WO2015079867A1 - 透明樹脂積層体 - Google Patents
透明樹脂積層体 Download PDFInfo
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- WO2015079867A1 WO2015079867A1 PCT/JP2014/079075 JP2014079075W WO2015079867A1 WO 2015079867 A1 WO2015079867 A1 WO 2015079867A1 JP 2014079075 W JP2014079075 W JP 2014079075W WO 2015079867 A1 WO2015079867 A1 WO 2015079867A1
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- resin
- synthetic resin
- mass
- resin laminate
- laminate
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- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- 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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
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- 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
- B32B2457/00—Electrical equipment
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- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
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- 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
- B32B2571/00—Protective equipment
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- 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
- B32B2590/00—Signboards, advertising panels, road signs
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- 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
- B32B2607/00—Walls, panels
Definitions
- the present invention relates to a synthetic resin laminate, and more specifically, is used for a transparent substrate material and a protective material, and includes a polycarbonate base material layer, a resin layer containing a specific styrene copolymer resin and a specific vinyl resin ( And a synthetic resin laminate having excellent shape stability, surface hardness and / or heat resistance in a high temperature or high humidity environment.
- Patent Document 1 proposes a method of coating the surface with an ultraviolet curable resin or the like, and a method of applying a hard coat to a substrate obtained by coextruding a polycarbonate resin and an acrylic resin.
- a hard coat is applied to the surface of the polycarbonate resin, the required pencil hardness cannot be satisfied, and it may not be used for applications requiring the surface hardness.
- the surface hardness is improved to some extent by the method of applying the acrylic resin to the surface layer, the application spreads to the front panel of the information display device, etc., but this method has a two-layer structure of different materials and the acrylic resin and the polycarbonate resin. Due to the difference in water absorption characteristics, warping occurs with changes in the environment, so that problems occur in applications where environmental changes occur.
- Patent Document 2 discloses a laminate characterized by laminating a methylmethacrylate-styrene copolymer, which is a resin having a lower water absorption rate than an acrylic resin, on a polycarbonate resin as a method for suppressing warpage.
- a methylmethacrylate-styrene copolymer which is a resin having a lower water absorption rate than an acrylic resin
- 40 ° C / 90% of the environmental test is insufficient as a condition of high temperature and high humidity.
- Patent Document 3 discloses a laminate characterized by laminating a high-hardness modified polycarbonate resin on a polycarbonate resin, but does not mention water absorption characteristics or shape stability when the environment changes.
- the present invention provides a synthetic resin laminate that is used for transparent substrate materials and protective materials and has excellent shape stability, surface hardness, and heat resistance that does not cause warping even in high-temperature and high-humidity environments. For the purpose.
- a styrene monomer unit unsaturated dicarboxylic acid on one side of a base material layer mainly composed of polycarbonate. Consists of 25 to 100% by weight of a specific styrene-unsaturated dicarboxylic acid copolymer comprising 10 to 30% by weight of an anhydride monomer unit and 10 to 35% by weight of a vinyl monomer, and ii) constitutes a vinyl monomer.
- the inventors have found that a synthetic resin laminate excellent in shape stability and surface hardness can be obtained by laminating a resin composition in which 75 to 0% by mass of a resin as a unit is polymer-alloyed, and the present invention has been achieved. That is, the present invention provides the following synthetic resin laminate and a transparent material using the synthetic resin laminate.
- a resin layer (high hardness layer) comprising a resin (A) containing a specific styrene-unsaturated dicarboxylic acid copolymer (a1) and a resin (a2) having a vinyl monomer as a structural unit ,
- a synthetic resin laminate obtained by laminating on one side of a resin layer (base material layer) containing polycarbonate (B), wherein (a1) is 45 to 70% by mass of a styrene monomer unit, unsaturated dicarboxylic acid A styrene-unsaturated dicarboxylic acid copolymer comprising 10-30% by weight of an acid anhydride monomer unit and 10-35% by weight of a vinyl monomer, the ratio of (a1) in the resin (A) Is a synthetic resin laminate, wherein the ratio (a2) is 75 to 0% by mass.
- ⁇ 2> The synthetic resin laminate according to ⁇ 1>, wherein the vinyl monomer unit (a1) is methyl methacrylate.
- A2) The synthetic resin laminate as described in ⁇ 1> or ⁇ 2> above, comprising 75 to 0% by mass.
- the resin layer containing the resin (A) has a thickness of 10 to 250 ⁇ m, the total thickness of the synthetic resin laminate is in the range of 0.1 to 2.0 mm, and the resin layer / synthetic resin laminate
- ⁇ 6> The synthetic resin laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the resin layer and / or the base material layer contains an ultraviolet absorber.
- ⁇ 7> The synthetic resin laminate according to any one of ⁇ 1> to ⁇ 6>, wherein a hard coat treatment is performed on the resin layer containing the resin (A).
- ⁇ 8> The above ⁇ 1>, wherein one or both surfaces of the synthetic resin laminate are subjected to any one or more of antireflection treatment, antifouling treatment, fingerprint resistance treatment, antistatic treatment, weather resistance treatment and antiglare treatment
- ⁇ 9> A transparent substrate material comprising the synthetic resin laminate according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 10> A transparent protective material comprising the synthetic resin laminate according to any one of ⁇ 1> to ⁇ 8>.
- a touch panel front protective plate including the synthetic resin laminate according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 12> A front plate for OA equipment or portable electronic equipment, comprising the synthetic resin laminate according to any one of ⁇ 1> to ⁇ 8>.
- the synthetic resin laminated body which is excellent in shape stability, surface hardness, and / or impact resistance, such as curvature prevention property in a high temperature or high humidity environment, is provided, and this synthetic resin laminated body is a transparent substrate material. And used as a protective material for transparency.
- portable display devices such as mobile phone terminals, portable electronic play equipment, portable information terminals, and mobile PCs
- stationary display devices such as notebook PCs, desktop PC liquid crystal monitors, and liquid crystal televisions, for example
- It is preferably used as a front plate for protecting these devices.
- the present invention relates to a resin composition in which 25 to 100% by mass of a specific styrene-unsaturated dicarboxylic acid copolymer (a1) and 75 to 0% by mass of a resin (a2) having a vinyl monomer as a structural unit are polymer-alloyed.
- a synthetic resin laminate obtained by laminating a resin layer (high hardness layer) containing a resin containing (A) on one side of a resin layer (base material layer) containing polycarbonate (B), wherein (a1) Is a styrene-unsaturated dicarboxylic acid copolymer comprising 45 to 70% by mass of styrene monomer units, 10 to 30% by mass of unsaturated dicarboxylic acid anhydride monomer units, and 10 to 35% by mass of vinyl monomers.
- the synthetic resin laminate is characterized in that the ratio of (a1) in the resin (A) is 25 to 100% by mass and the ratio of (a2) is 75 to 0% by mass.
- the (a1) used in the laminate of the present invention comprises 45 to 70% by mass of styrene monomer units, 10 to 30% by mass of unsaturated dicarboxylic anhydride monomer units, and 10 to 35 vinyl monomers. It is a styrene copolymer consisting of mass%.
- the styrene monomer is not particularly limited, and any known styrene monomer can be used. From the viewpoint of availability, styrene, ⁇ -methylstyrene, o-methylstyrene, m- Examples thereof include methyl styrene, p-methyl styrene, and t-butyl styrene. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrenic monomers may be mixed.
- Examples of the unsaturated dicarboxylic anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferred from the viewpoint of compatibility with vinyl monomers. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
- Examples of vinyl monomers include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and n methacrylate. And vinyl monomers such as butyl and 2-ethylhexyl methacrylate. From the viewpoint of compatibility with vinyl monomers, methyl methacrylate (MMA) is preferred. Two or more of these vinyl monomers may be mixed.
- MMA methyl methacrylate
- the weight average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (a1) is preferably 50,000 to 300,000, more preferably 100,000 to 250,000.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of (a1) should be measured using gel permeation chromatography using THF or chloroform as a solvent. Can do.
- the resin (a2) containing a vinyl monomer used in the present invention include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, Examples include homopolymerized vinyl monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable as the monomer unit. Further, a copolymer containing two or more kinds of the monomer units may be used.
- the weight average molecular weight of the resin (a2) containing a vinyl monomer is determined by the ease of mixing (dispersing) with the styrene-unsaturated dicarboxylic acid copolymer (a1) and the resin (A ) Determined by ease of manufacture. That is, if the weight average molecular weight of the resin (a2) containing a vinyl monomer is too large, the difference in melt viscosity between (a1) and (a2) becomes too large, so that the mixing (dispersion) of both becomes worse. There arises a problem that the transparency of the resin (A) deteriorates or stable melt-kneading cannot be continued.
- the weight average molecular weight of the resin (a2) containing a vinyl monomer is preferably in the range of 50,000 to 700,000, and more preferably in the range of 60,000 to 550,000. More preferably, it is in the range of 70,000 to 500,000.
- the composition ratio of the styrene-unsaturated dicarboxylic acid copolymer (a1) and the resin (a2) containing a vinyl monomer is such that the component (a1) is 100 to 25% by mass (a2).
- the component is 0 to 75% by mass.
- the component (a2) is 25 to 75% by mass with respect to the component (a1) of 75 to 25% by mass. More preferably, the component (a2) is 70 to 25% by mass with respect to the component (a1) of 30 to 75% by mass.
- the polycarbonate (B) used in the present invention contains a carbonate ester bond in the molecular main chain, that is, — [OR—OCO] —unit (where R is an aliphatic group, aromatic group, or aliphatic group). And those containing both an aromatic group and those having a straight chain structure or a branched structure) are not particularly limited, but in particular, a polycarbonate containing a structural unit of the following formula [1] is used. It is preferable to do. By using such a polycarbonate, a resin laminate excellent in impact resistance can be obtained.
- the weight average molecular weight of the polycarbonate (B) affects the impact resistance and molding conditions of the synthetic resin laminate. That is, when the weight average molecular weight is too small, the impact resistance of the synthetic resin laminate is lowered, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating a resin layer containing the resin (A) (hereinafter sometimes referred to as “high hardness layer”), which is not preferable. Moreover, since a high temperature is required depending on the molding method, the resin (A) is exposed to a high temperature, which may adversely affect its thermal stability.
- the weight average molecular weight of the polycarbonate (B) is preferably 25,000 to 75,000, more preferably 30,000 to 70,000. More preferably, it is 35,000-65,000.
- the method for forming the synthetic resin laminate of the present invention is not particularly limited. For example, a method of laminating an individually formed high hardness layer and a base material layer containing polycarbonate (B) and thermocompression bonding them, laminating an individually formed high hardness layer and a base material layer, A method of adhering with an adhesive, a method of coextrusion molding of resin (A) and polycarbonate (B), and a polycarbonate (B) in-mold molding using a pre-formed high hardness layer to integrate Although there are various methods such as a method, a co-extrusion method is preferable from the viewpoint of manufacturing cost and productivity.
- the production method of the polycarbonate (B) used in the present invention can be appropriately selected depending on the monomers used, such as a known phosgene method (interfacial polymerization method) and transesterification method (melting method).
- the production method of the resin (A) is not particularly limited, and necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then Banbury mixer, roll, Brabender.
- a mixer such as a tumbler, a Henschel mixer, or a super mixer
- Banbury mixer roll, Brabender.
- a known method such as melt kneading by a machine such as a single screw extruder, a twin screw extruder, or a pressure kneader can be applied.
- the thickness of the high hardness layer affects the surface hardness and impact resistance of the synthetic resin laminate. That is, when the thickness of the high hardness layer is too thin, the surface hardness is lowered, which is not preferable. When the thickness of the high hardness layer is too large, the impact resistance is deteriorated, which is not preferable.
- the thickness of the high hardness layer is preferably 10 to 250 ⁇ m, more preferably 30 to 200 ⁇ m. More preferably, it is 60 to 150 ⁇ m.
- the total thickness of the synthetic resin laminate affects the amount of deformation (warpage) and impact resistance when the synthetic resin laminate is exposed to high temperature and high humidity.
- the overall thickness is too thin, the amount of deformation (warpage) at the time of exposure to high temperature and high humidity increases and impact resistance decreases.
- the overall thickness is thick, the amount of deformation (warping) when exposed to high temperature and high humidity is small and impact resistance is ensured.
- the total thickness of the synthetic resin laminate is preferably 0.1 to 2.0 mm, and more preferably 0.3 to 2.0 mm. More preferably, it is 0.5 to 1.5 mm.
- the high-hardness layer and / or the base material layer can be used by mixing an ultraviolet absorber. If the content of the UV absorber is too low, the light resistance will be insufficient, and if the content is too high, excessive UV absorber will be scattered due to high temperature depending on the molding method, causing the molding environment and causing problems. Sometimes.
- the content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and still more preferably 0 to 1% by mass.
- Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy -4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc.
- Benzophenone UV absorber 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3 -T-Butyl-5-methylphenyl) benzotriazo , Benzotriazole ultraviolet absorbers such as (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, phenyl salicylate, 2,4-di-t-butyl Benzoate UV absorbers such as phenyl-3,5-di-t-butyl-4-hydroxybenzoate, and hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxy
- additives can be mixed and used for the high hardness layer and / or the base material layer.
- additives include antioxidants, anti-colorants, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers, and inorganic fillers. Examples include reinforcing materials.
- the method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
- a hard coat treatment may be applied to the surface on the high hardness layer side containing the resin (A) or the surface on the base material layer side.
- the hard coat layer is formed by a hard coat process using a hard coat paint that is cured using thermal energy and / or light energy.
- the hard coat paint that is cured using thermal energy include polyorganosiloxane-based and cross-linked acrylic-based thermosetting resin compositions.
- a hard coat paint that is cured using light energy for example, a photocurable resin in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers. Examples thereof include a composition.
- the hard coat coating applied on the high hardness layer and cured using thermal energy is, for example, 10 to 50% by mass of 100 parts by mass of organotrialkoxysilane and colloidal silica having a particle size of 4 to 20 nm.
- a thermosetting resin composition in which 1 to 5 parts by mass of an amine carboxylate and / or a quaternary ammonium carboxylate is added to 100 parts by mass of a resin composition comprising 50 to 200 parts by mass of a colloidal silica solution to be contained. It is done.
- the hard coat coating material applied on the high-hardness layer and cured using light energy includes, for example, 40 to 80% by mass of tris (acryloxyethyl) isocyanurate, tris (acryloxyethyl) isocyanurate, A photocurable resin obtained by adding 1 to 10 parts by mass of a photopolymerization initiator to 100 parts by mass of a resin composition comprising 20 to 60% by mass of a bifunctional and / or trifunctional (meth) acrylate compound capable of copolymerization Examples thereof include a composition.
- Examples of the hard coat paint to be cured using light energy applied on the base material layer in the present invention include 20 to 60% by mass of 1,9-nonanediol diacrylate and 1,9-nonanediol diacrylate.
- Examples thereof include a photocurable resin composition in which 1 to 10 parts by mass of a photopolymerization initiator is added to 100 parts by mass of a resin composition comprising 40 to 80% by mass of a compound comprising a functional epoxy (meth) acrylate oligomer. .
- the method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and blurring. .
- a pretreatment of the coated surface may be performed before the hard coat. Examples of treatment include known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition. Can be mentioned.
- each material of the high hardness layer, the base material layer and the hard coat is preferably filtered and purified by a filter treatment.
- a filter treatment By producing or laminating through a filter, it is possible to obtain a synthetic resin laminate having few appearance defects such as foreign matters and defects.
- the filter to be used is not particularly limited, and known filters can be used, and are appropriately selected depending on the use temperature, viscosity, and filtration accuracy of each material.
- the filter medium is not particularly limited, but polypropylene, cotton, polyester, viscose rayon or glass fiber nonwoven fabric or roving yarn roll, phenol resin impregnated cellulose, metal fiber nonwoven fabric sintered body, metal powder sintered body, breaker plate, Alternatively, any combination of these can be used. In view of heat resistance, durability, and pressure resistance, a type in which a metal fiber nonwoven fabric is sintered is preferable.
- the filtration accuracy is 50 ⁇ m or less, preferably 30 ⁇ m or less, and more preferably 10 ⁇ m or less for the resin (A) and the polycarbonate (B).
- the filtration accuracy of the hard coat agent is 20 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less because it is applied to the outermost layer of the synthetic resin laminate.
- a polymer filter used for thermoplastic resin melt filtration is classified into a leaf disk filter, a candle filter, a pack disk filter, a cylindrical filter and the like depending on its structure, and a leaf disk filter having a large effective filtration area is particularly suitable.
- the synthetic resin laminate of the present invention can be subjected to one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one side or both sides.
- the methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.
- Resin (a2) containing a styrene-unsaturated dicarboxylic acid copolymer (a1) and a vinyl monomer on the basis of a calibration curve obtained by previously dissolving standard polystyrene in chloroform and measured by gel permeation chromatography (GPC) And polycarbonate resin (B) were similarly measured by GPC.
- the weight average molecular weight of each resin of a1, a2, and B was calculated by comparing both, that is, by comparing standard polystyrene with a1, standard polystyrene with a2, and standard polystyrene with B. In either case, the value is in terms of polystyrene.
- the apparatus configuration of GPC is as follows. Device: Weights 2690 Column: Shodex GPC KF-805L 8 ⁇ ⁇ 300 mm 2-linked developing solvent: chloroform flow rate: 1 ml / min Temperature: 30 ° C Detector: UV ... 486nm Polycarbonate (B) RI: resin containing styrene-unsaturated dicarboxylic acid copolymer (a1) and vinyl monomer (a2)
- the water absorption rate was measured according to JIS-K7209 A method. First, a test piece of 60 mm ⁇ 60 mm ⁇ 1.0 mm prepared by press molding was prepared, and it was dried in an oven at 50 ° C. After 24 hours, the test piece was taken out of the oven and cooled in a desiccator adjusted to 23 ° C. After 1 hour, the weight of the test piece was measured and then put into water at 23 ° C. After 480 hours, the test piece was taken out of the water, the surface moisture was wiped off, and the weight was measured. The water absorption was calculated by dividing the difference between the weight immediately after drying in water and the weight immediately after drying by the weight immediately after drying, and multiplying that value by 100.
- the test piece was cut into a 10 cm ⁇ 6 cm square.
- the test piece was set in a two-point support type holder, placed in an environmental test machine set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more to adjust the state, and then warpage was measured (before treatment).
- the test piece was set in a holder, put into an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85%, and kept in that state for 120 hours. Further, the holder was moved into an environmental testing machine set at a temperature of 23 ° C. and a relative humidity of 50%, and the warpage was measured again after being held for 4 hours in this state (after treatment).
- the shape stability was evaluated using (the amount of warpage after treatment) ⁇ (the amount of warpage before treatment) as the amount of change in shape.
- ⁇ Pencil scratch hardness test> In accordance with JIS K 5600-5-4, the hardness of the hardest pencil that did not cause scars was gradually increased by pressing the pencil against the surface of the resin (A) at an angle of 45 degrees and a load of 750 g with respect to the surface. The hardness was evaluated.
- ⁇ Glass transition temperature measurement> DSC curve obtained by using a differential scanning calorimeter Pyris type 1 manufactured by Perkin Elmer, measured at a heating rate of 10 ° C./min after holding at 25 ° C. for 1 minute in a nitrogen atmosphere, and using a tangential method The intersection of the two tangent lines in was determined as the glass transition temperature. A glass transition temperature of 110 ° C. or higher was considered acceptable.
- Examples of the resin A and the polycarbonate resin B include the following materials, but are not limited thereto.
- A1 Styrene-unsaturated dicarboxylic acid copolymer: KX-378, Denki Kagaku Kogyo Co., Ltd.
- A2 Styrene-unsaturated dicarboxylic acid copolymer: KX-381, Denki Kagaku Kogyo Co., Ltd.
- A3 Resin containing vinyl monomer: Methyl methacrylate resin parapet HR-L manufactured by Kuraray Co., Ltd.
- A4 Resin containing a vinyl monomer: Atoglass HT121 manufactured by Arkema Co., Ltd.
- A5 Resin containing vinyl monomer: MS800 manufactured by Nippon Steel Chemical Co., Ltd.
- B1 Polycarbonate resin: Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
- the mixture was melt kneaded at a cylinder temperature of 260 ° C., extruded into a strand shape, and pelletized with a pelletizer.
- the pellets could be manufactured stably.
- the obtained pellets were transparent, the glass transition temperature was 110 ° C., and the water absorption was 0.9%.
- Production Example 2 [Production of Resin (A12) Pellets] 50% by mass of the styrene-unsaturated dicarboxylic acid copolymer KX-378 used in Production Example 1 and 50% by mass of parapet HR-L as a methyl methacrylate resin were mixed and pelletized. Pelletization was performed under the same conditions as in Production Example 1. The pellets could be manufactured stably. The obtained pellets were transparent, the glass transition temperature was 118 ° C., and the water absorption rate was 0.7%.
- Production Example 3 [Production of Resin (A13) Pellets] 75% by mass of the styrene-unsaturated dicarboxylic acid copolymer KX-378 used in Production Example 1 and 75% by mass of parapet HR-L as a methyl methacrylate resin were mixed and pelletized. Pelletization was performed under the same conditions as in Production Example 1. The pellets could be manufactured stably. The obtained pellets were transparent, the glass transition temperature was 121 ° C., and the water absorption was 0.6%.
- pellets were manufactured stably.
- the obtained pellets were transparent, the glass transition temperature was 114 ° C., and the water absorption rate was 0.5%.
- Production Example 9 [Production of photocurable resin composition (C11) coated on high hardness layer]
- a mixing vessel equipped with a stirring blade 60 parts by mass of tris (2-acryloxyethyl) isocyanurate (manufactured by Aldrich) and 40 parts by mass of neopentyl glycol oligoacrylate (manufactured by Osaka Organic Chemical Industry, trade name: 215D) 1 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Japan, trade name: DAROCUR TPO), 0.3 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Aldrich), Introduced a composition comprising 1 part by weight of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Ciba Japan, trade name: TINUVIN234) And stirred for 1 hour
- Production Example 10 [Production of photocurable resin composition (C12) coated on base material layer]
- a mixing tank equipped with a stirring blade 40 parts by mass of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 260) and a hexafunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., (Trade name: U-6HA) 40 parts by mass, 20 parts by mass of a condensate having a succinic acid / trimethylolethane / acrylic acid molar ratio of 1/2/4, and 2,4,6-trimethylbenzoyldiphenylphosphine 2.8 parts by mass of oxide (manufactured by Ciba Japan, trade name: DAROCUR TPO), 1 part by mass of benzophenone (manufactured by Aldrich), 2- (2H-benzotriazol-2-yl
- the mixture was melt kneaded at a cylinder temperature of 260 ° C., extruded into a strand shape, and pelletized with a pelletizer.
- the pellets could be manufactured stably.
- the obtained pellets were transparent, the glass transition temperature was 100 ° C., and the water absorption rate was 1.2%.
- Example 1 A synthetic resin laminate was molded using a multilayer extruder having a single-screw extruder having a shaft diameter of 40 mm, a single-screw extruder having a shaft diameter of 75 mm, and a multi-manifold die connected to each extruder.
- the resin (A11) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 40 mm and extruded under conditions of a cylinder temperature of 240 ° C. and a discharge rate of 4.0 kg / h.
- polycarbonate resin (B1: see Table 2) (trade name: Iupilon S-1000, aromatic polycarbonate of the above formula [1], mass average molecular weight: 33 , 000) was continuously introduced and extruded at a cylinder temperature of 270 ° C. and a discharge rate of 63.0 kg / h.
- the resin extruded by each extruder is laminated inside the multi-manifold, formed into a sheet, pushed from the T-die, and the mirror surface is transferred from the upstream by three mirror finish rolls with temperatures of 130 ° C, 120 ° C, and 190 ° C. While cooling, a laminate (E1) of (A11) and (B1) was obtained.
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the layer made of (A11) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 200 ⁇ m, and the result of the pencil scratch hardness test was 2H.
- Example 2 On the high hardness layer comprising (A11) of the laminate (E1) obtained in Example 1, the coating thickness after curing of the photocurable resin composition (C11) obtained in Production Example 9 was 3 to It apply
- the photocurable resin composition (C12) obtained in Production Example 10 was applied onto the base material layer made of (B1) using a bar coater so that the coating thickness after curing was 3 to 8 ⁇ m. Then, it was covered with a PET film and pressed.
- the PET film was peeled off by irradiating with UV light at a line speed of 1.5 m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a laminate (E2) having a hard coat layer composed of (C11) and (C12) was obtained.
- the result of the high temperature and high humidity exposure test was 9 ⁇ m, and the result of the pencil scratch hardness test was 4H.
- a body (E2) was obtained.
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A11) was 100 ⁇ m near the center.
- the result of the high temperature and high humidity exposure test was 300 ⁇ m, and the result of the pencil scratch hardness test was 4H.
- Example 3 A laminate (E4) of (A12) and (B1) was obtained in the same manner as in Example 1 except that the resin (A12) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A12) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 100 ⁇ m, and the result of the pencil scratch hardness test was H.
- Example 4 Lamination of (A12) and (B1) in the same manner as in Example 3 except that the discharge rate of the 40 mm single screw extruder was 7.0 kg / h and the discharge rate of the 75 mm single screw extruder was 60.0 kg / h.
- a body (E4) was obtained.
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A11) was 100 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 150 ⁇ m, and the result of the pencil scratch hardness test was 2H.
- Example 5 On the high hardness layer composed of (A12) of the laminate (E4) obtained in Example 4, the coating thickness after curing of the photocurable resin composition (C11) obtained in Production Example 9 was 3 to It apply
- the photocurable resin composition (C12) obtained in Production Example 10 was applied onto the base material layer made of (B1) using a bar coater so that the coating thickness after curing was 3 to 8 ⁇ m. Then, it was covered with a PET film and pressed.
- the PET film was peeled off by irradiating with UV light at a line speed of 1.5 m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a laminate (E5) having a hard coat layer composed of (C11) and (C12) was obtained.
- the result of the high-temperature and high-humidity exposure test was 200 ⁇ m, and the result of the pencil scratch hardness test was 4H.
- Example 6 A laminate (E6) of (A13) and (B1) was obtained in the same manner as in Example 1 except that the resin (A13) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A12) was 60 ⁇ m near the center.
- the result of the high temperature and high humidity exposure test was 90 ⁇ m, and the result of the pencil scratch hardness test was H.
- Example 7 A laminate (E7) of (A14) and (B1) was obtained in the same manner as in Example 1 except that the resin (A14) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A12) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 200 ⁇ m, and the result of the pencil scratch hardness test was 2H.
- Example 8 A laminate (E8) of (A15) and (B1) was obtained in the same manner as in Example 1 except that the resin (A15) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A12) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 120 ⁇ m, and the result of the pencil scratch hardness test was 2H.
- Example 9 On the high hardness layer comprising (A15) of the laminate (E8) obtained in Example 8, the coating thickness after curing of the photocurable resin composition (C11) obtained in Production Example 9 was 3 to It apply
- the photocurable resin composition (C12) obtained in Production Example 10 was applied onto the base material layer made of (B1) using a bar coater so that the coating thickness after curing was 3 to 8 ⁇ m. Then, it was covered with a PET film and pressed.
- the PET film was peeled off by irradiating with UV light at a line speed of 1.5 m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a laminate (E9) having a hard coat layer composed of (C11) and (C12) was obtained.
- the result of the high-temperature and high-humidity exposure test was 200 ⁇ m, and the result of the pencil scratch hardness test was 4H.
- Example 10 A laminate (E10) of (A16) and (B1) was obtained in the same manner as in Example 1 except that the resin (A16) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A12) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 100 ⁇ m, and the result of the pencil scratch hardness test was H.
- Example 11 A laminate (E11) of (A18) and (B1) was obtained in the same manner as in Example 1 except that the resin (A17) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A17) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 80 ⁇ m, and the result of the pencil scratch hardness test was 2H.
- Example 12 On the high hardness layer comprising (A17) of the laminate (E11) obtained in Example 11, the coating thickness after curing of the photocurable resin composition (C11) obtained in Production Example 9 was 3 to It applied using a bar coater so that it might become 8 micrometers, covered with PET film, and crimped
- the photocurable resin composition (C12) obtained in Production Example 10 was applied onto the base material layer made of (B1) using a bar coater so that the coating thickness after curing was 3 to 8 ⁇ m. Then, it was covered with a PET film and pressed.
- the PET film was peeled off by irradiating with UV light at a line speed of 1.5 m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a laminate (E12) provided with a hard coat layer composed of (C11) and (C12) was obtained.
- the result of the high-temperature and high-humidity exposure test was 150 ⁇ m, and the result of the pencil scratch hardness test was 3H.
- Example 13 A laminate (E13) of (A1) and (B1) was obtained in the same manner as in Example 1 except that the resin (A1) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A1) was 60 ⁇ m near the center.
- the result of the high temperature and high humidity exposure test was 40 ⁇ m, and the result of the pencil scratch hardness test was H.
- Example 14 A laminate (E14) of (A2) and (B1) was obtained in the same manner as in Example 1 except that the resin (A2) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A2) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 80 ⁇ m, and the result of the pencil scratch hardness test was H.
- Example 15 On the high hardness layer composed of (A2) of the laminate (E14) obtained in Example 14, the photocurable resin composition (C11) obtained in Production Example 9 has a coating thickness of 3 to 3 after curing. It apply
- the photocurable resin composition (C12) obtained in Production Example 10 was applied onto the base material layer made of (B1) using a bar coater so that the coating thickness after curing was 3 to 8 ⁇ m. Then, it was covered with a PET film and pressed.
- the PET film was peeled off by irradiating with UV light at a line speed of 1.5 m / min on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm.
- a laminate (E15) provided with a hard coat layer composed of (C11) and (C12) was obtained.
- the result of the high-temperature and high-humidity exposure test was 100 ⁇ m, and the result of the pencil scratch hardness test was 3H.
- Comparative Example 1 A laminate (F1) of (A3) and (B1) was obtained in the same manner as in Example 1 except that the resin (A3) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A3) was 60 ⁇ m near the center.
- the result of the high temperature and high humidity exposure test was 1000 ⁇ m, and the result of the pencil scratch hardness test was 3H.
- Comparative Example 2 A laminate (F2) of (A4) and (B1) was obtained in the same manner as in Example 1 except that the resin (A4) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A4) was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 1200 ⁇ m, and the result of the pencil scratch hardness test was 3H.
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (A3) was 60 ⁇ m near the center. Further, in the same manner as in Example 3, a laminate (F4) provided with a hard coat layer composed of (C11) and (C12) on the high hardness layer and the base material layer of the laminate (F3) was obtained.
- the result of the high-temperature and high-humidity exposure test was 500 ⁇ m, and the result of the pencil scratch hardness test was 3H.
- Comparative Example 4 A polycarbonate (B1) (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-1000, mass average molecular weight: 27,000) is used instead of the resin (A11), and a single screw extruder with a shaft diameter of 32 mm is used.
- a laminated body (F5) of (B1) and (B1) was obtained in the same manner as in Example 1 except that the cylinder temperature was 260 ° C and the roll temperature was 130 ° C, 140 ° C and 190 ° C from the upstream. The overall thickness of the obtained laminate was 1.0 mm, and the result of the pencil scratch hardness test was 2B.
- a laminate (F6) was obtained in which the laminate (F5) was provided with a hard coat layer composed of (C11) and (C12).
- the result of the high temperature and high humidity exposure test was 100 ⁇ m, and the result of the pencil scratch hardness test was HB.
- Comparative Example 5 A laminate (F7) of (D11) and (B1) was obtained in the same manner as in Example 1 except that the resin (D11) was used instead of the resin (A11).
- the total thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness layer made of (D11) was 60 ⁇ m near the center.
- the result of the high temperature and high humidity exposure test was 700 ⁇ m, and the result of the pencil scratch hardness test was 3H.
- a styrene monomer unit As shown in the examples and comparative examples, i) 45 to 70% by mass of a styrene monomer unit and 10 to 30% by mass of an unsaturated dicarboxylic acid anhydride monomer unit on one side of a base material layer mainly composed of polycarbonate. 25% to 100% by weight of a specific styrene-unsaturated dicarboxylic acid copolymer of 10% to 35% by weight of a vinyl monomer, and ii) 75% to 0% by weight of a resin having a vinyl monomer as a structural unit.
- a resin laminate in which a polymer-alloyed resin composition is laminated is a resin laminate of a comparative example in which a resin alone having a vinyl monomer as a constituent unit is laminated on a base material layer containing a polycarbonate resin as a main component. In comparison, it has high surface hardness and heat resistance, and has dimensional stability in a high temperature and high humidity environment.
- the synthetic resin laminate of the present invention has a small shape change amount (warpage amount) in a high temperature and high humidity environment and is excellent in shape stability, and is excellent in surface hardness, weather resistance and heat resistance. It was confirmed that
- the synthetic resin laminate of the present invention is characterized by excellent shape stability such as warpage prevention in high temperature and high humidity environments, surface hardness, impact resistance, weather resistance and heat resistance, and a transparent substrate material, It is suitably used as a transparent protective material and the like, and particularly suitably used as a display unit front plate, a touch panel substrate and a thermal bending sheet for OA devices and portable electronic devices.
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
特許文献1には、この欠点を改良する為に紫外線硬化樹脂などで表面をコーティングする方法や、ポリカーボネート樹脂とアクリル系樹脂を共押出した基板にハードコートを施す方法が提案されている。
しかし、ポリカーボネート樹脂の表面にハードコートを施したものでは、要求される鉛筆硬度を満たす事ができず、表面硬度を要求する用途には使用できない場合がある。
また、アクリル系樹脂を表層に施す方法では、表面硬度がある程度向上するので、情報表示機器前面板などに用途が広がるが、この方法は異なる材料の2層構成になりアクリル系樹脂とポリカーボネート樹脂との吸水特性の違いゆえ、環境の変化に伴い反りが発生するため、環境変化が生じる用途では不具合が発生する。
すなわち、本発明は、以下の合成樹脂積層体および該合成樹脂積層体を用いた透明性材料を提供するものである。
<2> 前記(a1)のビニル系単量体単位がメチルメタクリレートである事を特徴とする上記<1>に記載の合成樹脂積層体である。
<3> 前記樹脂(A)が、質量平均分子量50,000~300,000の前記スチレン系共重合体(a1)25~100質量%と質量平均分子量50,000~500,000のメチルメタクリレート樹脂(a2)75~0質量%から成ることを特徴とする上記<1>または<2>に記載の合成樹脂積層体である。
<4> 前記樹脂(A)を含む樹脂層の厚さが10~250μmであり、前記合成樹脂積層体の全体厚みが0.1~2.0mmの範囲であり、該樹脂層/合成樹脂積層体の全体厚みの比が0.01~0.5であることを特徴とする上記<1>~<3>のいずれかに記載の合成樹脂積層体である。
<5> 前記ポリカーボネート(B)の質量平均分子量が25,000~75,000であることを特徴とする上記<1>~<4>のいずれかに記載の合成樹脂積層体である。
<6> 前記樹脂層および/または前記基材層が紫外線吸収剤を含有することを特徴とする上記<1>~<5>のいずれかに記載の合成樹脂積層体である。
<7> 前記樹脂(A)を含む樹脂層の上にハードコート処理を施した上記<1>~<6>のいずれかに記載の合成樹脂積層体である。
<8> 前記合成樹脂積層体の片面または両面に、反射防止処理、防汚処理、耐指紋処理、帯電防止処理、耐候性処理および防眩処理のいずれか一つ以上を施した上記<1>~<7>のいずれかに記載の合成樹脂積層体である。
<9> 上記<1>~<8>のいずれかに記載の合成樹脂積層体を含む透明性基板材料である。
<10> 上記<1>~<8>のいずれかに記載の合成樹脂積層体を含む透明性保護材料である。
<11> 上記<1>~<8>のいずれかに記載の合成樹脂積層体を含むタッチパネル前面保護板である。
<12> 上記<1>~<8>のいずれかに記載の合成樹脂積層体を含む、OA機器または携帯電子機器のための前面板である。
本発明の積層体に用いられる前記(a1)は、スチレン系単量体単位45~70質量%、不飽和ジカルボン酸無水物単量体単位10~30質量%、ビニル系単量体10~35質量%からなるスチレン系共重合体である。
不飽和ジカルボン酸無水物単量体としては、マレイン酸、イタコン酸、シトラコン酸、アコニット酸等の酸無水物が挙げられ、ビニル系単量体との相溶性の観点から無水マレイン酸が好ましい。これらの不飽和ジカルボン酸無水物系単量体は2種以上を混合しても良い。
ビニル系単量体とは、例えばアクリロニトリル、メタアクリロニトリル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸n―ブチル、アクリル酸2エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸2エチルヘキシル等のビニル系単量体が挙げられる。ビニル系単量体との相溶性の観点からメタクリル酸メチル(MMA)が好ましい。これらのビニル系単量体は2種以上を混合しても良い。
本発明で用いられるビニル系単量体を含有する樹脂(a2)は、例えばアクリロニトリル、メタアクリロニトリル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸n―ブチル、アクリル酸2エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸2エチルヘキシル等のビニル系単量体を単独重合したものが挙げられ、特に単量体単位として、メタクリル酸メチルが好ましい。また、前記単量体単位を2種類以上含んだ共重合体でも良い。
本発明において、スチレン-不飽和ジカルボン酸共重合体(a1)とビニル系単量体を含有する樹脂(a2)の組成比は、(a1)成分が100~25質量%に対して(a2)成分が0~75質量%である。好ましくは、(a1)成分が75~25質量%に対して(a2)成分が25~75質量%である。より好ましくは(a1)成分が30~75質量%に対して(a2)成分が70~25質量%である。この組成比内にすることにより、透明性を維持しつつ、耐熱性および表面硬度、吸水率といった諸物性のバランスがとれた樹脂(A)となる。
本発明に使用されるポリカーボネート(B)は、分子主鎖中に炭酸エステル結合を含む、即ち、-[O-R-OCO]-単位(Rが脂肪族基、芳香族基、又は脂肪族基と芳香族基の双方を含むもの、さらに直鎖構造あるいは分岐構造を持つもの)を含むものであれば特に限定されるものではないが、特に下記式[1]の構造単位を含むポリカーボネートを使用することが好ましい。このようなポリカーボネートを使用することで、耐衝撃性に優れた樹脂積層体を得ることができる。
本発明の合成樹脂積層体の形成方法は特に限定されない。例えば、個別に形成した高硬度層とポリカーボネート(B)を含む基材層とを積層して両者を加熱圧着する方法、個別に形成した高硬度層と基材層とを積層して、両者を接着剤によって接着する方法、樹脂(A)とポリカーボネート(B)とを共押出成形する方法、予め形成しておいた高硬度層を用いて、ポリカーボネート(B)をインモールド成形して一体化する方法、などの各種方法があるが、製造コストや生産性の観点からは、共押出成形する方法が好ましい。
本発明において、高硬度層の厚さは、合成樹脂積層体の表面硬度や耐衝撃性に影響する。つまり、高硬度層の厚さが薄すぎると表面硬度が低くなり、好ましくない。高硬度層の厚さが大きすぎると耐衝撃性が悪くなり好ましくない。高硬度層の厚さは10~250μmが好ましく、30~200μmがより好ましい。さらに好ましくは60~150μmである。
ハードコートの密着性を向上させる目的で、ハードコート前に塗布面の前処理を行うことがある。処理例として、サンドブラスト法、溶剤処理法、コロナ放電処理法、クロム酸処理法、火炎処理法、熱風処理法、オゾン処理法、紫外線処理法、樹脂組成物によるプライマー処理法などの公知の方法が挙げられる。
製造例で得られた積層樹脂の物性測定、および実施例ならびに比較例で得られた合成樹脂積層体の評価は以下のように行った。
あらかじめ標準ポリスチレンをクロロホルムに溶かしてゲルパーミエーションクロマトグラフィ(GPC)で測定した検量線を基準にして、スチレン-不飽和ジカルボン酸共重合体(a1)とビニル系単量体を含有する樹脂(a2)とポリカーボネート樹脂(B)を同様にGPCで測定した。両者の比較、すなわち、標準ポリスチレンとa1、標準ポリスチレンとa2、および標準ポリスチレンとBの比較により、a1、a2、およびBのそれぞれの樹脂の重量平均分子量を算出した。いずれの場合も、ポリスチレン換算の値である。
GPCの装置構成は以下の通りである。
装置:Wates 2690
カラム:Shodex GPC KF-805L 8φ×300mm 2連結
展開溶媒:クロロホルム
流速:1ml/min
温度:30℃
検出器:UV・・・486nm ポリカーボネート(B)
RI・・・スチレン-不飽和ジカルボン酸共重合体(a1)とビニル系単量体を含有する樹脂(a2)
JIS-K7209 A法に準処し吸水率測定を行った。まずプレス成型で作成した60mm×60mm×1.0mmの試験片を作成し、それを50℃のオーブンに入れて乾燥させた。24時間後、試験片をオーブンから取り出し、23℃に温調したデシケーター中で冷却した。1時間後、試験片の重量を測定し、その後23℃の水中に投入した。480時間後、水中から試験片を取り出し、表面の水分を拭き取った後、重量を測定した。水中投入後の重量と乾燥直後の重量の差を乾燥直後の重量で除し、その値に100を乗じることで、吸水率を算出した。
試験片を10cm×6cm四方に切り出した。試験片を2点支持型のホルダーにセットして温度23℃、相対湿度50%に設定した環境試験機に24時間以上投入して状態調整した後、反りを測定した(処理前)。次に試験片をホルダーにセットして温度85℃、相対湿度85%に設定した環境試験機の中に投入し、その状態で120時間保持した。さらに温度23℃、相対湿度50%に設定した環境試験機の中にホルダーごと移動し、その状態で4時間保持後に再度反りを測定した(処理後)。反りの測定には、電動ステージ具備の3次元形状測定機を使用し、取り出した試験片を上に凸の状態で水平に静置し、1mm間隔でスキャンし、中央部の盛り上がりを反りとして計測した。(処理後反り量)-(処理前反り量)を形状変化量として、形状安定性を評価した。
JIS K 5600-5-4に準拠し、表面に対して角度45度、荷重750gで樹脂(A)の表面に次第に硬度を増して鉛筆を押し付け、傷跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として評価した。
パーキンエルマー社製の示差走査熱量計Pyris1型を用いて、窒素雰囲気下、25℃で1分間保持後、10℃/分の昇温速度下で測定し、接線法を用いて得られたDSC曲線における2つの接線の交点をガラス転移温度として求めた。ガラス転移温度が110℃以上で合格とした。
樹脂Aおよびポリカーボネート樹脂Bについて、下記に示す材料を例示するが、これに限定されるわけではない。
A1:スチレン-不飽和ジカルボン酸系共重合体:電気化学工業(株)KX-378
A2:スチレン-不飽和ジカルボン酸系共重合体:電気化学工業(株)KX-381
A3:ビニル系単量体を含有する樹脂:クラレ(株)製メチルメタクリレート樹脂パラペットHR-L
A4:ビニル系単量体を含有する樹脂:アルケマ(株)製アトグラスHT121
A5:ビニル系単量体を含有する樹脂:新日鉄化学(株)製MS800
B1:ポリカーボネート樹脂:三菱エンジニアリングプラスチックス(株)製ユーピロンS-1000
スチレン-不飽和ジカルボン酸系共重合体(a1)としてKX-378(電気化学工業製、重量平均分子量:170,000、スチレン系単量体:不飽和ジカルボン酸無水物単量体:ビニル系単量体の比であるb1:b2:b3=65:15:20)25質量%と、ビニル系単量体を構成単位とする樹脂(a2)であるメチルメタクリレート樹脂としてパラペットHR-L(クラレ製)75質量%と、りん系添加剤PEP36(ADEKA製) 500ppm、およびステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%を仕込みブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度260℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化した。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、110℃であり、吸水率は0.9%であった。
製造例1で用いたスチレン-不飽和ジカルボン酸系共重合体KX-378を50質量%、メチルメタクリレート樹脂として、パラペットHR-Lを50質量%の比率で混合し、ペレット化した。ペレット化は製造例1と同様の条件で行った。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、118℃であり、吸水率は0.7%であった。
製造例1で用いたスチレン-不飽和ジカルボン酸系共重合体KX-378を75質量%、メチルメタクリレート樹脂として、パラペットHR-Lを25質量%の比率で混合し、ペレット化した。ペレット化は製造例1と同様の条件で行った。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、121℃であり、吸水率は0.6%であった。
スチレン-不飽和ジカルボン酸系共重合体としてKX-381(電気化学工業製、重量平均分子量:185,000、b1:b2:b3=55:20:25)25質量%と、メチルメタクリレート樹脂としてパラペットHR-Lを75質量%と、りん系添加剤PEP36(ADEKA製) 500ppm、およびステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%を仕込みブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度260℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化した。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、114℃であり、吸水率は0.9%であり、鉛筆硬度は2Hであった。
スチレン-不飽和ジカルボン酸系共重合体(a1:後述の表1中のB)としてKX-381(電気化学工業製、重量平均分子量:185,000、b1:b2:b3=55:20:25)50質量%と、メチルメタクリレート樹脂(a2:後述の表1中のA)としてパラペットHR-Lを50質量%と、りん系添加剤PEP36(ADEKA製) 500ppm、およびステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%を仕込みブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度260℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化した。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、121℃であり、吸水率は0.8%であり、鉛筆硬度はHであった。
スチレン-不飽和ジカルボン酸系共重合体(a1:後述の表1中のB)としてKX-381(電気化学工業製、重量平均分子量:185,000、b1:b2:b3=55:20:25)75質量%と、メチルメタクリレート樹脂(a2:後述の表1中のA)としてパラペットHR-Lを25質量%と、りん系添加剤PEP36(ADEKA製) 500ppm、およびステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%を仕込みブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度260℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化した。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、127℃であり、吸水率は0.7%であり、鉛筆硬度はHであった。
製造例7〔樹脂(A17)ペレットの製造〕
スチレン-不飽和ジカルボン酸系共重合体としてKX-381(電気化学工業製、重量平均分子量:185,000、b1:b2:b3=55:20:25)50質量%と、メチルメタクリレートースチレン樹脂としてエスチレンMS800(新日鉄化学製)を50質量%と、りん系添加剤PEP36(ADEKA製) 500ppm、およびステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%を仕込みブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度260℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化した。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、114℃であり、吸水率は0.5%であった。
撹拌翼を備えた混合槽に、トリス(2-アクロキシエチル)イソシアヌレート(Aldrich社製)60質量部と、ネオペンチルグリコールオリゴアクリレート(大阪有機化学工業社製、商品名:215D)40質量部と、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド(チバ・ジャパン社製、商品名:DAROCUR TPO)1質量部と、1-ヒドロキシシクロヘキシルフェニルケトン(Aldrich社製)0.3質量部と、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(チバ・ジャパン社製、商品名:TINUVIN234)1質量部からなる組成物を導入し、40℃に保持しながら1時間撹拌して光硬化性樹脂組成物(C11:後述の表2参照)を得た。
撹拌翼を備えた混合槽に、1,9-ノナンジオールジアクリレート(大阪有機化学工業社製、商品名:ビスコート#260)40質量部と、6官能ウレタンアクリレートオリゴマー(新中村化学工業社製、商品名:U-6HA)40質量部と、コハク酸/トリメチロールエタン/アクリル酸のモル比が1/2/4である縮合物20質量部と、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド(チバ・ジャパン社製、商品名:DAROCUR TPO)2.8質量部と、ベンゾフェノン(Aldrich社製)1質量部と、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(チバ・ジャパン社製、商品名:TINUVIN234)1質量部からなる組成物を導入し、40℃に保持しながら1時間撹拌して光硬化性樹脂組成物(C12)を得た。
スチレン-不飽和ジカルボン酸系共重合体としてKX-378(電気化学工業製、重量平均分子量:170,000、b1:b2:b3=65:15:20)10質量%と、メチルメタクリレート樹脂としてパラペットHR-L(クラレ製)90質量%と、りん系添加剤PEP36(ADEKA製) 500ppm、およびステアリン酸モノグリセリド(製品名:H-100、理研ビタミン製)0.2%を仕込みブレンダーで20分混合後、スクリュー径26mmの2軸押出機を用い、シリンダー温度260℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化した。ペレットは安定して製造できた。
得られたペレットは透明であり、ガラス転移温度は、100℃であり、吸水率は1.2%であった。
軸径40mmの単軸押出機と、軸径75mmの単軸押出機と、各押出機と連結したマルチマニホールドダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径40mmの単軸押出機に製造例1で得た樹脂(A11)を連続的に導入し、シリンダー温度240℃、吐出量4.0kg/hの条件で押し出した。また軸径75mmの単軸押出機にポリカーボネート樹脂(B1:表2参照)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000、上記式[1]の芳香族ポリカーボネート、質量平均分子量:33,000)を連続的に導入し、シリンダー温度270℃、吐出量63.0kg/hで押し出した。各押出機で押し出された樹脂をマルチマニホールド内部で積層し、シート状にしてTダイから押し、上流側から温度130℃、120℃、190℃とした3本の鏡面仕上げロールで鏡面を転写しながら冷却し、(A11)と(B1)の積層体(E1)を得た。得られた積層体の全体厚みは1.0mm、(A11)から成る層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は200μmであり、鉛筆引っかき硬度試験の結果は2Hであった。
実施例1で得た積層体(E1)の(A11)から成る高硬度層上に、製造例9で得た光硬化性樹脂組成物(C11)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。また、(B1)から成る基材層上に製造例10で得た光硬化性樹脂組成物(C12)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。続いて、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、高硬度層および基材層上にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(E2)を得た。高温高湿暴露試験の結果は9μmであり、鉛筆引っかき硬度試験の結果は4Hであった。40mm単軸押出機の吐出量を7.0kg/h、75mm単軸押出機の吐出量を60.0kg/hとした以外は、実施例1と同様にして(A11)と(B1)の積層体(E2)を得た。
得られた積層体の全体厚みは1.0mm、(A11)から成る高硬度層の厚みは中央付近で100μmであった。高温高湿暴露試験の結果は300μmであり、鉛筆引っかき硬度試験の結果は4Hであった。
樹脂(A11)の代わりに樹脂(A12)を使用した以外は、実施例1と同様にして(A12)と(B1)の積層体(E4)を得た。得られた積層体の全体厚みは1.0mm、(A12)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は100μmであり、鉛筆引っかき硬度試験の結果はHであった。
40mm単軸押出機の吐出量を7.0kg/h、75mm単軸押出機の吐出量を60.0kg/hとした以外は、実施例3と同様にして(A12)と(B1)の積層体(E4)を得た。得られた積層体の全体厚みは1.0mm、(A11)から成る高硬度層の厚みは中央付近で100μmであった。高温高湿暴露試験の結果は150μmであり、鉛筆引っかき硬度試験の結果は2Hであった。
実施例4で得た積層体(E4)の(A12)から成る高硬度層上に、製造例9で得た光硬化性樹脂組成物(C11)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。また、(B1)から成る基材層上に製造例10で得た光硬化性樹脂組成物(C12)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。続いて、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、高硬度層および基材層上にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(E5)を得た。高温高湿暴露試験の結果は200μmであり、鉛筆引っかき硬度試験の結果は4Hであった。
樹脂(A11)の代わりに樹脂(A13)を使用した以外は、実施例1と同様にして(A13)と(B1)の積層体(E6)を得た。得られた積層体の全体厚みは1.0mm、(A12)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は90μmであり、鉛筆引っかき硬度試験の結果はHであった。
樹脂(A11)の代わりに樹脂(A14)を使用した以外は、実施例1と同様にして(A14)と(B1)の積層体(E7)を得た。得られた積層体の全体厚みは1.0mm、(A12)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は200μmであり、鉛筆引っかき硬度試験の結果は2Hであった。
樹脂(A11)の代わりに樹脂(A15)を使用した以外は、実施例1と同様にして(A15)と(B1)の積層体(E8)を得た。得られた積層体の全体厚みは1.0mm、(A12)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は120μmであり、鉛筆引っかき硬度試験の結果は2Hであった。
実施例8で得た積層体(E8)の(A15)から成る高硬度層上に、製造例9で得た光硬化性樹脂組成物(C11)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。また、(B1)から成る基材層上に製造例10で得た光硬化性樹脂組成物(C12)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。続いて、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、高硬度層および基材層上にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(E9)を得た。高温高湿暴露試験の結果は200μmであり、鉛筆引っかき硬度試験の結果は4Hであった。
樹脂(A11)の代わりに樹脂(A16)を使用した以外は、実施例1と同様にして(A16)と(B1)の積層体(E10)を得た。得られた積層体の全体厚みは1.0mm、(A12)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は100μmであり、鉛筆引っかき硬度試験の結果はHであった。
樹脂(A11)の代わりに樹脂(A17)を使用した以外は、実施例1と同様にして(A18)と(B1)の積層体(E11)を得た。得られた積層体の全体厚みは1.0mm、(A17)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は80μmであり、鉛筆引っかき硬度試験の結果は2Hであった。
実施例11で得た積層体(E11)の(A17)から成る高硬度層上に、製造例9で得た光硬化性樹脂組成物(C11)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布しPETフィルムで覆って圧着した。また、(B1)から成る基材層上に製造例10で得た光硬化性樹脂組成物(C12)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。続いて、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、高硬度層および基材層上にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(E12)を得た。高温高湿暴露試験の結果は150μmであり、鉛筆引っかき硬度試験の結果は3Hであった。
樹脂(A11)の代わりに樹脂(A1)を使用した以外は、実施例1と同様にして(A1)と(B1)の積層体(E13)を得た。得られた積層体の全体厚みは1.0mm、(A1)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は40μmであり、鉛筆引っかき硬度試験の結果はHであった。
樹脂(A11)の代わりに樹脂(A2)を使用した以外は、実施例1と同様にして(A2)と(B1)の積層体(E14)を得た。得られた積層体の全体厚みは1.0mm、(A2)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は80μmであり、鉛筆引っかき硬度試験の結果はHであった。
実施例14で得た積層体(E14)の(A2)から成る高硬度層上に、製造例9で得た光硬化性樹脂組成物(C11)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。また、(B1)から成る基材層上に製造例10で得た光硬化性樹脂組成物(C12)を、硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。続いて、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し硬化させてPETフィルムを剥離し、高硬度層および基材層上にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(E15)を得た。高温高湿暴露試験の結果は100μmであり、鉛筆引っかき硬度試験の結果は3Hであった。
樹脂(A11)の代わりに樹脂(A3)を使用した以外は、実施例1と同様にして(A3)と(B1)の積層体(F1)を得た。得られた積層体の全体厚みは1.0mm、(A3)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は1000μmであり、鉛筆引っかき硬度試験の結果は3Hであった。
樹脂(A11)の代わりに樹脂(A4)を使用した以外は、実施例1と同様にして(A4)と(B1)の積層体(F2)を得た。得られた積層体の全体厚みは1.0mm、(A4)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は1200μmであり、鉛筆引っかき硬度試験の結果は3Hであった。
樹脂(A11)の代わりに、メチルメタクリレート-スチレン共重合体(A5)(新日鐵化学製MS樹脂。商品名:MS800)を、ポリカーボネート(B1)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000、質量平均分子量:27,000)を使用して、軸径32mmの単軸押出機のシリンダー温度を220℃に、ロール温度を上流から130℃、140℃、190℃とした以外は、実施例1と同様にして(A5)と(B1)の積層体(F3)を得た。得られた積層体の全体厚みは1.0mm、(A3)から成る高硬度層の厚みは中央付近で60μmであった。さらに実施例3と同様にして積層体(F3)の高硬度層及び基材層上にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(F4)を得た。高温高湿暴露試験の結果は500μmであり、鉛筆引っかき硬度試験の結果は3Hであった。
樹脂(A11)の代わりに、ポリカーボネート(B1)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000、質量平均分子量:27,000)を使用して、軸径32mmの単軸押出機のシリンダー温度を260℃に、ロール温度を上流から130℃、140℃、190℃とした以外は、実施例1と同様にして(B1)と(B1)の積層体(F5)を得た。得られた積層体の全体厚みは1.0mmであり、鉛筆引掻き硬度試験の結果は、2Bであった。さらに実施例3と同様にして積層体(F5)にそれぞれ(C11)および(C12)から成るハードコート層を備えた積層体(F6)を得た。高温高湿暴露試験の結果は100μmであり、鉛筆引っかき硬度試験の結果はHBであった。
樹脂(A11)の代わりに樹脂(D11)を使用した以外は、実施例1と同様にして(D11)と(B1)の積層体(F7)を得た。得られた積層体の全体厚みは1.0mm、(D11)から成る高硬度層の厚みは中央付近で60μmであった。高温高湿暴露試験の結果は700μmであり、鉛筆引っかき硬度試験の結果は3Hであった。
Claims (12)
- 特定のスチレン-不飽和ジカルボン酸系共重合体(a1)とビニル系単量体を構成単位とする樹脂(a2)を含有する樹脂(A)を含む樹脂層(高硬度層)を、ポリカーボネート(B)を含有する樹脂層(基材層)の片面に積層させて成る合成樹脂積層体であって、前記(a1)がスチレン系単量体単位45~70質量%、不飽和ジカルボン酸無水物単量体単位10~30質量%、ビニル系単量体10~35質量%からなるスチレン-不飽和ジカルボン酸系共重合体であり、樹脂(A)中の前記(a1)の比率が25~100質量%であり、前記(a2)の比率が75~0質量%であることを特徴とする合成樹脂積層体。
- 前記(a1)のビニル系単量体単位がメチルメタクリレートであることを特徴とする請求項1に記載の合成樹脂積層体。
- 前記樹脂(A)が、質量平均分子量50,000~300,000の前記スチレン系共重合体(a1)25~100質量%と質量平均分子量50,000~500,000のメチルメタクリレート樹脂(a2)75~0質量%から成ることを特徴とする請求項1または請求項2に記載の合成樹脂積層体。
- 前記樹脂(A)を含む樹脂層の厚さが10~250μmであり、前記合成樹脂積層体の全体厚みが0.1~2.0mmの範囲であり、該樹脂層/合成樹脂積層体の全体厚みの比が0.01~0.5であることを特徴とする請求項1~請求項3のいずれかに記載の合成樹脂積層体。
- 前記ポリカーボネート(B)の質量平均分子量が25,000~75,000であることを特徴とする請求項1~請求項4のいずれかに記載の合成樹脂積層体。
- 前記樹脂層および/または前記基材層が紫外線吸収剤を含有することを特徴とする請求項1~請求項5のいずれかに記載の合成樹脂積層体。
- 前記樹脂(A)を含む樹脂層の表面にハードコート処理を施した請求項1~請求項6のいずれかに記載の合成樹脂積層体。
- 前記合成樹脂積層体の片面または両面に、反射防止処理、防汚処理、耐指紋処理、帯電防止処理、耐候性処理および防眩処理のいずれか一つ以上を施した請求項1~請求項7のいずれかに記載の合成樹脂積層体。
- 請求項1~8のいずれかに記載の合成樹脂積層体を含む透明性基板材料。
- 請求項1~8のいずれかに記載の合成樹脂積層体を含む透明性保護材料。
- 請求項1~8のいずれかに記載の合成樹脂積層体を含むタッチパネル前面保護板。
- 請求項1~8のいずれかに記載の合成樹脂積層体を含む、OA機器または携帯電子機器のための前面板。
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2014
- 2014-10-31 EP EP14866753.8A patent/EP3075533B1/en active Active
- 2014-10-31 JP JP2015550623A patent/JP6571528B2/ja active Active
- 2014-10-31 US US15/039,192 patent/US20170136748A1/en not_active Abandoned
- 2014-10-31 KR KR1020167016662A patent/KR20160090847A/ko not_active Application Discontinuation
- 2014-10-31 CN CN201480063248.0A patent/CN105745075B/zh active Active
- 2014-10-31 WO PCT/JP2014/079075 patent/WO2015079867A1/ja active Application Filing
- 2014-11-11 TW TW103139051A patent/TWI655091B/zh active
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2019
- 2019-06-04 JP JP2019104429A patent/JP2019162885A/ja active Pending
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KR102368754B1 (ko) | 2014-07-09 | 2022-02-28 | 미츠비시 가스 가가쿠 가부시키가이샤 | 합성 수지 적층체 |
KR20170031154A (ko) * | 2014-07-09 | 2017-03-20 | 미츠비시 가스 가가쿠 가부시키가이샤 | 합성 수지 적층체 |
JPWO2016006589A1 (ja) * | 2014-07-09 | 2017-04-27 | 三菱瓦斯化学株式会社 | 合成樹脂積層体 |
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KR20190042023A (ko) * | 2016-08-18 | 2019-04-23 | 미츠비시 가스 가가쿠 가부시키가이샤 | 2단 경화성 적층판 |
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Also Published As
Publication number | Publication date |
---|---|
EP3075533B1 (en) | 2018-02-21 |
JP2019162885A (ja) | 2019-09-26 |
KR20160090847A (ko) | 2016-08-01 |
JPWO2015079867A1 (ja) | 2017-03-16 |
CN105745075A (zh) | 2016-07-06 |
TW201532817A (zh) | 2015-09-01 |
JP6571528B2 (ja) | 2019-09-04 |
EP3075533A4 (en) | 2017-07-26 |
EP3075533A1 (en) | 2016-10-05 |
TWI655091B (zh) | 2019-04-01 |
US20170136748A1 (en) | 2017-05-18 |
CN105745075B (zh) | 2018-12-04 |
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