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WO2018143211A1 - Corps moulé, et procédé de fabrication de celui-ci - Google Patents

Corps moulé, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2018143211A1
WO2018143211A1 PCT/JP2018/003012 JP2018003012W WO2018143211A1 WO 2018143211 A1 WO2018143211 A1 WO 2018143211A1 JP 2018003012 W JP2018003012 W JP 2018003012W WO 2018143211 A1 WO2018143211 A1 WO 2018143211A1
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WIPO (PCT)
Prior art keywords
block copolymer
resin
layer
acrylic
acrylic block
Prior art date
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
Application number
PCT/JP2018/003012
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English (en)
Japanese (ja)
Inventor
真 赤井
啓志 大島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
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Kuraray Co Ltd
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Filing date
Publication date
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Publication of WO2018143211A1 publication Critical patent/WO2018143211A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type

Definitions

  • the present invention relates to a molded article having a layer made of a resin containing a specific acrylic block copolymer and a layer made of a polar resin, and a method for producing the same.
  • Composite products of hard plastic and soft material are widely used in automobiles, building materials, electrical products, daily necessities, and all other fields.
  • a protective member case, cover, etc.
  • polycarbonate or the like is used for the hard type
  • polyvinyl chloride, polystyrene elastomer, polyurethane for the soft type.
  • System elastomers and the like are used, and some hard and soft types are also integrated.
  • Soft type materials have been proposed by companies as shock absorbing materials.
  • Patent Document 1 a styrene-based thermoplastic elastomer composition suitable for uses such as a vibration isolating material, an impact absorbing material, a cover material, and a cushioning material is studied.
  • Patent Document 2 it has excellent melt adhesiveness with a polar base resin, and is provided with elasticity, vibration proofing, anti-destructive functions, etc. with a soft touch by covering or joining the surface of the base resin layer.
  • Thermoplastic resin formulations are being investigated.
  • Patent Document 3 an impact absorbing material made of an elastomer composition for protecting various electronic devices and the like from impacts and vibrations is studied.
  • Patent Document 4 an acrylic block copolymer that is excellent in flexibility, transparency, and adhesion to a base material and has excellent vibration damping properties compared to a comparable styrene-based elastomer is studied.
  • Patent Documents 1 to 3 do not describe the transparency of the composition, and are inappropriate for applications requiring transparency.
  • Patent Document 4 describes a wide range of uses using an acrylic block copolymer, but it is not specific, and there is no description about adhesiveness with a polar resin. Therefore, a composition having transparency, impact absorption and adhesion with a polar resin could not be obtained, and there was room for improvement.
  • the problem to be solved by the present invention is to provide a molded body having a resin layer having transparency, impact absorption, adhesion to a polar resin, and flexibility.
  • the present inventors have found that when a specific acrylic block copolymer is used, transparency, impact absorption, adhesion to a polar resin, and flexibility are improved.
  • the present inventors have found that a molded body having a combined resin layer can be obtained, and further studied based on the knowledge to complete the present invention.
  • the present invention [1] A molded body having a layer (I) made of a resin containing an acrylic block copolymer and a layer (II) made of a polar resin,
  • the acrylic block copolymer has a structure in which a polymer block (a2) mainly composed of a methacrylic acid ester unit is bonded to both ends of a polymer block (a1) mainly composed of an acrylate ester unit in the molecule.
  • the resin containing the acrylic block copolymer has a total light transmittance of 3% thickness of 90% or more, an adhesive strength with the polar resin of 50 N / 40 mm or more at a peeling rate of 100 mm / min, and a tensile dynamic A molded product having a tan ⁇ measured by viscoelasticity measurement at 23 ° C.
  • a molded body having a resin layer having transparency, shock absorption, adhesion to a polar resin, and flexibility is provided by adopting the above configuration.
  • the molded product of the present invention has a layer (I) made of a resin containing an acrylic block copolymer and a layer (II) made of a polar resin.
  • the acrylic block copolymer has a structure in which a polymer block (a2) mainly composed of a methacrylic acid ester unit is bonded to both ends of a polymer block (a1) mainly composed of an acrylate unit. At least one of them, the weight average molecular weight is 10,000 to 200,000, and the content of the polymer block (a2) is 10 to 65 mass% or less.
  • the resin containing the acrylic block copolymer has a total light transmittance of 3% thickness of 90% or more, an adhesive strength with the polar resin of 50 N / 40 mm or more at a peeling rate of 100 mm / min, Tan ⁇ measured at 23 ° C. and a frequency of 11 Hz in the dynamic viscoelasticity measurement is 0.20 or more.
  • the acrylic block copolymer in the present invention has a structure in which a polymer block (a2) mainly composed of a methacrylic acid ester unit is bonded to both ends of a polymer block (a1) mainly composed of an acrylate ester unit, that is, , (A2)-(a1)-(a2) (in the structure, “-” indicates a chemical bond) in the molecule.
  • the content of the acrylate ester unit in the polymer block (a1) is usually 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.
  • the acrylate ester as the acrylate ester unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and acrylic.
  • Tert-butyl acid amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, acrylic Examples include phenoxyethyl acid, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, and the like.
  • acrylic esters from the viewpoint of improving flexibility, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, phenoxyethyl acrylate, acrylic Acrylic acid alkyl esters such as 2-methoxyethyl acid are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferred.
  • the polymer block (a1) may be composed of one kind of these acrylate esters or may be composed of two or more kinds.
  • the polymer block (a1) is a unit derived from an acrylate ester having a reactive group such as glycidyl acrylate or allyl acrylate; or the following methacrylate ester, as long as the object and effect of the present invention are not hindered.
  • Units derived from other polymerizable monomers other than acrylic acid esters such as methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile, olefins, and the like may be included as a copolymerization component.
  • the unit derived from the acrylate ester having a reactive group or the unit derived from another polymerizable monomer is preferably a small amount from the viewpoint of expressing the effect of the present invention, and both of the units in the polymer block (a1) are used.
  • the total content is preferably 10% by mass or less, more preferably 2% by mass or less.
  • the content of the methacrylic acid ester unit in the polymer block (a2) is usually 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.
  • the methacrylic acid ester as the methacrylic acid ester unit include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, methacrylic acid.
  • Tert-butyl acid amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacryl Examples include phenoxyethyl acid, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, and the like.
  • methacrylate esters from the viewpoint of improving transparency and heat resistance, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate And alkyl methacrylates such as methyl methacrylate are more preferred.
  • the polymer block (a2) may be composed of one of these methacrylic acid esters or may be composed of two or more.
  • the polymer block (a2) is a unit derived from a methacrylic acid ester having a reactive group such as glycidyl methacrylate or allyl methacrylate; or the acrylate ester as long as the object and effect of the present invention are not hindered.
  • Units derived from other polymerizable monomers other than methacrylic acid esters such as methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile, olefins, etc. may be included as a copolymerization component.
  • the unit derived from the methacrylic acid ester having a reactive group or the unit derived from another polymerizable monomer is a small amount, and the total content of both in the polymer block (a2) is preferably 10 It is at most 2% by mass, more preferably at most 2% by mass.
  • the molecular chain form of the acrylic block copolymer is not particularly limited as long as it has at least one structure in which the polymer block (a2) is bonded to both ends of the polymer block (a1) in the molecule.
  • any of linear, branched, radial and the like may be used, but among these, a triblock body represented by (a2)-(a1)-(a2) is preferable.
  • the molecular weight and composition of (a2) at both ends of (a1) may be the same or different from each other.
  • the resin containing the acrylic block copolymer constituting the layer (I) is represented by (a2)-(a1) together with the acrylic block copolymer. It may further contain an acrylic diblock copolymer.
  • the acrylic block copolymer is a polymer block different from these polymer blocks (a1) and (a2), other than acrylic ester and methacrylic ester. It may have a polymer block (c) derived from the monomer.
  • the form of the bond between the polymer block (c) and the polymer block (a1) and the polymer block (a2) is not particularly limited. For example, (a2)-((a1)-(a2)) n- ( c), and structures such as (c)-(a2)-((a1)-(a2)) n- (c) (n is an integer of 1 to 20).
  • Examples of the monomer constituting the polymer block (c) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as 1,3-butadiene, isoprene and myrcene; styrene, Aromatic vinyl such as ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene; vinyl acetate, vinylpyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ⁇ -Caprolactone, valerolactone and the like.
  • olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene
  • conjugated dienes such as 1,3-butadiene, isoprene and myrcene
  • the acrylic block copolymer used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain end as necessary.
  • the weight average molecular weight of the acrylic block copolymer is 10,000 to 200,000 from the viewpoint of the transparency of the resulting layer (I), impact absorption, and adhesiveness to polar resins. From the above viewpoint, the weight average molecular weight of the acrylic block copolymer is preferably 30,000 to 180,000, and more preferably 50,000 to 160,000. When the weight average molecular weight of the acrylic block copolymer is 10,000 or more, sufficient melt tension can be maintained in injection molding or extrusion molding, and a good molded body can be obtained. Moreover, the mechanical properties such as the breaking strength of the obtained molded article are excellent.
  • the acrylic block copolymer has a weight average molecular weight of 200,000 or less, the surface of the molded body obtained by injection molding or extrusion molding has fine grainy irregularities and unmelted material (high molecular weight body). Produced products are less likely to occur, and a molded article having an excellent appearance is easily obtained.
  • the molecular weight distribution represented by the ratio (Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic block copolymer is in the range of 1.01 or more and less than 1.50. It is preferable that it is in the range of 1.01 or more and 1.35 or less. By taking such a range, it is possible to make the content of the unmelted material that causes the generation of scum in the layer (I) extremely small.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this specification are those in terms of polystyrene measured by gel permeation chromatography, and should be measured by the method described later in the examples. Can do.
  • the content of the polymer block (a2) in the acrylic block copolymer is from 10 to 65% by mass, and from 12% by mass or more, from the viewpoints of transparency, impact absorption, and adhesion to polar resins. It is preferably 13% by mass or more, more preferably 14% by mass or more, particularly preferably 15% by mass or more, and preferably 60% by mass or less, 55% by mass. % Or less, more preferably 45% by weight or less, and particularly preferably 40% by weight or less.
  • the content of the polymer block (a2) in the acrylic block copolymer is smaller than the above range, the sticking feeling of the resin containing the acrylic block copolymer constituting the layer (I) increases, and the molding material Tend to be unsuitable.
  • the content of the polymer block (a2) in the acrylic block copolymer is larger than the above range, the resin containing the acrylic block copolymer constituting the layer (I) becomes hard and the impact is reduced. Absorptivity is lost, and there is a tendency for adhesion to polar resins to decrease.
  • the method for producing the acrylic block copolymer is not particularly limited, and a method according to a known method can be employed.
  • a method of living polymerizing monomers constituting each block is generally used.
  • a technique for such living polymerization for example, a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral salt such as an alkali metal or alkaline earth metal salt (Japanese Patent Publication No. 7-25859).
  • a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound see JP-A-11-335432
  • a method of polymerizing using an organic rare earth metal complex as a polymerization initiator JP-A-6-6.
  • JP-A-6-6 -93060
  • a method of radical polymerization using an ⁇ -halogenated ester compound as an initiator in the presence of a copper compound (Macromol. Chem. Phys.) 201, 1108-1114 (2000) ))).
  • the acrylic acid ester used when producing the polymer block (a1) mainly composed of the acrylic acid ester unit may be a mixed monomer in which two or more kinds are mixed in advance, such as an acrylic acid alkyl ester and an acrylic acid aromatic ester. It is preferable to use a mixed monomer. In this case, a mixed monomer of 50 to 90% by mass of acrylic acid alkyl ester and 50 to 10% by mass of acrylic acid aromatic ester is preferable, and 60 to 80% by mass of acrylic acid alkyl ester and 40 to 20% of acrylic acid aromatic ester are preferable. More preferably, it is a mixed monomer of mass%.
  • the layer (I) in the present invention is made of a resin containing an acrylic block copolymer.
  • the resin constituting the layer (I) may be composed of only an acrylic block copolymer, or may be a resin composition containing an acrylic block copolymer and other components. .
  • the kind of components other than the acrylic block copolymer in the resin composition is not particularly limited, and examples thereof include various polymers, additives, fillers and the like as described later.
  • the content of the acrylic block copolymer in the resin containing the acrylic block copolymer constituting the layer (I) is preferably 55% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. 100 mass%.
  • an acrylic polymer mainly composed of a methacrylic acid ester unit is preferable.
  • the acrylic polymer preferably contains 80% by mass or more of methacrylic acid ester units, and preferably contains 90% by mass or more.
  • the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and methacrylic acid.
  • Amyl isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, methacryl Examples include 2-ethoxyethyl acid, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornenyl methacrylate, and isobonyl methacrylate. Of these, methyl methacrylate is particularly preferred.
  • the acrylic polymer may contain other monomer units other than methacrylic acid ester units.
  • examples of such other monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and sec-butyl acrylate.
  • Tert-butyl acrylate amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate
  • Acrylic acid esters such as 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, and isobornyl acrylate; acrylic acid, methacrylic acid, anhydrous Unsaturated carboxylic acids such as oleic acid, maleic acid and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, is
  • the method for producing the acrylic polymer is not particularly limited. Moreover, you may use a commercial item as an acrylic polymer. Examples of such commercially available products include “Parapet H1000B” (MFR: 22 g / 10 min (230 ° C., 37.3 N)), “Parapet GF” (MFR: 15 g / 10 min (230 ° C., 37.3 N)), “ “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)), “Parapet HRL” (MFR: 2.0 g / 10 min (230 ° C., 37.3 N)), “Parapet HRS” ( MFR: 2.4 g / 10 min (230 ° C., 37.3 N)) and “Parapet G” (MFR: 8.0 g / 10 min (230 ° C., 37.3 N)) [all trade names, manufactured by Kuraray Co., Ltd. ] Etc. are mentioned.
  • the content thereof is preferably 1 to 45% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 15% by mass. It is.
  • the above resin composition may contain other polymer as required in addition to the acrylic block copolymer and the acrylic polymer.
  • Other polymers include, for example, olefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymers, high Styrene resins such as impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid; nylon 6 Polyamide resins such as nylon 66 and polyamide elastomers; ester polyurethane elastomers, ether polyurethane elastomers, non-yellowing ester polyurethane elastomers, non-y
  • the resin composition described above may be used in various known additives (for example, rubbers, lubricants, antioxidants, light stabilizers, colorants, antistatic agents, flame retardants, etc.) as long as the effects of the present invention are not impaired. ), Fillers (for example, fiber reinforcing agents such as glass fibers, inorganic fillers, etc.) and the like.
  • Fillers for example, fiber reinforcing agents such as glass fibers, inorganic fillers, etc.
  • rubbers that can be included as additives include acrylic rubbers; silicone rubbers; styrene thermoplastic elastomers such as SEPS, SEBS, and SIS; and olefin rubbers such as IR, EPR, and EPDM.
  • SEPS styrene thermoplastic elastomers
  • SEBS styrene thermoplastic elastomers
  • olefin rubbers such as IR, EPR, and EPDM.
  • One or more can be used.
  • additives and fillers examples include mineral oil softeners such as paraffinic oils and naphthenic oils for improving fluidity during molding; the purpose is to improve heat resistance, weather resistance, etc.
  • Inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate; inorganic fiber or organic fiber such as glass fiber and carbon fiber for reinforcement; heat stabilizer; Light stabilizers; adhesives; tackifiers; plasticizers; antistatic agents; foaming agents; colorants;
  • a heat stabilizer, an antioxidant and the like in order to further improve heat resistance and weather resistance.
  • the transparency of the resin containing the acrylic block copolymer constituting the layer (I) is such that the total light transmittance of 3 mm thickness is 90% or more, preferably 91% or more, more preferably 92% or more. is there. If the total light transmittance with a thickness of 3 mm is 90% or more, the molded product having the layer (I) and the layer (II) produced by injection molding or extrusion molding has good transparency and excellent design.
  • the total light transmittance of 3 mm thickness can be measured with a haze meter using a molded product having a thickness of 3 mm obtained by injection molding a resin containing an acrylic block copolymer constituting the layer (I). Specifically, it can be measured by the method described later in the examples.
  • the resin containing the acrylic block copolymer constituting the layer (I) has an adhesive force with the polar resin constituting the layer (II) of 50 N / 40 mm or more at a peeling rate of 100 mm / min, preferably 60 N / 40 mm. It is above, More preferably, it is 70 N / 40mm or more.
  • the adhesive strength with the polar resin is 50 N / 40 mm or more at a peeling rate of 100 mm / min, the adhesion between the layer (I) and the layer (II) made of the polar resin will be good, and the molded product will have sufficient strength Can be obtained.
  • the upper limit is not particularly limited and is preferably as high as possible, but is usually 800 N / 40 mm or less.
  • the adhesive strength with the polar resin is about 100 mm ⁇ 40 mm in which a layer made of a resin containing an acrylic block copolymer is laminated by insert molding on a layer having a thickness of 1 mm made of a polar resin and a total thickness of 2 mm. , And can be measured according to ISO 11339, specifically, by the method described later in the examples.
  • the rubbery component formed by (a1) forms a matrix. It becomes easy to do. Therefore, the peak of tan ⁇ derived from the block (a1) tends to be large, and the value of tan ⁇ at 23 ° C. tends to be high.
  • the resin containing the acrylic block copolymer constituting the layer (I) has a tan ⁇ measured by tensile dynamic viscoelasticity measurement at 23 ° C. and a frequency of 11 Hz of 0.20 or more, preferably 0.21 or more. More preferably, it is 0.22 or more.
  • the layer (I) has excellent shock absorption, and the resulting molded article of the present invention has excellent shock absorption, for example, protects electronic equipment from shock. Therefore, it can be suitably used as a protective member (case, cover, etc.). Although it does not specifically limit about an upper limit, Usually, it is 3.0 or less.
  • the tan ⁇ can be measured by a viscoelasticity measuring device, and specifically can be measured by a method described later in the examples.
  • the resin containing the acrylic block copolymer constituting the layer (I) has an A hardness at 23 ° C. of preferably 20 to 75, more preferably 22 to 73, and further preferably 24 to 71. If the A hardness at 23 ° C. is 20 to 75, the flexibility of the layer (I) is improved and the flexibility of the resulting molded article is also improved.
  • the method for preparing the resin composition is not particularly limited, but the dispersibility of each component In order to increase the viscosity, a method of mixing by melt kneading is recommended.
  • the acrylic block copolymer and the acrylic polymer may be melt-kneaded.
  • these components are mixed simultaneously with the melt-kneading of the acrylic block copolymer and the acrylic polymer.
  • the acrylic block copolymer may be mixed with these components and then mixed with the acrylic polymer.
  • the mixing operation can be performed using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer.
  • a twin screw extruder from the viewpoint of improving kneadability and compatibility between the acrylic block copolymer and the acrylic polymer.
  • the temperature at the time of mixing and kneading may be appropriately adjusted according to the melting temperature of the acrylic block copolymer and acrylic polymer to be used, and is usually mixed at a temperature within the range of 110 to 300 ° C.
  • the resin composition containing an acrylic block copolymer can be obtained in any form such as pellets or powder.
  • the resin composition thus obtained can be molded by the method described later to obtain layer (I).
  • a resin containing a polar polymer can be used as the polar resin constituting the layer (II).
  • the polar resin may be composed of only a polar polymer, or may be a polar resin composition containing a polar polymer and other components.
  • the kind of components other than the polar resin in the polar resin composition is not particularly limited, and examples thereof include various polymers, additives, fillers and the like mentioned in the resin constituting the layer (I).
  • the content of the polar polymer in the polar resin constituting the layer (II) is preferably 55% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and may be 100% by mass.
  • thermoplastic hard polar resin can be used as the polar resin constituting the layer (II).
  • a thermoplastic hard polar resin can be used.
  • ethylene ionomer polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, Styrenic resins such as AES resin, AAS resin, ACS resin, MBS resin; acrylic resin such as polymethyl methacrylate; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid; nylon 6 Polyamide resins such as nylon 66; polyurethane resins such as ester polyurethane, ether polyurethane, non-yellowing ester polyurethane, non-yellowing carbonate polyurethane; polycarbonate, polyvinyl chloride, polyvinyl chloride , Polyvinyl alcohol, ethylene - vinyl alcohol copoly
  • the polar resin preferably has a solubility parameter in the range of 8 to 13 (cal / cm 3 ) 1/2 , and more preferably in the range of 8 to 11 (cal / cm 3 ) 1/2 . If the solubility parameter is within the above range, the difference from the solubility parameter of the layer (I) tends to be small, so that the wettability is increased at the resin interface and the adhesiveness is also improved.
  • a solubility parameter shall be defined by the method as described in an Example.
  • the polar resin preferably has a flexural modulus of 2,000 to 3,500 MPa at 23 ° C., more preferably 2,200 to 3,300 MPa, and still more preferably 2,300 to 3,000 MPa. If the bending elastic modulus at 23 ° C. is 2,000 MPa or more, sufficient rigidity can be secured even if the layer (II) made of the polar resin is thin, and if it is 3,500 MPa or less, it will be described later. The moldability of the molded body is also improved.
  • the polar resin preferably has a 3 mm-thick total light transmittance of 88% or more, more preferably 89% or more, and still more preferably 90% or more. If the total light transmittance with a thickness of 3 mm is 88% or more, the transparency of the layer (II) made of the polar resin will be good, and the resulting molded article will have good transparency and excellent design.
  • the total light transmittance with a thickness of 3 mm can be measured with a haze meter using a molded product with a thickness of 3 mm obtained by injection molding the polar resin constituting the layer (II). Specifically, in the examples It can measure by the method mentioned later.
  • the molded article of the present invention has a layer (I) made of a resin containing the above acrylic block copolymer and a layer (II) made of a polar resin.
  • a layer (I) made of a resin containing the above acrylic block copolymer
  • a layer (II) made of a polar resin.
  • other layers may be included, but the layer (I) and the layer (II) are preferably adjacent to each other.
  • the molded product of the present invention has a layer (I) that is excellent in transparency, flexibility, and impact absorption.
  • the layer (II) can impart transparency and rigidity to the molded article of the present invention. For this reason, the molded article of the present invention is excellent in transparency and has the characteristics that the layer (II) has rigidity and the layer (I) has excellent flexibility and impact absorption.
  • the thickness of the layer (I) and the layer (II) constituting the molded body of the present invention is not particularly limited, but the thickness of the layer (I) is 0.1 from the viewpoint that the molded body is excellent in flexibility and impact absorption.
  • Is preferably 10 to 10 mm, more preferably 0.3 to 5 mm, still more preferably 0.5 to 3 mm, and may be 0.7 to 2 mm, and more preferably 1 to 1.5 mm.
  • the thickness of the layer (II) is preferably from 0.3 to 10 mm, more preferably from 0.5 to 5 mm, still more preferably from 1 to 3 mm.
  • the molded article of the present invention can be molded using a generally used molding method or molding apparatus.
  • at least one of the layer (I) and the layer (II) is formed by a molding method such as extrusion molding, extrusion lamination, injection molding, compression molding, blow molding, calender molding, vacuum molding, or the like, a solution casting method, or the like.
  • the molded article of the present invention can be produced.
  • the molded article of the present invention is produced by injection molding or extrusion molding, at least one of the layer (I) and the layer (II) may be injection molded or extrusion molded.
  • the layer ( When forming I) the resin composition may be used for injection molding or extrusion molding.
  • a method for producing the molded article of the present invention for example, a method in which the layer (I) and the layer (II) are separately molded in advance and then laminated (method 1); A method of forming layer (I) by arranging a resin (acrylic block copolymer or resin composition containing the same) containing a molten acrylic block copolymer in the layer (II) that has been left (Method 2) ); A method of forming a layer (II) by arranging a molten polar resin in the layer (I) prepared in advance (Method 3); a resin containing an acrylic block copolymer in a molten state (acrylic) A block copolymer or a resin composition containing the block copolymer) and a molten polar resin are arranged on each other by a method such as coextrusion to form the layer (I) and the layer (II) (Method 4).
  • the methods 2 to 4 are preferable because the adhesive force between the layer (I) and the layer (II) is improved, and the method 2 is more preferable because the desired molded article can be easily obtained.
  • the resin containing the acrylic block copolymer is excellent in melt fluidity, it is preferable to form the layer (I) by injection molding.
  • the pre-molded layer (II) is placed in the mold.
  • insert molding in which a resin containing an acrylic block copolymer in a molten state (an acrylic block copolymer or a resin composition containing the same) is injected.
  • the use of the molded product of the present invention is not particularly limited, but it is used in various applications such as the optical field, food field, medical field, consumer field, automobile field, electric / electronic field, and architectural field because of the above characteristics. Can do.
  • a protective member for electronic devices such as smartphone terminals (cases, covers, etc.)
  • it is excellent in shock absorption, so that it is possible to protect smartphone terminals from damage due to impact or collision due to falling, and transparent Design and design can be imparted because of its excellent properties and flexibility, and it can be easily detached.
  • liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, in-vehicle liquid crystal displays, liquid crystal monitors, light control panels, OA equipment displays, AV equipment displays, electroluminescence display elements, touch panels, etc.
  • liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, in-vehicle liquid crystal displays, liquid crystal monitors, light control panels, OA equipment displays, AV equipment displays, electroluminescence display elements, touch panels, etc.
  • polar resin adhesion for example, architectural interior / exterior materials, curtain walls, roof materials, roofing materials, window materials, gutters, exteriors, wall materials, flooring materials. It can also be used for multilayer products such as construction materials, road construction members, retroreflective films and sheets, agricultural films and sheets, lighting covers, signboards, and translucent sound insulation walls.
  • Weight average molecular weight (Mw) and number average molecular weight (Mn) The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic block copolymer were determined by gel permeation chromatography (hereinafter abbreviated as GPC) in terms of polystyrene equivalent molecular weight. Details are as follows. ⁇ Equipment: GPC equipment “HLC-8020” manufactured by Tosoh Corporation Separation column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C. ⁇ Detection method: Differential refractive index (RI)
  • composition ratio of each polymer block The composition ratio of each polymer block and the composition ratio of each polymer block in the acrylic block copolymer were determined by 1 H-NMR ( 1 H-nuclear magnetic resonance) measurement. . Details are as follows. ⁇ Device: JEM Nuclear Magnetic Resonance Device “JNM-LA400” ⁇ Deuterated solvent: Deuterated chloroform
  • Solubility parameter of the polar resin was converted to a unit by referring to the numerical value [(MPa) 1/2 ] described in “Polymer Handbook 4th Edition” (edited by Willy Interscience) [( cal / cm 3 ) 1/2 ] was used.
  • the solubility parameters of resins not described in the “Polymer Handbook” are derived from molecular structures reported in literatures such as “KL Hoy, Journal of Paint Technology, 42 (541), 76 (1970)”.
  • the numerical value [(MPa) 1/2 ] was calculated by the Hoy calculation method to be estimated, and the same unit conversion [(cal / cm 3 ) 1/2 ] as described above was used.
  • the bending elastic modulus of polar resin at 23 ° C. is determined by the injection temperature (cylinder temperature) of each polar resin described in (4) using an injection molding machine (“UH1000-80” manufactured by Nissei Plastic Industry Co., Ltd.). And a mold temperature), a molded body having a size of 80 mm ⁇ 10 mm and a thickness of 4 mm was produced. About the obtained molded object, based on ISO 178, the bending elastic modulus was measured.
  • Table 1 shows each physical property value of the polar resin used in the following Examples and Comparative Examples.
  • PC Polycarbonate
  • PS Polystyrene
  • PS SX100 (PS Japan Corporation)
  • PMMA Parapet HR-L (Kuraray Co., Ltd.)
  • the compound was dried and purified by a conventional method and degassed with nitrogen. Moreover, the transfer and supply of the compounds were performed under a nitrogen atmosphere.
  • Synthesis Example 1 [Preparation of organoaluminum compound: isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum] After drying with sodium, 25 ml of dry toluene obtained by distillation under an argon atmosphere and 11 g of 2,6-di-t-butyl-4-methylphenol were placed in a 200 ml flask whose internal atmosphere was replaced with argon. Added and dissolved with stirring at room temperature. By adding 6.8 ml of triisobutylaluminum to the obtained solution and stirring at 80 ° C.
  • organoaluminum compound [isobutylbis (2,6-di-t-butyl-4-methylphenoxy)] was obtained.
  • the structure of the resulting acrylic block copolymer (A1) is a triblock of methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer block (PMMA).
  • the copolymer had a PMMA content (content of polymer block (a2)) of 23.5% by mass, a weight average molecular weight of 70,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.20.
  • PMMA acid methyl polymer block
  • PMMA content content of polymer block (a2) 16.0% by mass
  • weight average molecular weight 150,000 weight average molecular weight 150,000
  • molecular weight distribution weight average molecular weight / Number average molecular weight 1.20.
  • Examples 1 to 8 As the resin constituting the layer (I), the acrylic block copolymers (A1) to (A6) obtained in Synthesis Examples 2 to 7, or the acrylic block copolymer and the acrylic polymer (“Parapet”) are used. GF “(manufactured by Kuraray Co., Ltd.) was used, and the resin obtained by extruding and cutting after melt kneading at 230 ° C with a twin screw extruder at the blending ratio shown in Table 2 below was used. . As the resin constituting this and the layer (II), the polar resin described in Table 1 is used and an injection molding machine (Nissei Resin Industry Co., Ltd.
  • “UH1000-80”) is used to insert 100 mm ⁇ 40 mm and a total thickness of 2 mm.
  • An adhesive molded body was produced.
  • a layer (II) having a size of 100 mm ⁇ 40 mm and a thickness of 1 mm was used with the injection molding machine under the injection temperature (cylinder temperature and mold temperature) conditions of each polar resin described in (4).
  • a plurality of molded bodies were prepared in advance, and the molded body of the obtained layer (II) was set in an injection mold having a size of 100 mm ⁇ 40 mm and a thickness of 2 mm, and the cylinder temperature was 210 ° C. and the mold temperature was 50 ° C.
  • a resin constituting the layer (I) was injected into the gap to produce an insert bonded molded body.
  • the adhesive force between layer (I) and layer (II) was measured according to said (3).
  • the physical properties of the resin constituting the layer (I) were evaluated according to the above (4) to (6). The obtained results are shown in Table 2.
  • Comparative Examples 1 to 4 Except having changed resin which comprises layer (I) as described in Table 3, the molded object was manufactured by the method similar to an Example, and the physical property was evaluated. The obtained results are shown in Table 3.
  • the resins used in Comparative Examples 2 to 4 are as follows. Thermoplastic elastomer: “HIBLER 7125 (Kuraray Co., Ltd.)” Thermoplastic polyurethane elastomer: “Elastolan 1198A (manufactured by BASF)” Thermoplastic polyurethane elastomer (no yellowing): “Milactolan XN2004 (manufactured by Tosoh Corporation)”
  • the layer (I) in the molded bodies obtained in Examples 1 to 8 of the present invention has good transparency, adhesion to PC and flexibility.
  • the adhesiveness to PS and PMMA is also good, and it is considered that the same effect can be obtained in other examples.
  • the layer (I) has excellent shock absorption, and in Example 6, it is particularly excellent. Furthermore, it has low hardness and excellent flexibility.
  • the molded articles of Examples 1 to 8 are excellent in transparency, impact absorption, and flexibility.
  • Comparative Example 1 has good transparency but poor performance.
  • Comparative Example 2 is a thermoplastic elastomer that does not contain an acrylic block copolymer and is inferior in transparency.
  • Comparative Examples 3 and 4 are thermoplastic polyurethane elastomers that do not contain an acrylic block copolymer and are inferior in flexibility. Comparative Example 4 is also inferior in shock absorption.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Graft Or Block Polymers (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention fournit un corps moulé qui possède une couche de résine conciliant des propriétés de transparence, d'absorption des chocs, d'adhérence à une résine polaire et de souplesse. Plus précisément, l'invention concerne un corps moulé qui possède une couche (I) qui est constituée d'une résine contenant un copolymère séquencé acrylique, et une couche (II) qui est constituée d'une résine polaire. Le copolymère séquencé acrylique possède à l'intérieur de chaque molécule au moins une structure dans laquelle chaque séquence de polymère d'ester d'acide méthacrylique (a2) est liée aux deux extrémités d'une séquence de polymère d'ester d'acide acrylique (a1), et présente une masse moléculaire moyenne en poids comprise entre １００００ et ２０００００, et une teneur en séquence de polymère (a2) comprise entre 10 et 65% en masse. La résine contenant ledit copolymère séquencé acrylique présente une transmittance totale de la lumière pour 3mm d'épaisseur supérieure ou égale à 90%, une force d'adhésion vis-à-vis de ladite résine polaire supérieure ou égale à ５０Ｎ／４０ｍｍ à une vitesse de pelage de １００ｍｍ／minute, et une valeur ｔａｎδ mesurée à 23°C et à une fréquence de 11Hz selon une mesure de viscoélasticité dynamique à la traction, supérieure ou égale à 0,20.
PCT/JP2018/003012 2017-02-03 2018-01-30 Corps moulé, et procédé de fabrication de celui-ci Ceased WO2018143211A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022215500A1 (fr) * 2021-04-07 2022-10-13

Families Citing this family (1)

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JP7070344B2 (ja) * 2018-11-01 2022-05-18 三菱エンジニアリングプラスチックス株式会社 パネル積層体及びその製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241568A (ja) * 2001-02-19 2002-08-28 Kanegafuchi Chem Ind Co Ltd 熱可塑性樹脂組成物、およびフィルムまたはシート
JP3150674U (ja) * 2009-03-09 2009-05-28 株式会社クラレ グリップ
JP2014514389A (ja) * 2011-03-24 2014-06-19 スリーエム イノベイティブ プロパティズ カンパニー 難燃テープ
JP2014515049A (ja) * 2011-03-24 2014-06-26 スリーエム イノベイティブ プロパティズ カンパニー 難燃接着剤
JP2014164052A (ja) * 2013-02-22 2014-09-08 Dainippon Printing Co Ltd 粘着層付き位相差フィルム及びこれを用いた光学部材
WO2016167292A1 (fr) * 2015-04-17 2016-10-20 株式会社クラレ Composition de résine méthacrylique
WO2017002904A1 (fr) * 2015-06-30 2017-01-05 三菱樹脂株式会社 Film optique multicouche et plaque polarisante

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241568A (ja) * 2001-02-19 2002-08-28 Kanegafuchi Chem Ind Co Ltd 熱可塑性樹脂組成物、およびフィルムまたはシート
JP3150674U (ja) * 2009-03-09 2009-05-28 株式会社クラレ グリップ
JP2014514389A (ja) * 2011-03-24 2014-06-19 スリーエム イノベイティブ プロパティズ カンパニー 難燃テープ
JP2014515049A (ja) * 2011-03-24 2014-06-26 スリーエム イノベイティブ プロパティズ カンパニー 難燃接着剤
JP2014164052A (ja) * 2013-02-22 2014-09-08 Dainippon Printing Co Ltd 粘着層付き位相差フィルム及びこれを用いた光学部材
WO2016167292A1 (fr) * 2015-04-17 2016-10-20 株式会社クラレ Composition de résine méthacrylique
WO2017002904A1 (fr) * 2015-06-30 2017-01-05 三菱樹脂株式会社 Film optique multicouche et plaque polarisante

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022215500A1 (fr) * 2021-04-07 2022-10-13
WO2022215500A1 (fr) * 2021-04-07 2022-10-13 株式会社クラレ Composition de résine contenant un copolymère séquencé acrylique

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