TW201840407A - Molded body and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide a molded body having a resin layer with transparency, shock absorption, adhesiveness with a polar resin, and flexibility. Provided is a molded body comprising: a layer (I) made of a resin including an acrylic block copolymer; and a layer (II) made of a polar resin, wherein the acrylic block copolymer has, in a molecule, at least one structure in which methacrylic ester polymer blocks (a2) are respectively bonded to both ends of an acrylic ester polymer block (a1), has a weight average molecular weight of 10,000-200,000, and includes the polymer block (a2) in an amount of 10-65 mass%, and the resin including the acrylic block copolymer has a total light transmittance as a 3-mm thickness sheet of 90% or higher, an adhesiveness with the polar resin of 50 N/40 mm or higher at a peeling speed of 100 mm/min, and a tanδ measured by the tensile dynamic viscoelasticity measurement at 23 DEG C and a frequency of 11 Hz, of 0.20 or higher.

Description

   Shaped body and manufacturing method thereof   

The present invention relates to a molded article having a layer containing a resin containing a specific acrylic block copolymer and a layer containing a polar resin, and a method for producing the same.

Composite products of hard plastics and soft materials are widely used in all fields of automobiles, construction materials, electrical products, daily necessities, and other fields. For example, as protective members (cases, covers, etc.) for protecting electronic devices such as mobile phones, polycarbonate is used for hard protective members, and polyvinyl chloride is used for soft protective members. Polystyrene-based elastomers, polyurethane-based elastomers, and the like use a part of a protective member that integrates hard and soft types. In addition, soft materials have been proposed by various companies as impact absorbing materials.

For example, Patent Document 1 studies a styrene-based thermoplastic elastomer composition suitable for applications such as a shock-proof material, an impact-absorbing material, a cover material, and a buffer material. Patent Document 2 studies a thermoplastic resin blend that is excellent in melt adhesion with a polar base resin, and is coated or bonded to the surface of the base resin layer and has a soft feel on the surface, and provides elasticity, shock resistance, and damage prevention functions. . Patent Document 3 studies an impact absorbing material including an elastomer composition for protecting various electronic devices and the like from impact or vibration. Patent Document 4 studies an acrylic block copolymer that is excellent in flexibility, transparency, and adhesion to a substrate, and is superior in vibration damping property to a styrene elastomer of the same degree.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-169666

Patent Document 2: Japanese Patent Application Laid-Open No. 2009-91384

Patent Document 3: Japanese Patent Application Laid-Open No. 2010-275457

Patent Document 4: Japanese Patent Application Laid-Open No. 2009-79120

However, Patent Documents 1 to 3 do not describe the transparency of the composition, and are not suitable for applications requiring transparency. In addition, Patent Document 4 widely describes the use of an acrylic block copolymer, but it is not specific, and there is no description about the adhesiveness with a polar resin. Therefore, a composition having both transparency, impact absorption, and adhesiveness with a polar resin cannot be obtained, and there is still room for improvement.

In view of the foregoing, a problem to be solved by the present invention is to provide a molded body of a resin layer having transparency, impact absorption, adhesion to a polar resin, and flexibility.

The inventors of the present case made intensive research in order to solve the above-mentioned problems, and as a result, they found that when a specific acrylic block copolymer is used, they have both transparency, impact absorption, adhesion to a polar resin, and flexibility. Based on this knowledge, the molded body of the resin layer was further researched to complete the present invention.

That is, the present invention is: [1] A formed article comprising a layer (I) containing a resin containing an acrylic block copolymer and a layer (II) containing a polar resin, wherein the acrylic block copolymer is in the molecule It has a structure in which at least one polymer block (a1) having a methacrylate unit as a main body is bonded to both ends of the polymer block (a1) having an acrylate unit as a main body, and has a weight average molecular weight of 10,000 to 200,000, the content of the polymer block (a2) is 10 to 65% by mass, and the total light transmittance of the resin-based 3mm thickness including the aforementioned acrylic block copolymer is 90% or more, at a peeling speed of 100mm / min, and The adhesive force of the aforementioned polar resin is 50N / 40mm or more. As measured by tensile dynamic viscoelasticity, the tanδ measured at 23 ° C and a frequency of 11Hz is 0.20 or more. [2] The molded article according to [1], wherein The solubility parameter is 8 to 13 (cal / cm ³ ) ^1/2 ; [3] The molded body such as [1] or [2], wherein the flexural modulus of elasticity at 23 ° C. of the foregoing polar resin is 2,000 to 3,500 MPa; [ 4] The formed body according to any one of [1] to [3], wherein a total thickness of 3 mm of the foregoing polar resin is The linear transmittance is 88% or more; [5] The molded article according to any one of [1] to [4], in which the A hardness of the resin containing the aforementioned acrylic block copolymer is 23 ° C at 20 to 75; 6] The formed article according to any one of [1] to [5], wherein the thickness of the layer (I) is 0.1 to 10 mm; [7] A protective member for an electronic device, comprising the member as described in [1] to [6] [8] A protective member for an electronic device such as [7], which is a protective member for a smart phone; [9] A manufacturing method, such as any one of [1] to [6] The method for manufacturing a molded article or a protective member for an electronic device such as [7] or [8] is performed by injection molding or extrusion molding.

According to the present invention, it is possible to provide a molded body of a resin layer having transparency, impact absorption, adhesion to a polar resin, and flexibility by adopting the above-mentioned configuration.

    [Form of Implementing Invention]    

Hereinafter, the present invention will be described in detail.

The molded article of the present invention includes a layer (I) containing a resin containing an acrylic block copolymer and a layer (II) containing a polar resin. Here, the acrylic block copolymer-based molecule has at least one polymer block having a methacrylate unit as a main component, which is bonded to both ends of the polymer block (a1) having an acrylate unit as a main component. The structure of (a2) has a weight average molecular weight of 10,000 to 200,000, and the content of the polymer block (a2) is 10 to 65% by mass. In addition, the total light transmittance of a resin-based 3 mm thickness containing an acrylic block copolymer is 90% or more, and the adhesive force with the polar resin is 50 N / 40 mm or more at a peeling speed of 100 mm / min. The elasticity was measured, and tan δ measured at 23 ° C. and a frequency of 11 Hz was 0.20 or more.

    [Acrylic block copolymer]    

The acrylic block copolymer in the present invention has at least one polymer intercalated with a methacrylate unit as a main polymer at both ends of the polymer block (a1) having the acrylate unit as a main body in the molecule. The structure of the segment (a2), that is, the structure of (a2)-(a1)-(a2) ("-" in the structure represents a chemical bond).

The content of the acrylate 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. Examples of the acrylate to be the acrylate unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, secondary butyl acrylate, and the like. Tertiary butyl acrylate, pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isoamyl acrylate, acrylic acid Phenyl ester, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, and the like. Among such acrylates, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, Alkyl acrylates such as phenoxyethyl acrylate and 2-methoxyethyl acrylate are more preferably n-butyl acrylate and 2-ethylhexyl acrylate. The polymer block (a1) may be composed of one type of these acrylates, or may be composed of two or more types.

In addition, as long as the object and effect of the present invention are not impaired, the polymer block (a1) may include a unit derived from an acrylate having a reactive group, such as glycidyl acrylate, allyl acrylate, or the like; or Units of polymerizable monomers other than acrylic acid esters such as methacrylic acid, methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile, and olefins, etc., are used as copolymerization components. From the standpoint of exhibiting the effects of the present invention, these units derived from the acrylate having a reactive group or units derived from other polymerizable monomers are preferably in a small amount, and the total content of the two in the polymer block (a1) is smaller. It is preferably 10% by mass or less, and more preferably 2% by mass or less.

The content of the methacrylate 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. Examples of the methacrylate to be the methacrylate unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-methacrylate Butyl ester, isobutyl methacrylate, secondary butyl methacrylate, tertiary butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate Ester, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isoamyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid Phenoxyethyl, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, and the like. Among these methacrylates, from the viewpoint of improving transparency and heat resistance, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid are preferred. Alkyl methacrylate such as tertiary butyl ester, cyclohexyl methacrylate, isoamyl methacrylate, and the like are more preferably methyl methacrylate. The polymer block (a2) may be composed of one kind of these methacrylates, or may be composed of two or more kinds.

In addition, as long as the object and effect of the present invention are not impaired, the polymer block (a2) may include units derived from methacrylate having a reactive group, such as glycidyl methacrylate, allyl methacrylate, and the like; Alternatively, a unit derived from a polymerizable monomer other than a methacrylate such as acrylate, methacrylic acid, acrylic acid, aromatic vinyl compound, acrylonitrile, methacrylonitrile, or olefin, etc., as a copolymerization component. These units derived from a methacrylate having a reactive group or units derived from other polymerizable monomers are preferably in a small amount, and the total content of both in the polymer block (a2) is preferably 10% by mass or less. It is more preferably 2% by mass or less.

The molecular chain form of the acrylic block copolymer is not particularly limited as long as it has a structure having at least one polymer block (a2) bonded to both ends of the polymer block (a1) in the molecule, for example It may be any of linear, branched, radial, etc. Among them, a triblock represented by (a2)-(a1)-(a2) is preferred. Here, the molecular weight, composition, and the like of (a2) at both ends of (a1) may be the same or different from each other. In addition, as long as the object and effect of the present invention are not impaired, the acrylic block copolymer-containing resin constituting the layer (I) may be used together with the acrylic block copolymer described above, and may further include the components (a2)-(a1). Represents an acrylic diblock copolymer.

As long as the object and effect of the present invention are not impaired, the acrylic block copolymer may have polymer blocks (c) derived from monomers other than acrylates and methacrylates as these polymer blocks ( polymer blocks other than a1) and (a2). The bonding form of the polymer block (c) with the polymer block (a1) and the polymer block (a2) is not particularly limited, and examples thereof include (a2)-((a1)-(a2) )) Structures such as _n- (c) or (c)-(a2)-((a1)-(a2)) _n- (c) (n is an integer from 1 to 20).

Examples of the monomer constituting the polymer block (c) include olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; 1,3-butadiene and isoprene Conjugated dienes such as olefin, laurylene, etc .; aromatic ethylene such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene; vinyl acetate, vinylpyridine, acrylonitrile, Methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε-caprolactone, valerolactone and the like.

The acrylic block copolymer used in the present invention may have functional groups such as a hydroxyl group, a carboxyl group, an acid anhydride, and an amine group in a molecular chain or a molecular chain terminal, if necessary.

The weight average molecular weight of the acrylic block copolymer is 10,000 to 200,000 from the viewpoints of transparency, impact absorption, and adhesiveness with the polar resin of the obtained layer (I). 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 during injection molding or extrusion molding, and a good molded body can be obtained. In addition, the obtained molded article is excellent in mechanical properties such as breaking strength and the like. On the other hand, if the weight average molecular weight of the acrylic block copolymer is 200,000 or less, the surface of a molded body obtained by injection molding or extrusion molding is unlikely to have minute wrinkled irregularities or is caused by non-melting. The pits of the material (high molecular weight body) can easily obtain a molded body having an excellent appearance.

In addition, 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 may be in the range of 1.01 or more and less than 1.50, and more preferably It is in the range of 1.01 to 1.35. By adopting such a range, it is possible to make the content of the unmelted material in the layer (I) the cause of pitting extremely small.

The weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are polystyrene equivalents measured by gel, permeation, and chromatography, and can be measured by methods described later in the examples. .

The content of the polymer block (a2) in the acrylic block copolymer is 10 to 65% by mass, preferably 12% by mass or more, from the viewpoints of transparency, impact absorption, and adhesiveness with a polar resin. It is preferably 13% by mass or more, even more preferably 14% by mass or more, and particularly preferably 15% by mass or more. In addition, it is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less. When the content of the polymer block (a2) in the acrylic block copolymer is smaller than the above range, the stickiness of the acrylic block copolymer-containing resin constituting the layer (I) increases, which may make it unsuitable. As a molding material. On the other hand, when 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 harder. The impact absorptivity is lost, and the adhesiveness with a polar resin tends to further decrease.

The method for producing the acrylic block copolymer is not particularly limited, and a method according to a known method can be adopted. For example, a method of living-polymerizing monomers constituting each block is generally used. Examples of such a living polymerization method include a method of performing anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt (see Japanese Patent No. Japanese Patent Publication No. 7-25859); a method in which an organic alkali metal compound is used as a polymerization initiator and anionic polymerization is performed in the presence of an organic aluminum compound (see Japanese Patent Application Laid-Open No. 11-335432); an organic rare earth metal is mixed For polymerizing a polymer as a polymerization initiator (see Japanese Patent Application Laid-Open No. 6-93060); and a method for radical polymerization using an α-halogenated ester compound as a starter in the presence of a copper compound (see Macromolecular Chemical Physics (Macromol. Chem. Phys.) 201, pp. 1108 ~ 1114 (2000)) and so on. Another example is a method in which a monomer constituting each block is polymerized using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent, and is produced as a mixture containing an acrylic block copolymer. Method, etc. Among these methods, in particular, it is possible to obtain an acrylic block copolymer with high purity, and it is easy to control molecular weight or composition ratio, and it is economical. It is recommended to use an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound. An anionic polymerization method is carried out.

The acrylate used in the production of the polymer block (a1) having the acrylate unit as a main component can be prepared as a mixed monomer in which two or more kinds are mixed in advance, and it is preferable to use an acrylate and an aromatic acrylate. Mixed monomers. In this case, it is preferably a mixed monomer of 50 to 90% by mass of an alkyl acrylate and 50 to 10% by mass of an aromatic acrylate, more preferably 60 to 80% by mass of an alkyl acrylate and 40 to 20 of an aromatic acrylate. Mass% mixed monomer.

    [Resin containing acrylic block copolymer]    

The layer (I) in the present invention contains a resin containing an acrylic block copolymer. The resin constituting the layer (I) may be a resin containing only an acrylic block copolymer, or a resin composition containing an acrylic block copolymer and other components. The types of components other than the acrylic block copolymer in the resin composition are not particularly limited, and various polymers, additives, fillers, and the like described below can be mentioned. The content of the acrylic block copolymer in the acrylic block copolymer-containing resin constituting the layer (I) is preferably 55% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. It may be 100% by mass.

As a component other than an acrylic block copolymer in the said resin composition, the acrylic polymer which mainly has a methacrylate unit as a main body is preferable.

The acrylic polymer preferably contains 80% by mass or more of methacrylate units, and more preferably contains 90% by mass or more. Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. Ester, secondary butyl methacrylate, tertiary butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Pentadecyl ester, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxylate Ethyl ester, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornyl methacrylate, isofluorenyl methacrylate, and the like. Among them, particularly preferred is methyl methacrylate.

The acrylic polymer may contain monomer units other than methacrylate units. Examples of the monomers that serve as the other monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and secondary butyl acrylate. , Tertiary butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, benzene acrylate Acrylates such as oxyethyl, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornene acrylate, isoamyl acrylate, etc. ; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutene, 1-octene, etc .; butadiene Conjugated diene such as olefin, isoprene, laurylene, etc .; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene; allylamine, Methacrylamide, acrylonitrile, Methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like.

The method for producing the acrylic polymer is not particularly limited. A commercially available product can be used as the acrylic polymer. Examples of the commercially available products include "Parapet H1000B" (MFR: 22g / 10 minutes (230 ° C, 37.3N)) and "Parapet GF" (MFR: 15g / 10 minutes (230 ° C, 37.3N) ), "Parapet EH" (MFR: 1.3g / 10 minutes (230 ° C, 37.3N)), "Parapet HRL" (MFR: 2.0g / 10 minutes (230 ° C, 37.3N)), "Parapet HRS" (MFR : 2.4 g / 10 minutes (230 ° C, 37.3N)) and "Parapet G" (MFR: 8.0g / 10 minutes (230 ° C, 37.3N)) [all are trade names, manufactured by Kuraray Co., Ltd.] and the like.

When the above-mentioned resin composition contains the above-mentioned acrylic polymer, its content is preferably 1 to 45% by mass, more preferably 3 to 30% by mass, and even more preferably 5 to 15% by mass.

The resin composition may contain other polymers in addition to the acrylic block copolymer and the acrylic polymer as necessary. Examples of other polymers include olefin-based resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; and ethylene-based ionic polymers; Styrene resins such as polystyrene, styrene-maleic anhydride copolymer, impact-resistant polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate -Styrene copolymer; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid; Polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; esters Polyurethane elastomer, ether-based polyurethane elastomer, non-yellowing ester-based polyurethane elastomer, non-yellowing carbonate-based polyurethane elastomer, etc. Polyurethane resin; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, modified polyphenylene ether, poly Phenyl sulfide, silicone rubber modified resin, etc. Among them, AS resins and polyvinylidene fluoride are preferred from the viewpoint of compatibility with the acrylic block copolymer.

In addition, the above-mentioned resin composition may contain various known additives (for example, rubber, lubricants, antioxidants, light stabilizers, colorants, antistatic agents, flame retardants) as long as the effects of the present invention are not impaired. Etc.), fillers (for example, fiber reinforcing agents such as glass fibers, inorganic fillers, etc.) and the like. Examples of the rubber contained in the additive include acrylic rubber; silicone rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM. 1 or more types. Examples of other additives or fillers include mineral oil softeners such as paraffin-based oils and naphthenic oils, which are used to improve the fluidity during forming processing, and increase or increase in heat resistance and weather resistance. Inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate, etc .; inorganic fibers or organic fibers for reinforcing glass fibers, carbon fibers, etc .; heat stabilizers Antioxidants; Light stabilizers; Adhesives; Tackifiers; Plasticizers; Antistatic agents; Foaming agents; Colorants; Dyes; Among such additives, in order to further improve heat resistance and weather resistance, it is practically preferable to add a heat stabilizer, an antioxidant, and the like.

The transparent light-based 3 mm thickness of the resin containing the acrylic block copolymer constituting the layer (I) has a total light transmittance of 90% or more, preferably 91% or more, and more preferably 92% or more. When the total light transmittance of a thickness of 3 mm is 90% or more, the transparency of the formed body having the layer (I) and the layer (II) produced by injection molding or extrusion molding is good and the creativity is excellent. The total light transmittance of the 3 mm thickness can be measured by a haze meter using a molded article having a thickness of 3 mm obtained by injection-molding the resin containing the acrylic block copolymer constituting the layer (I). Specifically, In the examples, measurement can be performed by a method described later.

When the total content of the block (a1) in the acrylic block copolymer is in the range of 35 to 90% by mass, particularly 55 to 87% by mass, the flexibility is improved, and the rubber-like component formed by (a1) is changed. It becomes easy to form a matrix, and it becomes easy to arrange | position at the interface with a polar resin, and there exists a tendency for adhesive force to become easy to improve. At a peeling speed of 100 mm / minute, 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, preferably 60 N / 40 mm or more. More preferably, it is 70N / 40mm or more. When the adhesion force to the polar resin is 50 N / 40 mm or more at a peeling speed of 100 mm / minute, the adhesion between the layer (I) and the layer (II) containing the polar resin becomes good, and a molding having sufficient strength can be obtained. body. There is no particular limitation on the upper limit, and the higher the better, but it is usually 800 N / 40 mm or less. Adhesion to this polar resin enables a laminated body containing a resin containing an acrylic block copolymer to have a thickness of 1 mm and a layer containing a polar resin having a thickness of 1 mm, and a laminated body having a total thickness of 2 mm according to ISO 11339. The measurement is performed, and specifically, in the examples, the measurement can be performed by a method described later.

When the total content of the block (a1) in the acrylic block copolymer is in the range of 35 to 90% by mass, and particularly in the range of 55 to 87% by mass, the rubber-like component formed by (a1) easily forms a matrix. Therefore, the peak of tan δ derived from the block (a1) tends to increase, and the value of tan δ at 23 ° C tends to increase. The resin containing the acrylic block copolymer constituting the layer (I) is measured by tensile dynamic viscoelasticity, and tan δ measured at 23 ° C. and a frequency of 11 Hz is 0.20 or more, preferably 0.21 or more, and more preferably 0.22 or more. If the tan δ is 0.20 or more, the layer (I) is excellent in impact absorption. Therefore, the obtained molding system of the present invention is excellent in impact absorption. For example, it can be suitably used as protection for protecting electronic equipment from impact. Component (shell or cover, etc.). The upper limit is not particularly limited, but is usually 3.0 or less. The tan δ can be measured by a viscoelasticity measuring device. Specifically, in the examples, it can be measured by a method described later.

The resin having an acrylic block copolymer constituting the layer (I) preferably has an A hardness at 23 ° C. of 20 to 75, more preferably 22 to 73, and even more preferably 24 to 71. When the A hardness at 23 ° C is 20 to 75, the flexibility of the layer (I) is improved, and the flexibility of the obtained molded body is also improved.

When the resin constituting the layer (I) is a resin composition containing an acrylic block copolymer and other components, the method for preparing the resin composition is not particularly limited, but in order to improve the dispersibility of each component It is recommended to carry out melt kneading and mixing. For example, when preparing a resin composition containing an acrylic block copolymer and the acrylic polymer, the acrylic block copolymer and the acrylic polymer may be melt-kneaded. Here, when the other polymers, additives, fillers, and the like described above are mixed with the resin composition, these components may be mixed simultaneously with the melt-kneading of the acrylic block copolymer and the acrylic polymer, or the components may be mixed. The acrylic block copolymer is mixed with these components, and then mixed with the acrylic polymer.

The mixing operation can be performed using, for example, a known mixing or kneading device such as a kneading extruder, an extruder, a mixing roll, or a closed kneader. In particular, it is preferable to use a biaxial extruder from the viewpoint of improving the kneadability and mutual solubility of the acrylic block copolymer and the acrylic polymer. The temperature during mixing and kneading can be appropriately adjusted according to the melting temperature of the acrylic block copolymer and the acrylic polymer to be used, and usually the mixing is performed at a temperature in the range of 110 to 300 ° C. By operating in this manner, a resin composition containing an acrylic block copolymer can be obtained in an arbitrary form such as particles or powder. The resin composition obtained by operating in this manner is formed into a layer (I) by a method described later.

    [Polar resin]    

As the polar resin constituting the layer (II), a resin containing a polar polymer can be used. This polar resin may be a polar resin composition or a polar resin composition including a polar polymer and other components. The types of components other than the polar resin in the polar resin composition are not particularly limited, and examples thereof include various polymers, additives, and fillers 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, even more preferably 80% by mass or more, and may also be 100% by mass.

As the polar resin constituting the layer (II), a thermoplastic rigid polar resin can be used, and examples thereof include ethylene-based ionic polymers; polystyrene, styrene-maleic anhydride copolymer, and impact-resistant polystyrene. , AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and other styrenic resins; acrylic resins such as polymethyl methacrylate; methyl methacrylate-styrene copolymers; polyterephthalic acid Polyester resins such as ethylene glycol, polybutylene terephthalate, and polylactic acid; polyamide resins such as nylon 6, nylon 66; ester polyurethanes, ether polyurethanes Polyurethane resins such as non-yellowing ester-based polyurethanes, non-yellowing carbonate-based polyurethanes; polycarbonate, polyvinyl chloride, polyvinylidene chloride, poly Vinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, modified polyphenylene ether, polyphenylene sulfide, etc. Among these, polycarbonate, polystyrene, and hard acrylic resin are preferred from the viewpoint of adhesiveness with layer (I).

The polar resin is preferably one having a solubility parameter within a range of 8 to 13 (cal / cm ³ ) ^1/2 , and more preferably one having a solubility parameter within a range of 8 to 11 (cal / cm ³ ) ^1/2 . When the solubility parameter is within the above range, the difference between the solubility parameter and the layer (I) tends to be small, so that the wettability at the resin interface is also improved, and the adhesion is also good. In addition, in this specification, the solubility parameter is set by the method described in the Example.

The polar resin preferably has a flexural modulus of 23 ° C of 2,000 to 3,500 MPa, more preferably 2,200 to 3,300 MPa, and even more preferably 2,300 to 3,000 MPa. If the flexural modulus of elasticity at 23 ° C is 2,000 MPa or more, the rigidity can be sufficiently ensured even in a thin wall in a range capable of forming the layer (II) containing a polar resin, and if it is 3,500 MPa or less, it will be described later The moldability of the formed body is also good.

The polar resin is preferably one having a total light transmittance of 3 mm thickness or more, 88% or more, more preferably 89% or more, and even more preferably 90% or more. When the total light transmittance of the 3 mm thickness is 88% or more, the transparency of the layer (I) containing a polar resin is good, and the transparency of the obtained molded article is also good, and the creativity is excellent. The total light transmittance of the 3 mm thickness can be measured by a haze meter using a molded product having a thickness of 3 mm obtained by injection-molding the polar resin constituting the layer (II). Specifically, in the examples, the The measurement was performed by the method described later.

    [Formed body]    

The molding system of the present invention includes the layer (I) containing the acrylic block copolymer-containing resin and the layer (II) containing a polar resin. In the present invention, there may be other layers besides the layer (I) and the layer (II), and it is preferable that the layer (I) and the layer (II) are adjacent to each other.

The molded article of the present invention has a layer (I) having excellent transparency, flexibility, and impact absorption. On the other hand, it is possible to impart transparency and rigidity to the molded body of the present invention through the layer (II). Therefore, the molded article of the present invention can have properties including excellent transparency, rigidity through the layer (II), flexibility with the layer (I), and excellent shock absorption properties.

The thickness of the layer (I) and the layer (II) constituting the formed body of the present invention is not particularly limited, and the thickness of the layer (I) is preferably 0.1 to 10 mm from the viewpoint of excellent flexibility of the molding system and impact absorption. It is preferably 0.3 ~ 5mm, and even more preferably 0.5 ~ 3mm, which can be 0.7 ~ 2mm, or even 1 ~ 1.5mm. In addition, the thickness of the layer (II) is preferably 0.3 to 10 mm, more preferably 0.5 to 5 mm, and even more preferably 1 to 3 mm.

The formed article of the present invention can be formed by using a commonly used forming method or a forming apparatus. For example, the layer (I) and the layer can be formed by a heat-melting forming processing method such as extrusion molding, extrusion lamination, injection molding, compression molding, blow molding, calendar molding, vacuum molding, and the like, solution casting method, and the like. At least one of (II), thereby producing a formed body of the present invention. Among these, the molded body of the present invention is preferably manufactured by injection molding or extrusion molding. Here, when the molded article of the present invention is manufactured by injection molding or extrusion molding, at least one of the layer (I) and the layer (II) may be injection molded or extrusion molded. For example, in the case where the resin composition is used to form the layer (I), the resin composition may be used for injection molding or extrusion molding.

As a specific method for manufacturing the molded article of the present invention, for example, there may be mentioned a method in which the layer (I) and the layer (II) are individually formed in advance, and these layers are laminated (Method 1); II) A method (method 2) of disposing a resin containing an acrylic block copolymer (acrylic block copolymer or a resin composition containing the same) in a molten state to form a layer (I); a previously manufactured layer (I ) A method of disposing a polar resin in a molten state to form the layer (II) (method 3); a resin (acrylic block copolymer or acrylic block copolymer or A method (method 4) and the like in which a resin composition including the same) and a polar resin in a molten state are mutually arranged to form the layer (I) and the layer (II). Among these, methods 2 to 4 are preferred in order to improve the adhesion between the layer (I) and the layer (II), etc., and method 2 is more preferred from the purpose of easily obtaining a molded article or the like. Further, since the resin-based melt containing the acrylic block copolymer is excellent in fluidity, it is preferable to form the layer (I) by injection molding, and it is more preferable to use a layer (II) formed in advance in a mold. , And then insert molding the resin (acrylic block copolymer or resin composition containing the same) containing the acrylic block copolymer in a molten state.

    [Use]    

The use of the formed body of the present invention is not particularly limited, and it can be used in various applications such as the optical field, the food field, the medical field, the people's livelihood field, the automobile field, the electrical and electronic field, and the construction field from the point of having the above characteristics. For example, as a protective member (case, cover, etc.) for an electronic device such as a smart phone terminal, since it is excellent in shock absorption, it is possible to protect the smart phone terminal and the like from an impact or collision caused by dropping. In addition, since it is excellent in transparency and flexibility, design and creativity can be provided, and detachment is easy. As other uses, it can be suitably used in various housings, covers, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, clocks, VTRs, projection televisions, etc. Fresnel lens, various optical disc (VD, CD, DVD, MD, LD, etc.) substrate protection film, optical switch, optical connector, liquid crystal display, light guide film for liquid crystal display‧ sheet, flat panel display, light guide for flat panel display Film ‧ Sheet, Plasma Display, Light Guide Film for Plasma Display ‧ Sheet, Phase Difference Film ‧ Sheet, Polarizing Film ‧ Sheet, Polarizer Protection Film ‧ Sheet, Wavelength Plate, Light Diffusion Film ‧ Sheet, 稜鏡 Film ‧ Sheet , Reflective film, sheet, anti-reflective film, sheet, viewing angle expansion film, sheet, anti-glare film, sheet, brightness enhancement film, sheet, display element substrate for liquid crystal or electroluminescence, touch panel, and touch panel guide Light film, sheet, spacers between various front panels and various modules. Furthermore, it can be used for various liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, automotive LCD monitors, LCD monitors, dimming panels, OA device monitors, AV device monitors, and other electronic devices. An electroluminescence display element or a touch panel. In addition, from the point of excellent impact absorption or polar resin adhesion, for example, it can also be used for building interior and exterior decoration members, curtain walls, roof members, roof materials, window members, rain gutters, outdoor products, and wall surfaces. Materials, floor materials, decoration materials, road construction components, retro-reflective films ‧ sheets, agricultural films ‧ sheets, lighting covers, advertising boards, light-transmitting sound-proof walls, etc.

    [Example]    

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to them in any way. In addition, various physical properties in Examples and Comparative Examples were measured or evaluated by the following methods.

(1) 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 are determined by gel · permeation · chromatography (hereinafter referred to as GPC) and calculated in terms of molecular weight in terms of polystyrene. Details as follow.

‧Equipment: Tosoh Co., Ltd. GPC device "HLC-8020"

‧Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Co., Ltd.

‧Eluent: Tetrahydrofuran

‧Eluent flow: 1.0ml / min

‧Column temperature: 40 ℃

‧Detection method: differential refractive index (RI)

(2) 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 as follow.

‧Equipment: Nuclear magnetic resonance device "JNM-LA400" made by Japan Electronics Co., Ltd.

‧Deuterated solvent: deuterated chloroform

(3) Adhesiveness of resin constituting layer (I) to polar resin

For the molded bodies obtained in the examples and comparative examples (for a layer containing a polar resin with a thickness of 1 mm, a layer containing the resin constituting the layer (I) was laminated and laminated with a thickness of 100 mm × 40 mm and a total thickness of 2 mm), The adhesion force between the layer (I) and the layer (II) was measured with a tensile tester (manufactured by Instron) at a peeling speed of 100 mm / min in accordance with ISO 11339, and this was used as the resin (acrylic acid) constituting the layer (I). Adhesion of a block copolymer or a resin composition containing the same to a polar resin.

(4) Transparency

In the following examples or comparative examples, the resins (acrylic block copolymers or resin compositions containing the same) and polar resins constituting the layer (I) were respectively molded by injection molding machines (Sumitomo Heavy Industries, Ltd.) ("SE18DU", manufactured by Co., Ltd.), a molded body having a thickness of 50 mm x 50 mm and a thickness of 3 mm was produced at the following cylinder temperature and mold temperature, and measured by a direct reading haze meter (manufactured by Nippon Denshoku) in accordance with ISO 13468-1. The total light transmittance is used as an index of transparency.

‧Cylinder temperature: 210 ° C (in the examples or comparative examples, the resin constituting the layer (I)), 230 ° C (polystyrene, PMMA), 290 ° C (polycarbonate)

‧Mold temperature: 50 ° C (in the examples or comparative examples, the resin constituting the layer (I)), 60 ° C (polystyrene, PMMA), 90 ° C (polycarbonate)

(5) Dynamic viscoelasticity (shock absorption)

In the following examples or comparative examples, a resin (acrylic block copolymer or a resin composition containing the same) was used to constitute the layer (I), and a length of 20 mm and a width of 5 mm were produced at the following pressure molding temperature. Thin sheet with a thickness of 1mm. The obtained sheet was subjected to dynamic viscoelasticity measurement using a viscoelasticity spectrometer "Rheogel-E4000" (manufactured by UBM) under measurement conditions of a frequency of 11 Hz and a measurement temperature of -100 to 250 ° C. Loss tangent (tan δ).

‧Press forming temperature: 210 ℃

(6) A hardness

In the following examples or comparative examples, the resin (acrylic block copolymer or resin composition containing the same) constituting the layer (I) was used by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., " SE18DU "), a molded body of 50 mm x 50 mm and a thickness of 3 mm was produced at the following cylinder temperature and mold temperature. Three obtained molded bodies were stacked, and the A hardness after 15 seconds was measured according to ISO 7619-1.

‧Cylinder temperature: 210 ℃

‧Mold temperature: 50 ℃

(7) Solubility parameters

The solubility parameter of the polar resin is based on the value [(MPa) ^1/2 ] described in the "Polymer Handbook 4th Edition" (edited by Wiley-Interscience) as a reference, and the unit is converted using this value [(cal / cm ³ ) ^1/2 ]. In addition, the solubility parameters of resins not described in the "Polymer Handbook" are based on Hoy's molecular structure estimated from the literature reported in "KLHoy, Journal of Paint Technology, 42 (541), 76 (1970)" The calculation method calculates the value [(MPa) ^1/2 ], and uses the same unit conversion [(cal / cm ³ ) ^1/2 ] as described above.

(8) Flexural modulus

The bending elastic modulus of the polar resin at 23 ° C is the injection temperature (cylinder temperature and cylinder temperature) of each polar resin described in (4) by an injection molding machine ("UH1000-80" manufactured by Nissei Resin Industry Co., Ltd.). Under the conditions of mold temperature), a molded body of 80 mm × 10 mm and a thickness of 4 mm was produced. About the obtained molded object, the bending elastic modulus was measured according to ISO 178.

The physical properties of the polar resins used in the following examples and comparative examples are shown in Table 1.

Polycarbonate (PC): Iupilon S2000 (Mitsubishi Engineering Plastics Co., Ltd.)

Polystyrene (PS): SX100 (PS Japan Co., Ltd.)

PMMA: Parapet HR-L (Kuraray Co., Ltd.)

In the synthesis examples shown below, the compounds were dried and purified by a common method, and degassed with nitrogen. The compound transfer and supply were performed under a nitrogen atmosphere.

    [Synthesis Example 1] [Organic aluminum compound: Preparation of isobutylbis (2,6-di-tertiarybutyl-4-methylphenoxy) aluminum]    

After drying with sodium, 25 ml of dry toluene and 11 g of 2,6-di-tertiary-butyl-4-methylphenol obtained by distillation under an argon atmosphere were added to a 200-ml flask having an inner volume replaced by argon. Then, the solution was dissolved while stirring at room temperature. 6.8 ml of triisobutylaluminum was added to the obtained solution, and the mixture was stirred at 80 ° C. for about 18 hours to prepare a corresponding organoaluminum compound [isobutylbis (2,6-di- Tertiary butyl-4-methylphenoxy) aluminum] in toluene.

    [Synthesis Example 2] [Synthesis of acrylic block copolymer (A1)]    

In the presence of isobutyl bis (2,6-di-tertiarybutyl-4-methylphenoxy) aluminum obtained in Synthesis Example 1, secondary butyllithium was used as a polymerization initiator in toluene. The monomers (methyl methacrylate, n-butyl acrylate, and methyl methacrylate) corresponding to each block are successively added for living anionic polymerization, and the aluminum component and lithium component used are removed. The shaft extruder obtained pellets of an acrylic block copolymer (A1).

Structure of the obtained acrylic block copolymer (A1), which is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer block (PMMA) triblock copolymer, PMMA content (content of polymer block (a2)) of 23.5% by mass, weight average molecular weight of 70,000, and molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.20.

    [Synthesis Example 3] [Synthesis of acrylic block copolymer (A2)]    

The living anionic polymerization was performed in the same manner as in Synthesis Example 2 to obtain particles of the following acrylic block copolymer (A2).

That is, the structure of the obtained acrylic block copolymer (A2) is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer. Triblock copolymer of block (PMMA), PMMA content (content of polymer block (a2)) of 30.5% by mass, weight average molecular weight of 60,000, and molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.15.

    [Synthesis Example 4] [Synthesis of acrylic block copolymer (A3)]    

The living anionic polymerization was performed in the same manner as in Synthesis Example 2 to obtain particles of the following acrylic block copolymer (A3).

That is, the structure of the obtained acrylic block copolymer (A3) is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer. Triblock copolymer of block (PMMA), PMMA content (content of polymer block (a2)) of 38.5% by mass, weight average molecular weight of 65,000, and molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.10.

    [Synthesis Example 5] [Synthesis of acrylic block copolymer (A4)]    

The living anionic polymerization was performed in the same manner as in Synthesis Example 2 to obtain particles of the following acrylic block copolymer (A4).

That is, the structure of the obtained acrylic block copolymer (A4) is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer. Triblock copolymer of block (PMMA), PMMA content (content of polymer block (a2)) 16.0% by mass, weight average molecular weight 140,000, and molecular weight distribution (weight average molecular weight / number average molecular weight) 1.10.

    [Synthesis Example 6] [Synthesis of acrylic block copolymer (A5)]    

A living anion polymerization was carried out in the same manner as in Synthesis Example 2 except that the type of the monomer used was changed to obtain particles of the following acrylic block copolymer (A5).

That is, the structure of the obtained acrylic block copolymer (A5) is a methyl methacrylate polymer block (PMMA)-2-ethylhexyl acrylate polymer block (P2EHA)-methyl methacrylate The triblock copolymer of ester polymer block (PMMA) has a PMMA content (content of polymer block (a2)) of 22.8% by mass, a weight average molecular weight of 76,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.13.

    [Synthesis Example 7] [Synthesis of acrylic block copolymer (A6)]    

A living anion polymerization was performed in the same manner as in Synthesis Example 2 except that the ratio of the monomers used was changed to obtain particles of the following acrylic block copolymer (A6).

That is, the structure of the obtained acrylic block copolymer (A6) is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate / methyl acrylate copolymer block (P (nBA / MA) )-Triblock copolymer of methyl methacrylate polymer block (PMMA), PMMA content (content of polymer block (a2)) 16.0% by mass, weight average molecular weight 150,000, molecular weight distribution (weight average molecular weight / Number average molecular weight) 1.20.

    [Synthesis Example 8] [Synthesis of acrylic block copolymer (A7)]    

A living anion polymerization was performed in the same manner as in Synthesis Example 2 to obtain the following acrylic block copolymer (A7).

That is, the structure of the obtained acrylic block copolymer (A7) is a methyl methacrylate polymer block (PMMA) -n-butyl acrylate polymer block (PnBA) -methyl methacrylate polymer. Triblock copolymer of block (PMMA), PMMA content (content of polymer block (a2)) of 50.0% by mass, weight average molecular weight of 62,000, and molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.12.

    [Examples 1 to 8]    

As the resin constituting the layer (I), the acrylic block copolymers (A1) to (A6) obtained by using Synthesis Examples 2 to 7 or the aforementioned acrylic block copolymers and acrylic polymers ( "Parapet GF" (manufactured by Kuraray Co., Ltd.), obtained by melt-kneading at 230 ° C with a biaxial extruder at a mixing ratio shown in Table 2 below, and obtained by extrusion and cutting Resin. Using this resin and the polar resins described in Table 1 as the resin constituting the layer (II), an injection molding machine ("UH1000-80" by Nissei Plastics Industry Co., Ltd.) was used to produce an insert having a thickness of 100 mm x 40 mm and a total thickness of 2 mm. Next to the shaped body. As a method for producing an insert molding, a plurality of pieces of 100 mm × 40 mm in advance were prepared in advance under the injection temperature (cylinder temperature and mold temperature) of each of the polar resins described in (4) by the aforementioned injection molding machine. The molded body of the layer (II) having a thickness of 1 mm was mounted on an injection molding die having a thickness of 100 mm × 40 mm and a thickness of 2 mm. At a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C., The resin constituting the layer (I) is injected into the gap to produce an insert-molded body.

About the obtained compact, the adhesive force between the layer (I) and the layer (II) was measured according to the above (3). In addition, the physical properties of the resin constituting the layer (I) were evaluated in accordance with the above (4) to (6). The obtained results are shown in Table 2.

    [Comparative Examples 1 to 4]    

Except that the resin constituting the layer (I) was changed as described in Table 3, a molded article was produced by the same method as in the example, and its physical properties were evaluated. The obtained results are shown in Table 3. The resins used in Comparative Examples 2 to 4 are as follows.

Thermoplastic elastomer: "Hybrar 7125 (made by Kuraray Co., Ltd.)"

Thermoplastic polyurethane elastomer: "Elastollan 1198A (manufactured by BASF)"

Thermoplastic polyurethane elastomer (without yellowing): "Miractran XN2004 (manufactured by Tosoh Corporation)"

From the results of the above Tables 2 and 3, it can be seen that the layer (I) in the molded article obtained in Examples 1 to 8 of the present invention has good transparency, adhesion to PC, and softness. In Example 2, the adhesion to PS and PMMA was also good, and it is considered that the same effect can be obtained in other examples. In addition, Examples 1 to 8 are excellent in impact absorption properties of the layer (I), and are particularly excellent in Example 6. In addition, it has low hardness and excellent flexibility. From the above, it can be seen that the molding systems of Examples 1 to 8 are excellent in transparency, impact absorption, and flexibility.

On the other hand, Comparative Example 1 has good transparency, but other properties are inferior. Comparative Example 2 is a thermoplastic elastomer that does not contain an acrylic block copolymer and has poor transparency. Comparative Examples 3 and 4 are thermoplastic polyurethane elastomers which do not contain an acrylic block copolymer, and have poor flexibility. Regarding Comparative Example 4, impact absorption was also poor.

    [Industrial availability]    

According to the present invention, it is possible to provide a molded body having a resin layer having transparency, impact absorption, adhesion to a polar resin, and flexibility, and can be used in the optical field, food field, medical field, people's livelihood field, and automobile field. , Electrical, electronics, construction, etc.

Claims (9)

    A molded article comprising: a layer (I) containing a resin containing an acrylic block copolymer; and a layer (II) containing a polar resin, the acrylic block copolymer having at least one acrylate unit in the molecule The polymer block (a1) as the main body has a structure in which the polymer block (a2) having a methacrylate unit as the main body is bonded to both ends, respectively. The weight average molecular weight is 10,000 to 200,000, and the polymer block (a2) ) Content is 10 to 65% by mass, the total light transmittance of the resin-based 3mm thickness containing the acrylic block copolymer is 90% or more, and the adhesive force with the polar resin is 50N at a peeling speed of 100mm / minute / 40 mm or more, measured by tensile dynamic viscoelasticity, and tan δ measured at 23 ° C and a frequency of 11 Hz was 0.20 or more.     For example, the molded article of claim 1, wherein the polar resin has a solubility parameter of 8 to 13 (cal / cm ³ ) ^1/2 .     For example, the molded article according to claim 1 or 2, wherein the flexural modulus of the polar resin at 23 ° C is 2,000 to 3,500 MPa.         The formed article according to any one of claims 1 to 3, wherein a total light transmittance of 3 mm thickness of the polar resin is 88% or more.         The formed article according to any one of claims 1 to 4, wherein the A hardness of the resin containing the acrylic block copolymer at 23 ° C is 20 to 75.         The formed article according to any one of claims 1 to 5, wherein the thickness of the layer (I) is 0.1 to 10 mm.         A protective member for an electronic device, comprising the formed article according to any one of claims 1 to 6.         The protective member for an electronic device according to claim 7, which is a protective member for a smartphone.         A manufacturing method is a method of manufacturing a molded article according to any one of claims 1 to 6 or a protective member for an electronic device according to claim 7 or 8 by injection molding or extrusion molding.