WO2022168810A1 - 積層体及びその製造方法 - Google Patents

積層体及びその製造方法 Download PDF

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Publication number
WO2022168810A1
WO2022168810A1 PCT/JP2022/003713 JP2022003713W WO2022168810A1 WO 2022168810 A1 WO2022168810 A1 WO 2022168810A1 JP 2022003713 W JP2022003713 W JP 2022003713W WO 2022168810 A1 WO2022168810 A1 WO 2022168810A1
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Prior art keywords
formula
laminate
group
resin composition
meth
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Legal status (The legal status 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 status listed.)
Ceased
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PCT/JP2022/003713
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English (en)
French (fr)
Japanese (ja)
Inventor
将太 亀井
大志 中瀬古
昭武 植木
泰隆 福永
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Mitsubishi Gas Chemical Co Inc
MGC Filsheet Co Ltd
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Mitsubishi Gas Chemical Co Inc
MGC Filsheet Co Ltd
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Priority to CN202280013268.1A priority Critical patent/CN116917125A/zh
Priority to JP2022540873A priority patent/JP7217388B2/ja
Publication of WO2022168810A1 publication Critical patent/WO2022168810A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • the present invention relates to a laminate with a reduced amount of residual solvent and a method for producing the same.
  • a resin film laminate having a coating layer (hereinafter also referred to as "surface layer") has been used in various fields (see Patent Document 1).
  • a laminate of resin films is used in front panels and rear panels of mobile devices, interior parts of automobiles, and the like.
  • a laminate having a laminated structure in which a surface layer is laminated on a substrate layer is generally obtained by applying a resin composition containing an organic solvent to the substrate layer and then drying the resulting coated product.
  • a resin composition containing an organic solvent to the substrate layer and then drying the resulting coated product.
  • the present inventors have made intensive studies to solve the above problems. As a result, in the production of a laminate having at least a substrate layer and a surface layer, a plurality of solvents having predetermined boiling points are used, and the drying conditions are kept within a certain range. was found to be effectively suppressed.
  • the present invention has been completed through further studies based on such findings.
  • a laminate comprising at least a substrate layer and a surface layer provided on the surface of the substrate layer,
  • the resin composition contains a (meth)acryloyl polymer (C), and the (meth)acryloyl polymer (C) has a (meth)acrylic equivalent weight of 200 to 600 g/eq and a weight average of 5,000 to 200,000. has a molecular weight, A laminate having a residual solvent amount of 82 mg/m 2 or less.
  • m is an alkylene group having 1 to 4 carbon atoms or a single bond
  • n is an alkyl group having 1 to 4 carbon atoms or hydrogen
  • p is a single bond or an alkylene group having 1 or 2 carbon atoms
  • q is an alkyl group having 1 to 12 carbon atoms in total, which may contain at least one substituent of an epoxy group, a hydroxyl group, an acryloyl group, and a methacryloyl group, or hydrogen.
  • m is an alkylene group having 1 or 2 carbon atoms
  • n is an alkyl group having 1 or 2 carbon atoms
  • p is a single bond or a methylene group
  • q is an alkyl group having a total of 1 to 6 carbon atoms which may contain at least one substituent of a glycidyl group, a hydroxyl group, and an acryloyl group, or hydrogen.
  • m is a methylene group
  • n is a methyl group
  • p is a single bond
  • q is a methyl group
  • the laminate according to ⁇ 3> which is an alkyl group having 8 or less carbon atoms containing a hydroxyl group and an acryloyl group.
  • the (meth)acryloyl polymer (C) contains at least one of repeating units represented by the following formulas (II-a), (II-b), and (II-c) Laminate as described.
  • the formula (II-a) Based on the total number of moles of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b), and the repeating unit of the formula (II-c), the formula (II-a) The repeating unit is 30 to 85 mol%, the repeating unit of formula (II-b) is 5 to 30 mol%, and the repeating unit of formula (II-c) is 10 to 40 mol%.
  • the molar ratio of the repeating unit of formula (II-a), the repeating unit of formula (II-b), and the repeating unit of formula (II-c) is 4.5 to 5.5:1.
  • the (meth)acryloyl polymer (C) further contains a pentaerythritol-based polyfunctional acrylate compound.
  • the pentaerythritol-based polyfunctional acrylate compound is pentaerythritol tetraacrylate represented by the following formula (III-a), and dipentaerythritol hexaacrylate represented by formula (III-b), and pentaerythritol triacrylate.
  • the laminate according to ⁇ 8> which is one or more selected from the group consisting of: ⁇ 10>
  • ⁇ 11> The laminate according to any one of ⁇ 1> to ⁇ 10>, wherein the resin composition is radiation-curable.
  • the resin composition further contains a photopolymerization initiator.
  • the base layer contains a thermoplastic resin.
  • ⁇ 14> The laminate according to any one of ⁇ 1> to ⁇ 13>, which is a cured film.
  • ⁇ 15> A molded product obtained by thermoforming the laminate according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> A method for producing a laminate according to any one of ⁇ 1> to ⁇ 14>, the method comprising: Step 1 of applying a resin composition containing a radiation-curable resin and an organic solvent to the surface of a substrate layer to obtain a coated product; Step 2 of drying the obtained coated material to form a surface layer on the surface of the substrate layer including
  • the laminate comprises at least a substrate layer and a surface layer,
  • the resin composition contains an organic solvent (A) with a boiling point of less than 120° C.
  • the resin composition contains a (meth)acryloyl polymer (C), and the (meth)acryloyl polymer (C) has a (meth)acrylic equivalent weight of 200 to 600 g/eq and a weight average of 5,000 to 200,000. has a molecular weight,
  • a method wherein the residual solvent amount in the laminate is 82 mg/m 2 or less.
  • step 2 at least two drying ovens capable of heating the coated material to 60 ° C. or higher are used, The method according to ⁇ 16> or ⁇ 17>, wherein the drying oven temperature in the first drying oven is in the range of 60 to 90°C, and the drying oven temperature in the second drying oven is in the range of 100 to 130°C. ⁇ 19>
  • the thickness of the base layer is 0.1 mm to 1.0 mm, and the thickness of the layer of the resin composition applied to the surface of the base layer is 1.0 ⁇ m to 10 ⁇ m, ⁇ 16> The method according to any one of ⁇ 18>.
  • the present invention can provide a laminate in which the amount of residual solvent is significantly reduced without impairing properties required for a laminate for a molded article such as formability, scratch resistance, hardness and adhesion. . Since the laminate of the present invention has such excellent characteristics, it is possible to provide a molded article in which the amount of residual solvent is effectively suppressed during the molding process. Such molded articles are suitable for applications such as automobile interiors and housings for electronic devices.
  • the present invention also provides a method for producing a laminate with significantly reduced residual solvent content, and a molded article obtained from the laminate.
  • FIG. 1 is a cross-sectional view showing an example of a laminate 10 including a substrate layer 30 and a surface layer 20 provided on the surface of the substrate layer 30. As shown in FIG.
  • the inventors found that the amount of solvent remaining in the laminate can be significantly reduced in some cases.
  • the present inventors found that when a layer is laminated on a base material layer by printing or the like, if the initial drying temperature is high, the solvent will be trapped in the coating film. We discovered that the solvent residue was caused by
  • the laminate 10 of the present invention includes at least a substrate layer 30 and a surface layer 20 provided on the surface of the substrate layer 30 (FIG. 1).
  • the laminate is a molding laminate.
  • the laminate 10 of the present invention may comprise additional layers, such as masking layers, on the surface of the surface layer 20 that is not in contact with the substrate layer 30 .
  • the residual solvent amount in the laminate 10 is 82 mg/m 2 or less.
  • a laminate comprising at least a substrate layer and a surface layer provided on the surface of the substrate layer,
  • the resin composition contains a (meth)acryloyl polymer (C), and the (meth)acryloyl polymer (C) has a (meth)acrylic equivalent weight of 200 to 600 g/eq and a weight average of 5,000 to 200,000. has a molecular weight, A laminate having a residual solvent amount of 82 mg/m 2 or less is provided.
  • the base layer 30 may be composed of one layer, or may be composed of two or more layers.
  • the substrate layer 30 may be composed of, for example, a first resin layer 31 and a second resin layer 32 (FIG. 1).
  • the base material layer 30 contains resin, more preferably thermoplastic resin.
  • the type of thermoplastic resin is not particularly limited, but polycarbonate (PC) resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide ( PI), cycloolefin copolymer (COC), norbornene-containing resin, polyether sulfone, cellophane, aromatic polyamide, and other various resins are used.
  • the thermoplastic resin of the substrate layer preferably contains at least polycarbonate resin.
  • the substrate layer contains a thermoplastic resin.
  • -[O-R-OCO]-units (where R is an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic is not particularly limited as long as it contains both groups and further has a linear structure or a branched structure, but a polycarbonate having a bisphenol skeleton is preferable, and has a bisphenol A skeleton or a bisphenol C skeleton.
  • Polycarbonates are particularly preferred.
  • a mixture or copolymer of bisphenol A and bisphenol C may be used as the polycarbonate resin.
  • a bisphenol C-based polycarbonate resin for example, a polycarbonate resin containing only bisphenol C, or a polycarbonate resin containing a mixture or copolymer of bisphenol C and bisphenol A, the hardness of the substrate layer can be improved.
  • the viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, and still more preferably 22,500 to 25,000.
  • the acrylic resin contained in the base material layer is not particularly limited, but for example, homopolymers of various (meth)acrylic acid esters represented by polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), or PMMA or a copolymer of MMA and one or more other monomers, and a mixture of a plurality of these resins.
  • PMMA polymethyl methacrylate
  • MMA methyl methacrylate
  • PMMA methyl methacrylate
  • MMA methyl methacrylate
  • MMA methyl methacrylate
  • MMA methyl methacrylate
  • Examples of such (meth)acrylic resins include, but are not limited to, ACRYPET (manufactured by Mitsubishi Rayon Co., Ltd.), Delpet (manufactured by Asahi Kasei Chemicals Corp.), and Parapet (manufactured by Kuraray Co., Ltd.).
  • the laminate 10 is composed of, for example, a first resin layer 31 and a second resin layer 32 (FIG. 1), and the first resin layer 31 is an acrylic resin layer. and the second resin layer 32 may be a polycarbonate (PC) resin layer.
  • the surface layer 20 is laminated on the PMMA layer side surface of the substrate layer 30 comprising a polymethyl methacrylate (PMMA) resin layer 31 and a polycarbonate (PC) resin layer 32 . (Fig. 1).
  • the base layer may contain additives as components other than the thermoplastic resin.
  • additives as components other than the thermoplastic resin.
  • Antistatic agents, fluorescent whitening agents, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc. may also be added to the base layer.
  • the base material layer preferably contains 80% by mass or more of thermoplastic resin, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of thermoplastic resin. Further, among the thermoplastic resins of the substrate layer, the polycarbonate resin is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the thickness of the base layer is not particularly limited, it is preferably 0.1 mm to 1.0 mm.
  • the thickness of the base layer is, for example, 0.2 mm to 0.8 mm, or 0.3 mm to 0.7 mm.
  • the substrate layer has a thickness of 0.1 mm to 1.0 mm.
  • the surface layer 20 of the present invention is provided by applying a resin composition to the surface of the substrate layer 30 and drying the resin composition.
  • the substrate layer 30 is composed of a plurality of layers, for example, a first resin layer 31 and a second resin layer 32 (FIG. 1)
  • the surface layer 20 includes the first resin layer 31 and the It is laminated on the surface of the base material layer 30 provided with the second resin layer 32 on the side of the first resin layer 31 (FIG. 1).
  • the resin composition used for the surface layer of the present invention contains a (meth)acryloyl polymer (C) and an organic solvent.
  • the (meth)acryloyl polymer (C) has a (meth)acrylic equivalent weight of 200-600 g/eq.
  • the (meth)acrylic equivalent of the (meth)acryloyl polymer is preferably 200 to 500 g/eq, more preferably 220 to 450 g/eq, still more preferably 250 to 400 g/eq.
  • the (meth)acryloyl polymer (C) has a weight average molecular weight of 5,000 to 200,000.
  • the (meth)acryloyl polymer preferably has a mass average molecular weight of 10,000 to 150,000, more preferably 15,000 to 100,000, and still more preferably 20,000 to 50,000.
  • the value of the mass average molecular weight can be measured based on paragraphs 0061 to 0064 of JP-A-2007-179018. Details of the measurement method are shown below.
  • a calibration curve showing the relationship between the elution time and the molecular weight of polycarbonate was prepared by a universal calibration method using polystyrene as a standard polymer. Then, the elution curve (chromatogram) of polycarbonate was measured under the same conditions as in the case of the calibration curve described above. Furthermore, the weight average molecular weight (Mw) was calculated from the elution time (molecular weight) of the polycarbonate and the peak area (number of molecules) of the elution time.
  • (meth)acrylic includes both acrylic and methacrylic.
  • the (meth)acryloyl polymer (C) contained in the resin composition used for the surface layer preferably has a repeating unit represented by the following formula (I).
  • m is an alkylene group having 1 to 4 carbon atoms or a single bond
  • n is an alkyl group having 1 to 4 carbon atoms or hydrogen
  • p is a single bond.
  • q is an epoxy group, a hydroxyl group, an acryloyl group, and an alkyl group having 1 to 12 carbon atoms in total which may contain at least one substituent of a methacryloyl group , or hydrogen.
  • the (meth)acryloyl polymer (C) is more preferably the following repeating unit, i.e., in formula (I) above, m is an alkylene group having 1 or 2 carbon atoms, n is an alkyl group having 1 or 2 carbon atoms, p is a single bond or a methylene group, and q is a glycidyl group, a hydroxyl group, and an acryloyl group. It contains a repeating unit that is an alkyl group having 1 to 6 carbon atoms or hydrogen.
  • m is a methylene group
  • n is a methyl group
  • p is a single bond
  • q is an alkyl group having 5 or less carbon atoms including a methyl group and a glycidyl group (epoxy group).
  • repeating units that can be contained in the (meth)acryloyl polymer (C) include the following formulas (II-a), (II-b), and (II-c) ) are shown.
  • the repeating unit of the formula (II-a) is a repeating unit of the formula (II-a), a repeating unit of the formula (II-b) It is preferably from 30 to 85 mol %, more preferably from 40 to 80 mol %, based on the total number of moles of the units and repeating units of formula (II-c).
  • the repeating unit of formula (II-b) is preferably 5 to 30 mol %, more preferably 10 to 25 mol %, based on the total number of moles.
  • the repeating unit of formula (II-c) is preferably 10 to 40 mol %, more preferably 10 to 35 mol %, based on the total number of moles. In a preferred embodiment of the present invention, based on the total number of moles of repeating units of formula (II-a), repeating units of formula (II-b), and repeating units of formula (II-c), The repeating unit of the formula (II-a) is 30 to 85 mol%, the repeating unit of the formula (II-b) is 5 to 30 mol%, and the repeating unit of the formula (II-c) is 10 to 40 mol %.
  • the repeating unit of the formula (II-a) is 40 to 80 mol%
  • the repeating unit of the formula (II-b) is 10 to 25 mol%
  • the repeating unit of the formula (II-c) The unit is 10 to 35 mol %.
  • the molar ratio of the repeating unit of formula (II-a), the repeating unit of formula (II-b), and the repeating unit of formula (II-c) is Preferably, it is 4.5-5.5:1.5-2.5:2.5-3.5, for example 5:2:3.
  • a polyfunctional acrylate compound having multiple acrylate groups may be added to the (meth)acryloyl polymer (C).
  • Multifunctional acrylate compounds having multiple acrylate groups that may be added to the (meth)acryloyl polymer (C) may preferably contain 3 or more acrylate groups.
  • the polyfunctional acrylate compound having multiple acrylate groups that may be added to the (meth)acryloyl polymer (C) may be a pentaerythritol-based polyfunctional acrylate compound.
  • the (meth)acryloyl polymer (C) further contains a pentaerythritol-based polyfunctional acrylate compound.
  • a pentaerythritol-based polyfunctional acrylate compound for example, pentaerythritol tetraacrylate represented by the following formula (III-a), and dipentaerythritol hexaacrylate represented by the formula (III-b), and Pentaerythritol triacrylate and the like are used.
  • the pentaerythritol-based polyfunctional acrylate compound includes pentaerythritol tetraacrylate represented by the following formula (III-a) and dipentaerythritol hexa represented by the formula (III-b). It is one or more selected from the group consisting of acrylate and pentaerythritol triacrylate.
  • the polyfunctional acrylate compound having multiple acrylate groups that may be added to the (meth)acryloyl polymer (C) is preferably 70% by mass or less, more preferably 50% by mass or less.
  • the pentaerythritol-based polyfunctional acrylate compound is included in an amount of 70% by weight or less based on the total weight of the resin composition.
  • the pentaerythritol-based multifunctional acrylate compound is included in an amount of 50% by weight or less based on the total weight of the resin composition.
  • the resin composition used for the surface layer contains an organic solvent as a diluent.
  • the resin composition used for the surface layer contains an organic solvent (A) with a boiling point of less than 120°C and an organic solvent (B) with a boiling point of 120°C or higher as dilution solvents.
  • the boiling point means the boiling point under 1 atm.
  • the boiling point of the organic solvent (A) having a boiling point of less than 120°C is, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, and 80°C. , 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, etc. good.
  • the boiling point of the organic solvent (A) having a boiling point of less than 120°C is, for example, 40°C or more and less than 120°C, 45°C or more and less than 120°C, 50°C or more and less than 120°C, 55°C or more and 120°C.
  • the boiling point of the organic solvent (A) having a boiling point of less than 120°C is preferably 40°C or more and less than 120°C, more preferably 65°C or more and less than 120°C. , and more preferably 90°C or higher and lower than 120°C.
  • Examples of the organic solvent (A) having a boiling point of less than 120° C. that can be used in the present invention include methyl isobutyl ketone (MIBK; boiling point: 116° C.), acetone (boiling point: 56° C.), isopropyl alcohol (boiling point: 83° C.), methyl ethyl ketone (boiling point: 80° C.), 2-butanol (boiling point: 100° C.), toluene (boiling point: 111° C.), etc., but not limited thereto.
  • MIBK isobutyl ketone
  • acetone boiling point: 56° C.
  • isopropyl alcohol boiling point: 83° C.
  • methyl ethyl ketone boiling point: 80° C.
  • 2-butanol boiling point: 100° C.
  • toluene boiling point: 111° C.
  • the organic solvent (A) that can be used in the present invention may preferably be methyl isobutyl ketone (MIBK), isopropyl alcohol, methyl ethyl ketone, 2-butanol, toluene, more preferably methyl isobutyl ketone (MIBK), 2 -butanol, toluene, and more preferably methyl isobutyl ketone (MIBK).
  • MIBK is methyl isobutyl ketone
  • the boiling point of the organic solvent (B) having a boiling point of 120° C. or higher is, for example, 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C. , 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C °C, 250 °C, and the like.
  • the boiling point of the organic solvent (B) having a boiling point of 120° C. or higher is, for example, 120° C. or higher and 250° C. or lower, 120° C. or higher and 245° C. or lower, 120° C. or higher and 240° C. or lower, 120° C. or higher and 235° C.
  • the boiling point of the organic solvent (B) having a boiling point of 120° C. or higher is preferably 120° C. or higher and 250° C. or lower, more preferably 120° C. or higher and 205° C. or lower. , and more preferably 120° C. or higher and 160° C. or lower.
  • Examples of the organic solvent (B) having a boiling point of 120°C or higher that can be used in the present invention include cyclohexanone (boiling point: 155.6°C), methylcyclohexanol (174°C), methylcyclohexanone (163°C), Examples include, but are not limited to, phenylmethanol (205°C), diethylene glycol monobutyl ether (230°C), and the like.
  • the organic solvent (B) that can be used in the present invention is preferably cyclohexanone, methylcyclohexanol, methylcyclohexanone, phenylmethanol, more preferably cyclohexanone, methylcyclohexanol, methylcyclohexanone, and further More preferably, it may be cyclohexanone.
  • organic solvent (B) is cyclohexanone.
  • the resin composition used for the surface layer comprises an organic solvent (A) having a boiling point of less than 120°C and an organic solvent (B) having a boiling point of 120°C or higher. It is contained in the range of 7:3.
  • the resin composition of the present invention contains an organic solvent (A) having a boiling point of less than 120°C and an organic solvent (B) having a boiling point of 120°C or higher at a mass ratio of, for example, 3:7, 3.5. :7 (ie 1:2), 4:6, 5:5, 6:4, 7:3.5 (ie 2:1), 7:3.
  • the resin composition of the present invention contains an organic solvent (A) having a boiling point of less than 120°C and an organic solvent (B) having a boiling point of 120°C or higher at a mass ratio of, for example, 3:7-7:3, 3:7-7:3.5 (ie 2:1), 3:7-6:4, 3:7-5:5, 3:7-4:6, 3: 7-3.5:7 (ie 1:2); 3.5:7 (ie 1:2) to 7:3, 3.5:7 (ie 1:2) to 7:3.5 (ie 2:1), 3.5:7 (ie 1:2 ) to 6:4, 3.5:7 (ie 1:2) to 5:5, 3.5:7 (ie 1:2) to 4:6; 4:6-7:3, 4:6-7:3.5 (ie 2:1), 4:6-6:4, 4:6-5:5; 5:5 to 7:3, 5:5 to 7:3.5 (ie 2:1), 5:5 to 6:4; 6:4 to 7:3, 6:4 to 7:3.5 (ie 2:1); 7:3.5 (ie 2:1)
  • the resin composition contains an organic solvent (A) having a boiling point of less than 120°C and an organic solvent (B) having a boiling point of 120°C or higher, in a mass ratio of 3:7-7:3, 3:7-7:3.5 (ie 2:1), 3:7-6:4, 3:7-5:5; 3.5:7 (ie 1:2) to 7:3, 3.5:7 (ie 1:2) to 7:3.5 (ie 2:1), 3.5:7 (ie 1:2 ) to 6:4, 3.5:7 (ie 1:2) to 5:5; 4:6-7:3, 4:6-7:3.5 (ie 2:1), 4:6-6:4, 4:6-5:5; may be contained in a mass ratio of 3:7-7:3, 3:7-7:3.5 (ie 2:1), 3:7-6:4, 3:7-5:5; 3.5:7 (ie 1:2) to 7:3, 3.5:7 (ie 1:2) to 7:3.5 (ie 2:1), 3.5:7 (ie 1:2 ) to 6:4, 3.5:7 (ie
  • the resin composition used for the surface layer contains 30 to 50% by mass of an organic solvent (A) having a boiling point of less than 120° C., based on the total mass of the diluent solvent in the resin composition. and 70 to 50% by mass of an organic solvent (B) having a boiling point of 120° C. or higher.
  • the resin composition used for the surface layer contains the organic solvent (A) and the organic solvent (B) in a ratio within the above range, so that the coating property, moldability, and It has excellent tack-free property, and in addition to high hardness and excellent scratch resistance in the laminate after coating and drying the resin composition, it prevents defects such as pinholes and prevents defects such as pinholes.
  • the amount of residual solvent in can be adjusted appropriately.
  • the resin composition used for the surface layer preferably further contains a leveling agent in addition to the (meth)acryloyl polymer (C) described above.
  • a leveling agent for example, a fluorine-based additive, a silicone-based additive, or the like is used.
  • Fluorinated additives include Megafac RS-56, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 manufactured by DIC, Futergent 710FL, 220P, 208G, and 601AD manufactured by Neos. , 602A, 650A, 228P, and phtergent 240GFTX-218 (all of which are fluorine-containing UV-reactive group-containing oligomers).
  • BYK-UV3500 and BYK-UV3505 manufactured by BYK Chemie are used, and among these, BYK-UV3500 and the like are silicone additives. is preferred.
  • the resin composition used for the surface layer preferably contains a leveling agent of 0.1% by mass or more and 10% by mass or less based on the total mass of the resin composition, and the content of the leveling agent in the resin composition is It is more preferably 0.5% by mass or more and 7% by mass or less, and still more preferably 1% by mass or more and 5% by mass or less.
  • the resin composition used for the surface layer may be a curable resin composition.
  • the above resin composition is radiation curable.
  • the radiation-curable resin composition may be energy-ray-curable or heat-curable, preferably energy-ray-curable, more preferably UV-curable. Therefore, the resin composition used for the surface layer preferably further contains a photopolymerization initiator. In a preferred embodiment of the invention, the resin composition further contains a photopolymerization initiator.
  • Photoinitiators include IRGACURE 184 (1-hydroxy-cyclohexyl-phenyl-ketone), IRGACURE 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one), IRGACURE TPO (2,4,6 -trimethylbenzoyl-diphenyl-phosphine oxide), IRGACURE 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), EsacureONE (oligo(2-hydroxy-2-methyl-1-[4-( 1-methylvinyl)phenyl]propanone) and the like are used, and among these, IRGACURE TPO and the like are preferable as the photopolymerization initiator from the viewpoint of heat resistance.
  • the resin composition used for the surface layer contains, for example, 1% by mass or more and 6% by mass or less of a photopolymerization initiator based on the total mass of the resin composition.
  • the content of the photopolymerization initiator in the resin composition is more preferably 2% by mass or more and 5% by mass or less, and still more preferably 3% by mass or more and 4% by mass or less.
  • the resin composition used for the surface layer is selected from the group consisting of other additives such as heat stabilizers, antioxidants, flame retardants, flame retardant aids, ultraviolet absorbers, release agents, and colorants. It may also contain at least one additive.
  • additives such as heat stabilizers, antioxidants, flame retardants, flame retardant aids, ultraviolet absorbers, release agents, and colorants. It may also contain at least one additive.
  • antistatic agents, fluorescent whitening agents, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, inorganic oxide nanoparticles, etc. may be added to the resin composition as long as they do not significantly impair the desired physical properties. may be added.
  • the (meth)acryloyl polymer (C), the organic solvent (A), and the organic solvent (B) preferably contain 60% by mass or more, more preferably 80% by mass. % or more, particularly preferably 90 mass % or more.
  • the content of components other than the main three-component (meth)acryloyl polymer (C)), the organic solvent (A), and the organic solvent (B) in the resin composition is less than 40% by mass. Preferably, it is less than 20% by mass, and particularly preferably less than 10% by mass.
  • the resin composition used for the surface layer is produced by blending materials such as the above-described (meth)acryloyl polymer (C), organic solvent (A), organic solvent (B), and the like.
  • a resin composition is produced by mixing each component such as a (meth)acryloyl polymer using a tumbler.
  • the resin composition used for the surface layer of the present invention also has excellent moldability in an uncured state.
  • the moldability of the above resin composition is evaluated, for example, as follows. That is, after coating the above resin composition on the surface of the base material layer and drying it, the obtained coated product is placed on a mold having convex portions and heated to obtain air pressure moldability. can be evaluated based on whether or not the sheet-shaped resin composition is appropriately stretched following the protrusions and whether or not cracks occur when the above is carried out.
  • Laminate Manufacturing Method A laminate including a substrate layer is manufactured as follows.
  • a material such as a resin composition constituting the substrate layer is processed into a layer (sheet) by a conventional method to produce the substrate layer.
  • a material such as a resin composition constituting the substrate layer
  • it is a method by extrusion molding and cast molding.
  • extrusion molding pellets, flakes or powder of the resin composition used for the base material layer are melted and kneaded with an extruder, extruded from a T-die or the like, and the resulting semi-molten sheet is pressed between rolls.
  • a method of cooling and solidifying to form a sheet can be mentioned.
  • the composition of the base material layer is as described above.
  • the substrate layer may be composed of a single layer or may be composed of multiple layers.
  • the substrate layer 30 may be composed of, for example, a first resin layer 31 and a second resin layer 32 (FIG. 1).
  • the resin composition used for the surface layer produced as described above is applied to the outer surface of the substrate layer having a single layer or a plurality of layers to form a surface layer.
  • the composition and properties of the resin composition used for the surface layer are as described above.
  • the surface layer comprises Step 1 of applying a resin composition containing a radiation-curable resin and an organic solvent to the surface of a substrate layer to obtain a coated product; It is formed by a method including step 2 of drying the obtained coated material to form a surface layer on the surface of the substrate layer. According to the method of the present invention, a laminate having a residual solvent amount of 82 mg/m 2 or less can be obtained.
  • gravure coating, die coating, curtain coating, rod coating, bar coating, blade coating, knife coating, dip coating, etc. can be used as a method for applying the resin composition used for the surface layer to the substrate layer. can be done.
  • a suitable one may be selected from these according to the viscosity of the paint and the thickness of the coating layer. For example, when obtaining a surface layer having a dry film thickness of 5 ⁇ m with a paint having a viscosity of 10 mPa ⁇ s, it is desirable to use gravure coating suitable for low-viscosity thin film coating.
  • hot air drying infrared drying, far-infrared drying, drum heating drying, electromagnetic induction heating drying, and the like can be used as methods for drying the above-mentioned coated material. It is desirable to use hot air drying from the viewpoint of productivity and controllability.
  • Hot air supply methods include follow-flow and counter-flow, which supply hot air parallel to the direction in which the substrate is conveyed, slit nozzle methods that supply hot air perpendicular to the direction in which the substrate is conveyed, and diagonal directions that are intermediate between the two.
  • a method of supplying hot air is used.
  • a roll support method, a floating method, or the like can be used as a method for conveying the substrate in the drying furnace.
  • a zone in which the drying is not actively performed may be provided for the purpose of adjusting the appearance of the coated surface and adjusting the differential pressure between the inside and outside of the drying oven.
  • a cooling zone or the like may also be provided after passing through the drying oven.
  • a method of manufacturing a laminate as described above comprising: Step 1 of applying a resin composition containing a radiation-curable resin and an organic solvent to the surface of a substrate layer to obtain a coated product; Step 2 of drying the obtained coated material to form a surface layer on the surface of the substrate layer including
  • the laminate comprises at least a substrate layer and a surface layer,
  • the resin composition contains a (meth)acryloyl polymer (C), and the (meth)acryloyl polymer (C) has a (meth)acrylic equivalent weight of 200 to 600 g/eq and a weight average of 5,000 to 200,000. has a molecular weight, A method is provided in which the amount of residual solvent in the laminate is 82 mg/m 2 or less.
  • At least two drying ovens may be used in step 2.
  • at least two drying ovens are used in step 2, and the drying oven temperature in the last drying oven is higher than the drying oven temperature in the first drying oven.
  • At least two drying ovens capable of heating the coated material to 60°C or higher may be used in step 2 above.
  • the drying oven temperature in the first drying oven may be in the range of 60-90°C
  • the drying oven temperature in the second drying oven may be in the range of 100-130°C.
  • in step 2 at least two drying ovens capable of heating the coated material to 60°C or higher are used, and the drying oven temperature in the first drying oven is 60 to 90°C. range, and the drying oven temperature in the second drying oven is in the range of 100 to 130°C.
  • step 2 at least two drying ovens capable of heating the coated material to 60° C. or higher are used, and the drying oven temperature in the last drying oven is equal to that of the drying oven in the first drying oven. higher than temperature.
  • step 2 at least two drying ovens capable of heating the coated material to 60°C or higher are used, and the drying oven temperature in the first drying oven is in the range of 60 to 90°C. and the drying oven temperature in the final drying oven is in the range of 100 to 130°C.
  • the base layer has a thickness of 0.1 mm to 1.0 mm, and the resin composition layer applied to the surface of the base layer has a thickness of 1.0 ⁇ m. ⁇ 10 ⁇ m.
  • a masking film may be further laminated on the surface of the surface layer side of the laminate comprising the substrate layer and the surface layer thus obtained.
  • the thickness of the surface layer 20 is preferably 1.0 ⁇ m to 10 ⁇ m.
  • the thickness of the surface layer is, for example, 2.0 ⁇ m to 8.0 ⁇ m, or 3.0 ⁇ m to 7.0 ⁇ m.
  • the hardened surface layer has high hardness. Specifically, a pencil hardness of B or higher in the evaluation method of JIS K 5600-5-4:1999 can be achieved.
  • the surface of the cured surface layer preferably has a pencil hardness of F or higher, particularly preferably 2H or higher.
  • Adhesion The surface layer obtained by curing the resin composition also has excellent adhesion to the substrate layer. Specifically, as will be described later in detail, when applied to the base material layer and cured, the evaluation result determined by the evaluation method of JIS K 5600-5-6: 1999 is 0, and the evaluation Better results than results 1-5 were obtained.
  • the surface of the cured film on the surface layer side has excellent properties. That is, the surface on the surface layer side of the cured film has a high pencil hardness, preferably a pencil hardness of B or higher according to JISK 5600-5-4: 1999, high scratch resistance, and excellent adhesion, such as JISK Adhesion with an evaluation result of 0 level in 5600-5-6 is achieved.
  • a laminate having a residual solvent amount of 82 mg/m 2 or less may be provided.
  • the residual solvent amount in the laminate is 82 mg/m 2 or less, 80 mg/m 2 or less, 75 mg/m 2 or less, 70 mg/m 2 or less, 65 mg/m 2 or less, 60 mg/m 2 or less. , 55 mg/m 2 or less, 50 mg/m 2 or less, 45 mg/m 2 or less, 40 mg/m 2 or less, 35 mg/m 2 or less, 30 mg/m 2 or less, 25 mg/m 2 or less, and the like.
  • the smaller the amount of residual solvent in the laminate the better.
  • a laminate comprising at least a substrate layer and a surface layer provided on the surface of the substrate layer,
  • the resin composition contains a (meth)acryloyl polymer (C), and the (meth)acryloyl polymer (C) has a (meth)acrylic equivalent weight of 200 to 600 g/eq and a weight average of 5,000 to 200,000. has a molecular weight, A laminate having a residual solvent amount of 82 mg/m 2 or less can be obtained.
  • the laminate can be obtained as a cured film by drying and curing the coated product. When a masking film is attached, the masking film is removed and then cured. In a preferred embodiment of the invention the laminate is a cured film.
  • a molded article can be obtained by thermoforming the laminate described above.
  • a molded body obtained by thermoforming the laminate described above.
  • Example 1 By mixing cyclohexanone and methyl isobutyl ketone (MIBK) with an ultraviolet curable acryloyl polymer (Art Cure RA-3602MI manufactured by Negami Kogyo Co., Ltd.), the mass ratio of MIBK:cyclohexanone is 6:4, and the solid content concentration is 20 mass. adjusted to be %. Furthermore, a photopolymerization initiator IRGACURE 184 (3% by mass based on the solid content) was added to obtain a resin composition used for the surface layer.
  • MIBK methyl isobutyl ketone
  • an ultraviolet curable acryloyl polymer Article Cure RA-3602MI manufactured by Negami Kogyo Co., Ltd.
  • the resin composition used for the surface layer obtained as described above was applied to the PMMA side of a polycarbonate (PC)/polymethyl methacrylate (PMMA) film as a substrate layer to obtain a coated product. .
  • the coating process was performed using a 120-line gravure roll. After that, in the drying step, the coated material is dried at 60 ° C. in the first drying oven (“pre-drying oven” in the table below) and at 120 ° C. in the last drying oven (“post-drying oven” in the table below). As a result, a laminate was obtained in which a radiation-curable resin layer having a thickness of about 4 micrometers was formed as a surface layer on the surface of the PMMA side. The resulting laminate was evaluated for the amount of residual solvent, the presence or absence of pinholes, and the presence or absence of poor leveling. The evaluation results are shown in the table below.
  • Examples 2 to 10 Comparative Examples 1 to 16> A laminate was obtained in the same manner as in Example 1, except that the composition and drying temperature were changed to those shown in the table below. In the same manner as in Example 1, the resulting laminate was evaluated for the amount of residual solvent, the presence or absence of pinholes, and the presence or absence of leveling defects. The evaluation results are shown in the table below.
  • any of the laminates of the present invention can maintain the properties required for laminates for molded articles, such as moldability, scratch resistance, hardness, adhesion, and good appearance. It has the excellent feature of being significantly reduced. Therefore, the laminate of the present invention is suitable for applications such as automobile interiors and housings for electronic devices.

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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
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