and 2C-2 ( Molded product), film 1D-2, 2D-2 (molded product from which the thermoplastic resin layer is removed), film 1E-2, 2E-2 (film for molding processing having a laminated structure of hard coat layer / TAC base material) Were prepared respectively.
  • the obtained film was used and evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.
  • Acrylate-modified acrylic resin A: MMA / IOBA copolymer (UV curable acrylic resin, weight average molecular weight 120,000, including acryloyl group)
  • Acrylate-modified acrylic resin B: MMA / dicyclopentenyl acrylate copolymer (UV curable acrylic resin, weight average molecular weight 90,000, including acryloyl group)
  • Metalacrylate-modified acrylic resin C: MMA / IOBA copolymer (UV curable acrylic resin, weight average molecular weight 1
  • MMA methyl methacrylate
  • IOBA isobolonyl acrylate
  • MEK methyl ethyl ketone
  • ⁇ Synthesis of acrylate-modified acrylic resin B > 45 parts of methyl methacrylate (MMA), 30 parts of dicyclopentenyl acrylate, and 88 parts of glycidyl methacrylate in a methyl ethyl ketone (MEK) solvent as a radical polymerization initiator V-601 (2,2'-azobis (isobutyric acid)). Copolymerization was carried out by stirring at 65 ° C. for 3 hours using dimethyl and Fujifilm Wako Pure Chemical Industries, Ltd. Further, in the presence of tetraethylammonium chloride, it was reacted with 62.6 parts of acrylic acid to remove the solvent and purified to obtain an acrylate-modified acrylic resin B. The number average molecular weight of the obtained acrylate-modified acrylic resin B was 90,000.
  • MMA methyl methacrylate
  • IOBA isobolonyl acrylate
  • MEK methyl ethyl ketone
  • the vinyl ether-modified acrylic resin C was obtained by reacting with 40 parts of 2-chloroethyl vinyl ether to remove the solvent and purifying. Obtained.
  • the number average molecular weight of the obtained vinyl ether-modified acrylic resin D was 80,000.
  • A-DCP Tricyclodecanedimethanol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • DPHA Dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • AD-TMP Ditrimethylolpropane Tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • TMPTA Trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • Irgacure 127 Photopolymerization Initiator (manufactured by IGM Resins BV)
  • F-553 Megafuck F-553 (surfactant; manufactured by DIC Corporation)
  • PVA105 Polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd.)
  • the molding processing films of Examples 1 to 14 are compared with the molding processing films of Comparative Examples 1 to 3, and have a (meth) acrylic resin having a (meth) acryloyl group and a (meth) acryloyl. Since a monomer having a group is used, it is excellent in molding processability and acid resistance after curing.

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Abstract

Un mode de réalisation de la présente invention concerne : une composition de résine durcissable qui contient une résine (méth)acrylique qui comprend un groupe (méth)acryloyle ou un groupe éther vinylique, tout en ayant un poids moléculaire moyen en nombre de 10 000 à 500 000, un monomère qui comprend un groupe (méth)acryloyle ou un groupe éther vinylique, tout en ayant un poids moléculaire inférieur à 10 000 et un initiateur de polymérisation ; la composition de résine durcissable dans laquelle le monomère a une structure partielle représentée par la formule (1) ; un film pour moulage, ledit film utilisant la composition de résine durcissable ; un procédé de moulage qui utilise le film pour moulage ; et un article moulé. Dans la formule (1), chacun de R1 à R3 représente indépendamment un atome d'hydrogène, un groupe hydroxy, un groupe halogène, un groupe alkyle ayant de 1 à 18 atomes de carbone, un groupe ayant un groupe (méth)acryloyle ou un groupe ayant un groupe éther vinylique ; et au moins l'une des fractions R1 à R3 a un groupe (méth)acryloyle ou un groupe éther vinylique.
PCT/JP2021/018491 2020-05-15 2021-05-14 Composition de résine durcissable, film pour moulage, article moulé et procédé de moulage WO2021230370A1 (fr)

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