WO2022097677A1 - 樹脂シートの曲げ成形品の製造方法および曲げ成形品 - Google Patents

樹脂シートの曲げ成形品の製造方法および曲げ成形品 Download PDF

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WO2022097677A1
WO2022097677A1 PCT/JP2021/040578 JP2021040578W WO2022097677A1 WO 2022097677 A1 WO2022097677 A1 WO 2022097677A1 JP 2021040578 W JP2021040578 W JP 2021040578W WO 2022097677 A1 WO2022097677 A1 WO 2022097677A1
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Prior art keywords
resin
layer
mass
meth
base material
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PCT/JP2021/040578
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English (en)
French (fr)
Japanese (ja)
Inventor
敦大 鴇田
健太 野中
雅登 高崎
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三菱瓦斯化学株式会社
Ｍｇｃフィルシート株式会社
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Application filed by 三菱瓦斯化学株式会社, Ｍｇｃフィルシート株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN202180074515.4A priority Critical patent/CN116761709A/zh
Priority to JP2022560808A priority patent/JPWO2022097677A1/ja
Publication of WO2022097677A1 publication Critical patent/WO2022097677A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/02—Bending or folding
    • B29C53/04—Bending or folding of plates or sheets
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material

Definitions

  • the present invention relates to a method for manufacturing a bent molded product of a resin sheet and a bent molded product.
  • Resin molded bodies are used for automobile interior parts such as instrument covers, home appliances, OA equipment, personal computers, housings of small portable equipment, touch panel type display surfaces such as mobile phone terminals, and the like.
  • the resin molded body used for such an application is manufactured by molding a molding resin sheet.
  • Patent Document 1 describes a step of attaching a predetermined protective film to at least one surface of a polycarbonate resin laminate having a polycarbonate resin sheet or a polycarbonate resin layer as a base material, a step of shaping by cutting or punching, and a step of shaping while heating.
  • An invention relating to a method for producing a polycarbonate resin molded body including a step of bending is described.
  • Patent Document 1 describes that the polycarbonate resin molding obtained by the above method is used for antiglare products or protective products.
  • the method obtained by hot-bending a polycarbonate resin sheet can apply functionality typified by a hard coat function, a polarization function, etc. to the sheet in advance before the hot-bending process. It is described that it is more productive than performing the same treatment after processing and is preferably used.
  • Patent Document 2 states that a film provided with an ultraviolet (UV) curable hard coat layer is decoratively molded and then cured by UV irradiation. A decorative film to which a hard coat layer is applied by a method is described.
  • UV ultraviolet
  • Patent Document 3 describes a molded product made of a polycarbonate resin produced by an injection press molding method, which is subjected to a hard coat treatment by a dip coat method and has a hardness layer on both surfaces.
  • the present invention provides a method for producing a bent molded product that does not warp and has an excellent appearance.
  • the present inventors have conducted diligent research to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by removing the end portion having a warp, and the present invention has been completed. That is, the present invention is, for example, as follows.
  • the resin sheet has the high hardness resin layer on one surface of the base material layer and a hard coat layer on the other surface of the base material layer.
  • the high hardness resin is The following general formula (1): (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 18 carbon atoms.)
  • Resin (B1) which is a copolymer containing an aliphatic vinyl constituent unit (b) represented by.
  • Resin (B2) which is a copolymer containing 6 to 77% by mass of (meth) acrylic acid ester constituent unit, 15 to 71% by mass of styrene constituent unit, and 8 to 23% by mass of unsaturated dicarboxylic acid constituent unit;
  • Resin (B4) which is a copolymer containing 5 to 20% by mass of a styrene constituent unit, 60 to 90% by mass of a (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of an N-substituted maleimide constituent unit; And a resin (B5) which is a copolymer containing 50 to 95% by mass of styrene constituent units and 5 to 50% by mass of unsaturated dicarboxylic acid units;
  • the production method according to ⁇ 3> or ⁇ 4> above which comprises at least one selected from the group consisting of.
  • the resin (B3) has the following general formula (6):
  • ⁇ 7> A bent molded product manufactured by the manufacturing method according to any one of ⁇ 1> to ⁇ 6> above.
  • a method for manufacturing a bent molded product that does not warp and has an excellent appearance.
  • the method for producing a bent molded product according to the present invention includes a bending molding step of bending a resin sheet to obtain a bent molded body including an end having a warp, and a removing step of removing the end having the warp. including.
  • FIGS. 1 and 2 show a perspective view and a front view of a bent molded body having warpage at both ends, respectively.
  • the bend-molded article 1 of FIGS. 1 and 2 is obtained by hot-bending a resin sheet (80 mm ⁇ 170 mm, thickness: 2 mm) made of a base material layer of a polycarbonate resin by using a 50 mmR aluminum upper and lower mold. ..
  • the bent molded body 1 has ends 11 and 12 having a warp. As a result, the appearance of the bent molded product is distorted.
  • the end portions 11 and 12 having the warp have the warp over the entire end side.
  • the warped ends 11 and 12 are removed. As a result, it is possible to manufacture a bent molded product that does not warp and has an excellent appearance.
  • the bending molding step includes bending and molding a resin sheet to obtain a bent molded body including an end having a warp.
  • the resin sheet is not particularly limited, but preferably contains a thermoplastic resin that can be bent and molded by heat.
  • thermoplastic resin is not particularly limited, but is not particularly limited, but is a polycarbonate (PC) resin, a polyester resin (polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polybutylene naphthalate (PBN).
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • Resin, etc. Polyethylene resin, Polyurethane resin, Acrylic resin (methacrylic resin, Acrylic resin), Polyethylene resin (Polyethylene (PE) resin, Polyethylene (PP) resin, Polyvinyl chloride (PVC) resin, Polytetrafluoroethylene ( Examples thereof include polyethylene) resins, etc.), polystyrene resins, triacetyl cellulose-based resins, copolymers containing at least one monomer constituting these resins, and the like.
  • PE Polyethylene
  • PP Polyethylene
  • PVC Polyvinyl chloride
  • Polytetrafluoroethylene examples thereof include polyethylene) resins, etc.
  • polystyrene resins triacetyl cellulose-based resins, copolymers containing at least one monomer constituting these resins, and the like.
  • the resin sheet preferably contains a polycarbonate (PC) resin, a polyester resin, an acrylic resin, a polyolefin resin, and a copolymer containing at least one monomer constituting these resins from the viewpoint of high transparency.
  • PC polycarbonate
  • PET polyethylene terephthalate
  • methacrylic resin acrylic resin
  • PVC polyvinyl chloride
  • copolymer containing at least one monomer constituting these resins are more preferable.
  • the above-mentioned thermoplastic resin may be used alone or in combination of two or more.
  • the resin sheet contains a polycarbonate resin
  • the resin sheet contains a polycarbonate resin
  • the resin sheet has a base material layer containing the polycarbonate resin.
  • the resin sheet may further have a high hardness resin layer, a hard coat layer, and the like.
  • the resin sheet when the resin sheet includes a base material layer and a high hardness resin layer, the resin sheet has a two-layer structure (base material) including a base material layer and a high hardness resin layer arranged on the base material layer.
  • Base material including a base material layer and a high hardness resin layer arranged on the base material layer.
  • Layer-high hardness resin layer a first high hardness resin layer, a base material layer arranged on the first high hardness resin layer, and a base material layer arranged on the base material layer. It may have a three-layer structure including a second high-hardness resin layer (first high-hardness resin layer-base material layer-second high-hardness resin layer).
  • the resin sheet when the resin sheet includes a base material layer and a hard coat layer, the resin sheet has a two-layer structure (base material) including a base material layer and a hard coat layer arranged on the base material layer. Layer-hardcourt layer), a first hardcoat layer, a substrate layer arranged on the first hardcoat layer, and a second substrate layer arranged on the substrate layer. It may have a three-layer structure including a hard coat layer (first hard coat layer-base material layer-second hard coat layer).
  • the resin sheet when the resin sheet includes a base material layer, a high hardness resin layer, and a hard coat layer, the base material layer, the high hardness resin layer arranged on the base material layer, and the high hardness. It may have a three-layer structure (base material layer-high hardness resin layer-hard coat layer) including a hard coat layer arranged on the resin layer, or may be arranged on the hard coat layer and the hard coat layer. It may have a three-layer structure (hard coat layer-base material layer-high hardness resin layer) including the base material layer and the high hardness resin layer arranged on the base material layer.
  • the resin sheet includes a first hard coat layer, a base material layer arranged on the first hard coat layer, a high hardness resin layer arranged on the base material layer, and the high hardness resin. It may have a four-layer structure (first hard coat layer-base material layer-high hardness resin layer-second hard coat layer) including a second hard coat layer arranged on the layer, or a first. 1. High hardness resin layer, a base material layer arranged on the first high hardness resin layer, a second high hardness resin layer arranged on the base material layer, and the second high hardness. It may have a four-layer structure (first high-hardness resin layer-base material layer-second high-hardness resin layer-hard coat layer) including a hard coat layer arranged on the resin layer.
  • the resin sheet includes a first hard coat layer, a first high hardness resin layer arranged on the first hard coat layer, and a group arranged on the first high hardness resin layer.
  • the resin sheet preferably has a high hardness resin layer containing a high hardness resin on at least one surface of the base material layer containing the polycarbonate resin, and the high hardness on one surface of the base material layer. It is more preferable to have a resin layer and a hard coat layer on the other surface of the base material layer.
  • hard coat layer-base material layer-high hardness resin layer first high hardness resin layer-base material layer-second high hardness resin layer-hard coat layer, first hard coat layer-base material layer- Having a structure of a high hardness resin layer-a second hard coat layer, a first hard coat layer-a first high hardness resin layer-a base material layer-a second high hardness resin layer-a second hard coat layer.
  • a base material layer-a high hardness resin layer a base material layer-a high hardness resin layer-a hard coat layer, a first high hardness resin layer-a base material layer-a second high hardness resin layer-a hard coat layer. It is more preferable to have a structure of a first hard coat layer-a first high hardness resin layer-a base material layer-a second high hardness resin layer-a second hard coat layer.
  • a further layer may be present between the base material layer and the high hardness resin layer, and between the high hardness resin layer and the hard coat layer.
  • the further layer is not particularly limited, and examples thereof include an adhesive layer and a primer layer.
  • the base material layer contains a polycarbonate resin (a1).
  • the base material layer may further contain other resins, additives and the like.
  • Polycarbonate resin (a1) The polycarbonate resin (a1) has a carbonic acid ester bond in the main chain of the molecule, that is,-[OR-OCO] -unit (where R is an aliphatic group, an aromatic group, or an aliphatic group and aroma. It may contain both of the group groups, and may have a linear structure or a branched structure), but is not particularly limited, but an aromatic polycarbonate resin is preferable. In particular, it is preferable to use a polycarbonate resin containing the structural unit of the following formula (3a).
  • an aromatic polycarbonate resin for example, Iupiron S-2000, Iupiron S-1000, Iupiron E-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • Iupiron S-2000, Iupiron S-1000, Iupiron E-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • a polycarbonate resin to which a monohydric phenol as represented by the following general formula (3) is added as a terminal terminator has also been used. Also in the present invention, the polycarbonate resin to which the terminal terminator is added can be used as described above.
  • R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms; even if R 6 independently has a hydrogen atom, a halogen atom, and a substituent.
  • the "alkyl group” and the “alkenyl group” may be linear or branched, and may have a substituent.
  • the monohydric phenol represented by the general formula (3) is preferably represented by the following general formula (4).
  • R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
  • the carbon number of R5 in the general formula ( 3 ) or the general formula (4) is within a specific numerical range. Specifically, as the upper limit of the number of carbon atoms of R5 , 36 is preferable, 22 is more preferable, and 18 is particularly preferable. Further, as the lower limit of the number of carbon atoms of R5, 8 is preferable, and 12 is more preferable.
  • the solubility of the monohydric phenol (terminal terminator) in the organic solvent tends to be high, and the polycarbonate resin is manufactured. It is preferable because the productivity of the above is high.
  • the productivity is high and the economy is good in producing the polycarbonate resin.
  • the monovalent phenol is particularly excellent in organic solvent solubility, and can greatly increase the productivity in producing the polycarbonate resin and also improve the economic efficiency.
  • the polycarbonate resin using such a monovalent phenol include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company).
  • the glass transition point of the polycarbonate resin does not become too high, and the polycarbonate resin has suitable thermoformability. preferable.
  • either or both of the parahydroxybenzoic acid hexadecyl ester and the parahydroxybenzoic acid 2-hexyldecyl ester shall be used as the terminal terminator. Is particularly preferable.
  • the weight average molecular weight of the polycarbonate resin (a1) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and further preferably 20,000 to 65,000. preferable.
  • the weight average molecular weight of the polycarbonate resin (a1) is 15,000 or more, the impact resistance can be increased, which is preferable.
  • the weight average molecular weight is 75,000 or less, the base material layer can be formed with a small heat source, and the thermal stability can be maintained even when the molding conditions become high temperature, which is preferable.
  • the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
  • the Tg of the polycarbonate resin (a1) is preferably 90 to 190 ° C, more preferably 100 to 170 ° C, and even more preferably 110 to 150 ° C.
  • the Tg of the polycarbonate resin (a1) can be controlled by appropriately adjusting the type and combination of the constituent units of the polycarbonate resin (a1), the weight average molecular weight, and the like.
  • the glass transition point is a temperature calculated by the midpoint method measured at a sample of 10 mg and a temperature rise rate of 10 ° C./min using a differential scanning calorimetry device.
  • the polycarbonate resin (a1) contained in the base material layer may be used alone or in combination of two or more.
  • the content of the polycarbonate resin (a1) in the base material layer is preferably 75 to 100% by mass, more preferably 90 to 100% by mass, and 100% by mass with respect to the total mass of the base material layer. % Is particularly preferable. When the content of the polycarbonate resin is 75% or more, the impact resistance can be further improved, which is preferable.
  • Resins include, but are not limited to, polyester resins and the like.
  • the polyester resin preferably contains mainly terephthalic acid as a dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid.
  • a polyester resin obtained by polycondensing a glycol component containing 20 to 40 mol% (total 100 mol%) of 1,4-cyclohexanedimethanol with 80 to 60 mol% of ethylene glycol as the main component. ) Is preferable.
  • the other resins may be used alone or in combination of two or more.
  • the content is preferably 0 to 25% by mass, more preferably 0 to 10% by mass, based on the total mass of the base material layer.
  • additives those usually used in the resin sheet can be used. Specifically, such as antioxidants, anticolorants, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and inorganic fillers. Reinforcement materials and the like can be mentioned. These additives may be used alone or in combination of two or more.
  • the amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass with respect to the total mass of the base material layer. ..
  • the method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire amount, and the like can be used.
  • the thickness of the base material layer is preferably 0.3 to 10 mm, more preferably 0.3 to 5 mm, and even more preferably 0.3 to 3.5 mm.
  • the high-hardness resin layer contains a high-hardness resin.
  • the high hardness resin is a resin having a hardness higher than that of the polycarbonate resin used as a base material, and has a pencil hardness of HB or higher, preferably HB to 3H, more preferably H to 3H, and even more preferably. It means 2H to 3H resin.
  • the pencil hardness of the high-hardness resin layer is the result of evaluation by a pencil scratch hardness test based on JIS K 5600-5-4: 1999.
  • the hardness of the hard coat anti-glare layer is gradually increased at an angle of 45 degrees and a load of 750 g, and the pencil is pressed against the surface, and the hardness of the hardest pencil that does not cause scratches is evaluated as the pencil hardness.
  • High-hardness resin is not particularly limited, but preferably contains at least one selected from the group consisting of resins (B1) to (B5).
  • the resin (B1) has a copolymer weight including a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl structural unit (b) represented by the general formula (2). It is a coalescence. At this time, the resin (B1) may further have other structural units.
  • (meth) acrylic means methacrylic and / or acrylic.
  • R 1 is a hydrogen atom or a methyl group, preferably a methyl group.
  • R 2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group and an isobornyl group. Of these, R 2 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is a (meth) acrylic acid ester structural unit, and R 1 is a methyl group.
  • the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is a methyl methacrylate structural unit.
  • the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) may contain only one type or two or more types in the resin (B1).
  • R 3 is a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a cyclohexyl group having no substituent.
  • the aliphatic vinyl structural unit (b) represented by the general formula (2) is a vinyl cyclohexane structural unit.
  • the aliphatic vinyl constituent unit (b) represented by the general formula (2) may contain only one type or two or more types in the resin (B1).
  • hydrocarbon group may be linear, branched or cyclic, or may have a substituent.
  • the other structural unit is not particularly limited, but after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to form the resin (B1).
  • the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to form the resin (B1).
  • Examples thereof include structural units derived from aromatic vinyl monomers containing non-hydrogenated aromatic double bonds, which are generated in the process of producing the above.
  • Specific other structural units include styrene structural units.
  • the other constituent units may contain only one type in the resin (B1) or may contain two or more types.
  • the total content of the (meth) acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is preferably 90 to 100 mol% with respect to all the constituent units of the resin (B1), and more. It is preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol%.
  • the content of the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is preferably 65 to 80 mol% with respect to all the structural units of the resin (B1), more preferably. It is 70 to 80 mol%.
  • the ratio of the (meth) acrylic acid ester structural unit (a) is 65 mol% or more, it is preferable because a resin layer having excellent adhesion to the base material layer and surface hardness can be obtained.
  • the ratio of the (meth) acrylic acid ester structural unit (a) is 80 mol% or less, warpage due to water absorption of the resin sheet is unlikely to occur, which is preferable.
  • the content of the aliphatic vinyl constituent unit (b) represented by the general formula (2) is preferably 20 to 35 mol%, more preferably 20 with respect to all the constituent units of the resin (B1). ⁇ 30 mol%.
  • the content of the aliphatic vinyl constituent unit (b) is 20 mol% or more, warping under high temperature and high humidity can be prevented, which is preferable.
  • the content of the aliphatic vinyl constituent unit (b) is 35 mol% or less, peeling at the interface with the substrate can be prevented, which is preferable.
  • the content of the other constituent units is preferably 10 mol% or less, more preferably 5 mol% or less, and 2 mol% or less with respect to all the constituent units of the resin (B1). Is particularly preferred.
  • the "copolymer” may have any structure of a random copolymer, a block copolymer, and an alternate copolymer.
  • the weight average molecular weight of the resin (B1) is not particularly limited, but is preferably 50,000 to 400,000, more preferably 70,000 to 300,000 from the viewpoint of strength and moldability. ..
  • the glass transition point of the resin (B1) is preferably 110 to 140 ° C, more preferably 110 to 135 ° C, and particularly preferably 110 to 130 ° C.
  • the resin sheet is less likely to be deformed or cracked in a thermal environment or a moist thermal environment, which is preferable.
  • the temperature is 140 ° C. or lower, it is preferable because it is excellent in processability when it is formed by continuous heat shaping by a mirror surface roll or a shaping roll or by batch type heat shaping by a mirror surface mold or a shaping die.
  • the resin (B1) examples include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical Company).
  • the above-mentioned resin (B1) may be used alone or in combination of two or more.
  • the structural unit represented by the general formula (1) (R 1 and R 2 are both methyl groups; methyl methacrylate) is 75 mol%, and the structural unit represented by the general formula (2) ( A polycarbonate resin (B1) which is a copolymer containing 25 mol% of R 3 is a hydrogen atom and R 4 is a cyclohexyl group; vinyl cyclohexane) is used, and the polycarbonate resin (a1) contains a constituent unit of the general formula (3a). It is particularly preferable to use a resin and use a monovalent phenol represented by the general formula ( 4 ) (R5 has 8 to 22 carbon atoms) as a terminal terminator.
  • the method for producing the resin (B1) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, an aromatic derived from the aromatic vinyl monomer is used. Those obtained by hydrogenating the double bond are suitable.
  • the aromatic vinyl monomer is not particularly limited, and examples thereof include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, the aromatic vinyl monomer is preferably styrene.
  • a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method, a solution polymerization method, or the like.
  • the bulk polymerization method is carried out by continuously supplying a monomer composition containing the above-mentioned monomer and a polymerization initiator to a complete mixing tank and continuously polymerizing at 100 to 180 ° C.
  • the monomer composition may contain a chain transfer agent, if necessary.
  • the polymerization initiator is not particularly limited, but is t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-).
  • the chain transfer agent is not particularly limited, and examples thereof include ⁇ -methylstyrene dimer.
  • Examples of the solvent used in the solution polymerization method include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane; ester solvents such as ethyl acetate and methyl isobutyrate, and ketone solvents such as acetone and methyl ethyl ketone; tetrahydrofuran, Ether-based solvents such as dioxane; alcohol-based solvents such as methanol and isopropanol can be mentioned. These solvents may be used alone or in combination of two or more.
  • hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane
  • ester solvents such as ethyl acetate and methyl isobutyrate
  • ketone solvents such as acetone and methyl ethyl ketone
  • tetrahydrofuran Ether-based solvents such as dio
  • the solvent used for the hydrogenation reaction to hydrogenate the aromatic double bond derived from the aromatic vinyl monomer after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer is the same as the above polymerization solvent. May be different.
  • hydrocarbon solvents such as cyclohexane and methylcyclohexane
  • ester solvents such as ethyl acetate and methyl isobutyrate
  • ketone solvents such as acetone and methyl ethyl ketone
  • ether solvents such as tetrahydrofuran and dioxane
  • alcohol solvents such as methanol and isopropanol. Examples include solvents.
  • the method of hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out by a batch method or a continuous flow method at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the reaction temperature is 60 ° C. or higher, the reaction time does not take too long, which is preferable. On the other hand, when the reaction temperature is 250 ° C. or lower, side reactions such as cleavage of molecular chains and hydrogenation of ester sites do not occur or hardly occur, which is preferable.
  • Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, and carbon, alumina, silica, silica-alumina, and diatomaceous earth. Examples thereof include a solid catalyst carried on a porous carrier such as.
  • the unhydrogenation rate of the aromatic double bond contained in the structural unit derived from the aromatic vinyl monomer is preferably less than 30%, more preferably less than 10%, and less than 5%. Is even more preferable.
  • the dehydrogenation rate is less than 30%, a resin having excellent transparency can be obtained, which is preferable.
  • the structural unit of the unhydrogenated portion can be another structural unit in the resin (B1).
  • the resin (B2) is a copolymer containing 6 to 77% by mass of the (meth) acrylic acid ester constituent unit, 15 to 71% by mass of the styrene constituent unit, and 8 to 23% by mass of the unsaturated dicarboxylic acid constituent unit. .. At this time, the resin (B2) may further have other structural units.
  • the (meth) acrylic acid ester monomer constituting the (meth) acrylic acid ester structural unit in the resin (B2) is not particularly limited, but is acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate. , 2Ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like.
  • the (meth) acrylic acid ester monomer is preferably methyl methacrylate.
  • the above-mentioned (meth) acrylic acid ester monomer may be contained alone as a (meth) acrylic acid ester constituent unit, or may be contained in combination of two or more kinds.
  • the content of the (meth) acrylic acid ester constituent unit is 6 to 77% by mass, preferably 20 to 70% by mass, based on the total mass of the resin (B2).
  • the styrene constituent unit in the resin (B2) is not particularly limited, and any known styrene-based monomer can be used.
  • the styrene monomer include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene and the like from the viewpoint of availability.
  • the styrene monomer is preferably styrene from the viewpoint of compatibility.
  • the above-mentioned styrene monomer may be contained alone as a styrene constituent unit, or may be contained in combination of two or more kinds.
  • the content of the styrene constituent unit is 15 to 71% by mass, preferably 20 to 66% by mass, based on the total mass of the resin (B2).
  • the unsaturated dicarboxylic acid anhydride monomer constituting the unsaturated dicarboxylic acid constituent unit in the resin (B2) is not particularly limited, and examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Will be. Of these, the unsaturated dicarboxylic acid anhydride monomer is preferably maleic anhydride from the viewpoint of compatibility with the styrene-based monomer.
  • the unsaturated dicarboxylic acid anhydride monomer described above may be contained alone as an unsaturated dicarboxylic acid constituent unit, or may be contained in combination of two or more.
  • the content of the unsaturated dicarboxylic acid constituent unit is 8 to 23% by mass, preferably 10 to 23% by mass, based on the total mass of the resin (B2).
  • Examples of other structural units in the resin (B2) include N-phenylmaleimide and the like.
  • the content of the other constituent units is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the constituent units of the resin (B2). Especially preferable.
  • the total content of the above-mentioned (meth) acrylic acid ester constituent unit, styrene constituent unit, and unsaturated dicarboxylic acid constituent unit is preferably 90 to 100 mol% with respect to all the constituent units of the resin (B2). It is more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol%.
  • the weight average molecular weight of the resin (B2) is not particularly limited, but is preferably 50,000 to 300,000, more preferably 80,000 to 200,000.
  • the glass transition point of the resin (B2) is preferably 90 to 150 ° C, more preferably 100 to 150 ° C, and particularly preferably 115 to 150 ° C.
  • the resin (B2) include Regisphi R100, R200, R310 (manufactured by Denka), Delpet 980N (manufactured by Asahi Kasei), hp55 (manufactured by Daicel Evonik) and the like.
  • the above-mentioned resin (B2) may be used alone or in combination of two or more.
  • the resin (B2) is used as the high hardness resin
  • the polycarbonate resin containing the structural unit of the general formula (3a) as the polycarbonate resin (a1).
  • a monovalent phenol represented by the general formula ( 4 ) (R5 has 8 to 22 carbon atoms) as the terminal terminator.
  • Examples of such a polycarbonate resin include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company) and Iupiron E-2000 (manufactured by Mitsubishi Engineering Plastics).
  • a copolymer (R100, R200, or R100, R200, or) composed of methyl methacrylate constituent unit 6 to 26% by mass, styrene constituent unit 55 to 21% by mass, and maleic anhydride constituent unit 15 to 23% by mass.
  • the resin (B2) of R310; manufactured by Denka) it is preferable to use the Iupizeta T-1380 as the polycarbonate resin (a1).
  • the method for producing the resin (B2) is not particularly limited, and examples thereof include a massive polymerization method and a solution polymerization method.
  • the resin (B3) is a polymer containing the structural unit (c) represented by the general formula (5). At this time, it is preferable that the polymer further contains the structural unit (d) represented by the general formula (6). Further, the resin (B3) may further contain other structural units.
  • the content of the structural unit (c) represented by the general formula (5) is preferably 50 to 100 mol%, preferably 60 to 100 mol%, based on all the structural units of the resin (B3). Is more preferable, and 70 to 100 mol% is particularly preferable.
  • the content of the structural unit (d) represented by the general formula (6) is preferably 0 to 50 mol%, preferably 0 to 40 mol%, based on all the structural units of the resin (B3). Is more preferable, and 0 to 30 mol% is particularly preferable.
  • Examples of the other structural unit in the resin (B3) include a structural unit represented by the following formula (3a).
  • the content of the other constituent units is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the constituent units of the resin (B3). Especially preferable.
  • the total content of the constituent unit (c) and the constituent unit (d) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, based on the total constituent units of the resin (B3). It is preferably 98 to 100 mol%, more preferably 98 to 100 mol%.
  • the weight average molecular weight of the resin (B3) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.
  • the glass transition point of the resin (B3) is preferably 105 to 150 ° C, more preferably 110 to 140 ° C, and particularly preferably 110 to 135 ° C.
  • the resin (B3) examples include Iupiron KH3410UR, KH3520UR, KS3410UR (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and the like.
  • the above-mentioned resin (B3) may be used alone or in combination of two or more.
  • the resin (B3) is used as the high hardness resin
  • the polycarbonate resin containing the structural unit of the general formula (3a) as the polycarbonate resin (a1).
  • a monovalent phenol represented by the general formula ( 4 ) (R5 has 8 to 22 carbon atoms) as the terminal terminator.
  • Examples of such a polycarbonate resin include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company).
  • Iupiron KS3410UR manufactured by Mitsubishi Engineering Plastics
  • Iupizeta T-1380 manufactured by Mitsubishi Gas Chemical Company
  • the resin (B3) is used as the high hardness resin, it is preferable to include a resin other than the resins (B1) to (B6).
  • a resin other than the resins (B1) to (B6) a resin containing the constituent unit (d) without containing the constituent unit (c) is preferable, and a resin consisting only of the constituent unit (d) is more preferable.
  • aromatic polycarbonate resins for example, Iupylon S-2000, Iupylon S-1000, Iupylon E-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • aromatic polycarbonate resins for example, Iupylon S-2000, Iupylon S-1000, Iupylon E-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • the resin (B3) is preferably 45% by mass or more, more preferably 55% by mass, based on the total resin contained in the high hardness resin layer. It is included in the above ratio.
  • the method for producing the resin (B3) is not particularly limited, but the resin (B3) can be produced by the same method as the above-mentioned method for producing the polycarbonate resin (a1) except that bisphenol C is used as the monomer.
  • the resin (B4) is a copolymer containing 5 to 20% by mass of a styrene constituent unit, 60 to 90% by mass of a (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of an N-substituted maleimide constituent unit. be.
  • the resin (B4) may further contain other structural units.
  • the styrene constituent unit in the resin (B4) is not particularly limited, and any known styrene-based monomer can be used.
  • the styrene monomer include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene and the like from the viewpoint of availability.
  • the styrene monomer is preferably styrene from the viewpoint of compatibility.
  • the above-mentioned styrene monomer may be contained alone as a styrene constituent unit, or may be contained in combination of two or more kinds.
  • the content of the styrene constituent unit is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass with respect to the total mass of the resin (B4).
  • the (meth) acrylic acid ester monomer constituting the (meth) acrylic acid ester structural unit in the resin (B4) is not particularly limited, but is acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate. , 2Ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like.
  • the (meth) acrylic acid ester monomer is preferably methyl methacrylate.
  • the above-mentioned (meth) acrylic acid ester monomer may be contained alone as a (meth) acrylic acid ester constituent unit, or may be contained in combination of two or more kinds.
  • the content of the (meth) acrylic acid ester constituent unit is 60 to 90% by mass, preferably 70 to 90% by mass, and preferably 80 to 90% by mass with respect to the total mass of the resin (B4). Is more preferable.
  • the N-substituted maleimide constituent unit in the resin (B4) includes N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, and N.
  • Examples thereof include structural units derived from N-arylmaleimide such as -carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide. Of these, a structural unit derived from N-phenylmaleimide is preferable from the viewpoint of compatibility with the acrylic resin.
  • the structural unit derived from the above-mentioned N-substituted maleimide may be contained alone as the N-substituted maleimide structural unit, or may be contained in combination of two or more.
  • the content of the N-substituted maleimide constituent unit is 5 to 20% by mass, preferably 5 to 15% by mass, and 5 to 10% by mass with respect to the total mass of the resin (B4). Is more preferable.
  • Examples of the other structural unit include a (meth) acrylic acid ester structural unit represented by the general formula (1), an aliphatic vinyl structural unit represented by the general formula (2), and the like.
  • the general formula (1) and the general formula (2) are the same as those of the resin (B1) described above.
  • the content of the other constituent units is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the constituent units of the resin (B4). Especially preferable.
  • the total content of the styrene constituent unit, the (meth) acrylic acid ester constituent unit, and the N-substituted maleimide constituent unit is preferably 90 to 100 mol% with respect to the total constituent unit of the resin (B4). It is more preferably 95 to 100 mol%, and even more preferably 98 to 100 mol%.
  • the weight average molecular weight of the resin (B4) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.
  • the glass transition point of the resin (B4) is preferably 110 to 150 ° C, more preferably 115 to 140 ° C, and particularly preferably 115 to 135 ° C.
  • the resin (B4) examples include Delpet PM120N (manufactured by Asahi Kasei Corporation).
  • the above-mentioned resin (B4) may be used alone or in combination of two or more.
  • the resin (B4) is used as the high hardness resin, it is preferable to use the polycarbonate resin containing the structural unit of the general formula (3a) as the polycarbonate resin (a1). Further, it is particularly preferable to use a monovalent phenol represented by the general formula ( 4 ) (R5 has 8 to 22 carbon atoms) as the terminal terminator.
  • a polycarbonate resin include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company).
  • the resin (B4) Delpet PM-120N composed of 7% styrene constituent unit, 86% (meth) acrylic acid ester constituent unit, and 7% N-substituted maleimide constituent unit is used, and the polycarbonate resin (a1) is used. It is preferable to use Iupizeta T-1380 as the above.
  • the method for producing the resin (B4) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.
  • the resin (B5) is a copolymer containing 50 to 95% by mass of a styrene constituent unit and 5 to 50% by mass of an unsaturated dicarboxylic acid constituent unit. Further, the resin (B5) may further contain other structural units.
  • the styrene constituent unit the styrene-based monomer described in the resin (B4) can be used.
  • these styrene constituent units may be used alone or in combination of two or more.
  • the content of the styrene constituent unit is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and 65 to 87% by mass with respect to the total mass of the resin (B5). Is even more preferable.
  • Examples of the unsaturated dicarboxylic acid anhydride monomer constituting the unsaturated dicarboxylic acid constituent unit include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Of these, maleic anhydride is preferable from the viewpoint of compatibility with the styrene-based monomer.
  • the unsaturated dicarboxylic acid anhydride monomer described above may be used alone or in combination of two or more.
  • the content of the unsaturated dicarboxylic acid constituent unit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 13 to 35% by mass with respect to the total mass of the resin (B5). Is more preferable.
  • Examples of the other structural units include a structural unit derived from the following general formula (1), a structural unit derived from the general formula (2), and the like.
  • R 1 and R 2 are the same as above.
  • R 3 and R 4 are the same as above.
  • the content of the other constituent units is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less, based on all the constituent units of the resin (B5). More preferred.
  • the total content of the styrene constituent unit and the unsaturated dicarboxylic acid constituent unit is preferably 10 to 90 mol%, more preferably 20 to 85 mol%, based on all the constituent units of the resin (B5). , 30-80 mol%, more preferably.
  • the weight average molecular weight of the resin (B5) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.
  • the glass transition point of the resin (B5) is preferably 110 to 150 ° C, more preferably 115 to 140 ° C, and particularly preferably 115 to 137 ° C.
  • resin (B5) examples include XIBOND140 and XIBOND160 (manufactured by Polyscope).
  • the above-mentioned resin (B5) may be used alone or in combination of two or more.
  • the resin (B5) is used as the high hardness resin
  • the polycarbonate resin containing the structural unit of the general formula (3a) is used as the polycarbonate resin (a1).
  • a monovalent phenol represented by the general formula ( 4 ) (R5 has 8 to 22 carbon atoms) is particularly preferable.
  • Examples of such a polycarbonate resin include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company).
  • the method for producing the resin (B5) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.
  • At least one selected from the group consisting of the above-mentioned resins (B1) to (B6) may be contained as an alloy.
  • alloys are not particularly limited, but are two types of resin (B1) alloy, two types of resin (B2) alloy, two types of resin (B3) alloy, and two types of resin (B4). Alloy, alloy of two kinds of resin (B5), alloy of resin (B1) and resin (B2), alloy of resin (B2) and resin (B4), resin (B2) and other high-hardness resin Examples thereof include an alloy, an alloy of a resin (B2) and an acrylic resin, and an alloy of a resin (B5) and an acrylic resin.
  • Examples of the other high-hardness resin include methyl methacrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.
  • acrylic resin examples include polymethyl methacrylate, a copolymer of methyl methacrylate and methyl acrylate, or ethyl acrylate.
  • commercially available products include Acrypet (manufactured by Mitsubishi Chemical Corporation), Sumipex (manufactured by Sumitomo Chemical Corporation), Parapet (manufactured by Kuraray Co., Ltd.) and the like.
  • alloys of resins having a higher glass transition temperature When using two types of resin alloys, it is preferable to use alloys of resins having a higher glass transition temperature.
  • the above alloy may be used alone or in combination of two or more.
  • the alloy manufacturing method is not particularly limited, and examples thereof include a method of melt-kneading at a cylinder temperature of 240 ° C. using a twin-screw extruder having a screw diameter of 26 mm, extruding into strands, and pelletizing with a pelletizer.
  • the high-hardness resin and alloy contained in the high-hardness resin layer may be one type or two or more types, and when two or more types are selected from the resins (B1) to (B5) and alloys, It can be selected from the same or different categories, and may further contain high hardness resins other than the resins (B1) to (B5).
  • the content of the high-hardness resin in the high-hardness resin layer is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 100% by mass with respect to the total mass of the high-hardness resin layer. % Is particularly preferable.
  • the high hardness resin layer may contain a resin other than the high hardness resin.
  • the other resin include methyl methacrylate-styrene copolymer, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and various other resins. Examples include polymers. These other resins may be used alone or in combination of two or more.
  • the content of the other resin is preferably 35% by mass or less, more preferably 25% by mass or less, and particularly preferably 10% by mass or less, based on the total mass of the high hardness resin layer. ..
  • the high hardness resin layer may contain additives and the like. As the additive, those described above can be used.
  • the thickness of the high hardness resin layer is preferably 10 to 250 ⁇ m, more preferably 30 to 200 ⁇ m, and particularly preferably 60 to 150 ⁇ m.
  • the thickness of the high hardness resin layer is 10 ⁇ m or more, the surface hardness is high, which is preferable.
  • the thickness of the high hardness resin layer is 250 ⁇ m or less, the impact resistance is high, which is preferable.
  • Laminating the high-hardness resin layer on the base material layer As described above, a further layer may exist between the base material layer and the high-hardness resin layer, but here, the high-hardness resin layer is placed on the base material layer. The case of laminating the above will be described.
  • the method of laminating the high-hardness resin layer on the base material layer is not particularly limited, and is a method of superimposing the individually formed base material layer and the high-hardness resin layer and heat-pressing both of them; the individually formed base.
  • the coextrusion method is not particularly limited.
  • a high-hardness resin layer is placed on one side of a base material layer with a feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a molding roll to form a desired laminate.
  • a high-hardness resin layer is arranged on one side of the base material layer in the multi-manifold die, extruded into a sheet shape, and then cooled while passing through a molding roll to form a desired laminated body. ..
  • the above method can be used in the same manner when the high hardness resin layer is laminated on a layer other than the base material layer.
  • the total thickness of the base material layer and the high hardness resin layer is preferably 0.5 to 3.5 mm, more preferably 0.5 to 3.0 mm, and even more preferably 1.2 to 3.0 mm.
  • the total thickness is 0.5 mm or more, the rigidity of the sheet can be maintained, which is preferable.
  • the total thickness is 3.5 mm or less, it is preferable because it is possible to prevent the sensitivity of the touch sensor from deteriorating when the touch panel is installed under the sheet.
  • the ratio of the thickness of the base material layer to the total thickness of the base material layer and the high hardness resin layer is preferably 75% to 99%, more preferably 80 to 99%, and particularly preferably 85 to 99%. be. Within the above range, both hardness and impact resistance can be achieved.
  • Hardcoat layer The hardcoat layer is not particularly limited, but is preferably produced by using an acrylic hardcoat. At this time, it is more preferable to treat the hard coat layer with anti-glare treatment.
  • acrylic hard coat means a coating film which formed a crosslinked structure by polymerizing a monomer or oligomer or a prepolymer containing a (meth) acryloyl group as a polymerization group.
  • the composition of the acrylic hard coat preferably contains a (meth) acrylic monomer, a (meth) acrylic oligomer, and a surface modifier.
  • the acrylic hard coat may further contain a photopolymerization initiator.
  • the photopolymerization initiator refers to a photoradical generator.
  • the content of the (meth) acrylic monomer is preferably 2 to 98% by mass with respect to the total mass of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier. It is more preferably to 50% by mass, and even more preferably 20 to 40% by mass.
  • the content of the (meth) acrylic oligomer is preferably 2 to 98% by mass with respect to the total mass of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier. , 50 to 94% by mass, more preferably 60 to 78% by mass.
  • the content of the surface modifier is preferably 0 to 15% by mass with respect to the total mass of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier. It is more preferably to 10% by mass, and even more preferably 2 to 5% by mass.
  • the content of the photopolymerizer is 0. With respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier. It is preferably 001 to 7 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass.
  • the (meth) acrylic monomer can be used as long as the (meth) acryloyl group is present as a functional group in the molecule.
  • Specific examples thereof include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers.
  • Examples of the monofunctional monomer include (meth) acrylic acid and (meth) acrylic acid ester.
  • bifunctional and / or trifunctional or higher (meth) acrylic monomer examples include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate.
  • 1,6-Hexanediol di (meth) acrylate bisphenol A diglycidyl ether di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol diacrylate hydroxypivalate, neopentyl glycol di (meth) acrylate, 1,4-Butanediol diacrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, polyethylene glycol diacrylate, 1,4-butanediol oligo acrylate, neopentyl glycol oligo acrylate , 1,6-hexanediol oligo acrylate, trimethylol propanetri (meth) acrylate, trimethylol propane ethoxytri (meth) acrylate, trimethylol propanepropoxytri (meth) acrylate, pentaerythritol
  • the hard coat layer may contain one type or two or more types of (meth) acrylic monomers.
  • (Meta) Acrylic Oligomer As the (meth) acrylic oligomer, a bifunctional or higher functional urethane (meth) acrylate oligomer (hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer) or a bifunctional or higher polyfunctional polyester (hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer).
  • a bifunctional or higher functional urethane (meth) acrylate oligomer hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer
  • a bifunctional or higher polyfunctional polyester hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer
  • Examples thereof include a polyfunctional polyester (meth) acrylate oligomer (hereinafter, also referred to as a polyfunctional polyester (meth) acrylate oligomer), a bifunctional or higher functional epoxy (meth) acrylate oligomer (hereinafter, also referred to as a polyfunctional epoxy (meth) acrylate oligomer), and the like.
  • a polyfunctional polyester (meth) acrylate oligomer hereinafter, also referred to as a polyfunctional polyester (meth) acrylate oligomer
  • a bifunctional or higher functional epoxy (meth) acrylate oligomer hereinafter, also referred to as a polyfunctional epoxy (meth) acrylate oligomer
  • polyfunctional urethane (meth) acrylate oligomer a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; polyols are poly.
  • examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with isocyanate and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.
  • Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • 2-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimerol propandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Examples include (meth) acrylate.
  • the polyisocyanate used in the urethanization reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates.
  • diisocyanate such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate
  • di or tri polyisocyanate such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, or polyisocyanate obtained by increasing the amount of diisocyanate.
  • polyols used in the urethanization reaction in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are generally used.
  • aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptan, and di.
  • examples thereof include trimethylolpropionic acid, dimethylolbutyrian acid, glycerin, hydrogenated bisphenol A and the like.
  • polyester polyol examples include those obtained by a dehydration condensation reaction between the above-mentioned polyols and a polycarboxylic acid.
  • polycarboxylic acid examples include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrous.
  • polyether polyol examples include polyalkylene glycols, the above-mentioned polyols, or polyoxyalkylene-modified polyols obtained by reacting phenols with alkylene oxides.
  • the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid and a polyol.
  • the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrous.
  • the polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptan, dimethylolpropionic acid, and dimethylol.
  • Examples thereof include butyionic acid, trimethylolpropane, trimethylolpropane, pentaerythritol, and dipentaerythritol.
  • the polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid.
  • the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.
  • the hard coat layer may contain one type or two or more types of (meth) acrylic oligomers.
  • Surface modifiers change the surface performance of hardcourt layers such as leveling agents, antistatic agents, surfactants, water and oil repellents, inorganic particles, and organic particles.
  • leveling agent examples include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, silicon-modified acrylic and the like. ..
  • antistatic agent examples include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, and anionic surfactant.
  • surfactant and the water- and oil-repellent agent examples include fluorine-containing surfactants, lipophilic group-containing oligomers, fluorine-containing groups, hydrophilic groups, lipophilic groups, UV-reactive group-containing oligomers, and other fluorine-containing surfactants.
  • fluorine-containing surfactants examples include activators and water and oil repellents.
  • examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles.
  • organic particles examples include acrylic particles and silicon particles.
  • the hard coat layer may contain one type or two or more types of surface modifiers.
  • Photopolymerization Initiator examples include a monofunctional photopolymerization initiator. Specifically, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocure 2959: manufactured by Merck]; ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone [Darocure 1173: Merck].
  • Acetphenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], 1-hydroxy-cyclohexylphenylketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether started.
  • Agents In addition, halogenated ketones, acylphosphinoxides, acylphosphonates and the like can be exemplified.
  • These photopolymerization initiators may be used alone or in combination of two or more.
  • the method of forming the hard coat layer is not particularly limited, but for example, a hard coat liquid is applied on a layer located under the hard coat layer (for example, a high hardness resin layer) and then photopolymerized.
  • a hard coat liquid is applied on a layer located under the hard coat layer (for example, a high hardness resin layer) and then photopolymerized.
  • the method of applying the hard coat liquid (polymerizable composition) is not particularly limited, and a known method can be used. For example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, handling method and the like can be mentioned. ..
  • a lamp having a light emission distribution with a light wavelength of 420 nm or less is used.
  • Examples thereof include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.
  • high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator, and heat short-wavelength light or reaction compositions that reduce the viscoelastic properties of the obtained polymer by cross-linking. It is preferable because it does not emit a large amount of long-wavelength light that causes evaporation.
  • the irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled for each performance of the target product.
  • the illuminance is preferably in the range of 0.1 to 300 mW / cm 2 .
  • the photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out light irradiation using a method that can eliminate the reaction inhibition due to oxygen.
  • One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen and irradiate the reactive composition with light through the film. Further, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen gas or carbon dioxide gas.
  • the air velocity of the inert gas is preferably 1 m / sec or less as a relative velocity with respect to the laminate coated with the hard coat liquid moving under the atmosphere of the inert gas. It is more preferably 0.1 m / sec or less.
  • the coated surface may be pretreated for the purpose of improving the adhesion of the hard coat layer.
  • Known treatment examples include a sandblast method, a solvent treatment method, a corona discharge treatment method, a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet treatment method, and a primer treatment method using a resin composition. Can be mentioned.
  • the method of anti-glare treatment is not particularly limited, and examples thereof include a method using an anti-glare type.
  • a high-hardness resin layer, a coating film obtained by applying a reactive composition, and an anti-glare type are laminated in this order.
  • a method of photopolymerizing the reactive composition to demold the antiglare type can be mentioned.
  • the photopolymer (hardcoat layer) of the reactive composition has a shape that reflects the rough surface of the antiglare type on the contact surface with the antiglare type.
  • the antiglare type material is not particularly limited as long as it transmits UV light, and glass, a transparent resin, or the like is used.
  • anti-glare treatment examples include a method of adding particles to the reactive composition, a method of treating the surface of the obtained hard coat layer, and the like.
  • the degree of anti-glare treatment of the hard coat layer can be adjusted by controlling the type of anti-glare type used (surface haze, thickness, etc.), the amount of particles to be added, and the like.
  • the hard coat layer may be further modified.
  • any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment can be applied.
  • These treatment methods are not particularly limited, and known methods can be used.
  • a method of applying a reflection-reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint, and the like can be mentioned.
  • the film thickness of the hardcoat layer is preferably 1 to 40 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring the film thickness from the coating film interface to the surface.
  • the surface roughness (Ra) of the hard coat layer is preferably 0.01 ⁇ m or more, more preferably 0.01 to 0.5 ⁇ m, and even more preferably 0.02 to 0.3 ⁇ m.
  • the surface roughness (Ra) of the hard coat layer is 0.01 ⁇ m or more, it is preferable because external light can be scattered by the uneven shape of the surface to prevent deterioration of visibility due to reflection of external light and reflection of an image.
  • the surface roughness (Ra) of the hard coat layer adopts the value obtained by calculating the center line average roughness (Ra) by the method specified in JIS-B-0601-1994.
  • the bending molding method is not particularly limited, but a method in which the resin sheet is heated to soften it and then bent is preferable.
  • the bending molding includes linear bending, R bending, hot press molding and the like.
  • the heating method is not particularly limited, and examples thereof include a pipe heater, a thermal infrared heater, a non-contact double-sided heating sandwich heater, drying in a dryer, and an electric furnace. These heating methods may be used alone or in combination of two or more.
  • the heating region may be a part (partial heating) of the resin sheet or the whole (whole heating).
  • partial heating it is preferable from the viewpoint of being able to bend with a small bending radius (bending R), low cost, and the like.
  • full surface heating it is preferable from the viewpoints that it can be bent and molded into various shapes, that it is less likely to warp, and that it is less likely to crack.
  • the softening temperature varies depending on the resin sheet used, but is preferably a softening point of ⁇ 50 ° C. of the resin constituting the base material layer (the resin having the highest content when two or more resins are contained), and is softened. It is more preferable that the point is ⁇ 30 ° C.
  • the softening temperature is preferably 100 to 150 ° C, more preferably 110 to 140 ° C.
  • the bending method does not have to use a mold, or a mold may be used.
  • the method of bending is preferably a method using a mold.
  • the mold may be a single-sided mold or an uneven (male-female) double-sided mold, but from the viewpoint of obtaining a highly accurate bent-molded product, it may be an uneven (male-female) double-sided mold. preferable.
  • the shape of the mold is not particularly limited and can be appropriately designed according to the shape of the obtained bent molded product.
  • L-type, V-type, U-type, P-type, O-type, Z-type and the like can be mentioned.
  • the material of the mold is not particularly limited, and examples thereof include wood molds; alloy molds such as die steel, aluminum, aluminum alloys, zinc alloys, and bismuth alloys; ceramic molds and the like. These materials may be used alone or in combination of two or more.
  • the heating temperature varies depending on the resin sheet used, but is preferably a softening point of ⁇ 50 ° C. of the resin constituting the base material layer (the resin having the highest content when two or more resins are contained), and is softened. It is more preferable that the point is ⁇ 30 ° C.
  • the heating temperature is preferably 100 to 150 ° C, more preferably 110 to 140 ° C.
  • the heating time varies depending on the heating region, heating temperature, presence / absence of mold, shape of mold, etc., but is preferably 10 seconds to 1 hour, more preferably 1 minute to 30 minutes, and 3 minutes to 15 minutes. Is more preferable.
  • the bent part includes an end having a warp.
  • non-uniform stress compressive stress on the inside of bending, tensile stress on the outside of bending
  • stress due to non-uniform cooling can occur on the resin sheet during bending.
  • the resin sheet has a plurality of layers (for example, a base material layer-a high hardness resin layer-a hard coat layer)
  • stress may occur between the layers because the materials constituting each layer are different. As a result, warpage may occur at the ends of the bent part.
  • warp means an unintended deformation caused by bending molding.
  • the "end portion” means at least a part of an end edge (hereinafter, also referred to as “end edge”) in contact with the bending line (bending center) in the bent molded body.
  • the "end having a warp” means a region of the end having a warp.
  • the "end having a warp” can be understood as the end having a warp.
  • FIG. 3 is a perspective view of a bent molded body obtained by bending into a V shape.
  • the bent molded body 3 is bent and molded into a V shape along the bending line 30.
  • at least a part of the end sides 31 and 32 in contact with the bending line 30 is an "end portion".
  • the region becomes the "end having the warp”.
  • all the end sides 31 are end portions having a warp (ends having a warp).
  • FIG. 4 is a perspective view of a bent molded body obtained by bending and molding into an L shape.
  • the bend-molded body 4 is bent and molded into an L shape along the bending line (bending center) 40.
  • at least a part of the end sides 41 and 42 in contact with the bending line is an "end portion".
  • the region becomes the "end having the warp”.
  • all the end sides 41 are end portions having a warp (ends having a warp).
  • the bent molded product may have warpage at both ends, or may have warpage at only one end.
  • FIG. 5 is a perspective view of a bent-molded body having a V-shaped bend-molded removal region.
  • the bent molded body 5 is bent and molded into a V shape along the bending line 50.
  • the bend-molded body 5 is designed to be larger than the finally manufactured bend-molded product. Specifically, it has removal regions 54 and 55 extending in the direction of the bending line (bending center) 50.
  • the removal areas 54 and 55 are arranged at both ends, and warpage occurs at the end sides 51 and 52 of the removal areas 54 and 55.
  • the resin sheet including the first removing region, the main body region, and the second removing region is bent and molded to form the first removing region and the first removing region. It is preferable that the step is to obtain a bent molded product including an end portion in which at least one of the second removal regions has a warp.
  • the removal step involves removing the warped edges.
  • the removal removes only the warped end when a warp is formed on a part of the end edge, and removes the warped end edge when the warp is formed on all the end edges. Even if a warp is formed on a part of the end edge (a warp is formed on a part of the end edge), not only the end portion having the warp but also the entire end edge is removed. good. Of these, from the viewpoint of productivity, it is preferable that the removing step includes removing the edge having a warp.
  • the removing step preferably includes removing the end portion having no warp, and more preferably includes removing the end portion having no warp.
  • the removal method is not particularly limited, and a known method can be appropriately adopted.
  • a small cutting machine FANUC Robodrill
  • FANUC Robodrill FANUC Robodrill
  • the removal region is not particularly limited, but at least the end portion having a warp is preferably removed, and it is more preferable to remove the end portion having a warp.
  • the bent molded product contains a removal region, it is preferable to remove the removal region.
  • bent molded product manufactured by the above-mentioned manufacturing method.
  • the bent molded product has no warp and is excellent in appearance.
  • Bent molded products are suitably used for automobile interior parts such as instrument covers, home appliances, OA equipment, personal computers, housings of small portable equipment, touch panel type display surfaces such as mobile phone terminals, and the like.
  • Example 1 A resin sheet having a structure of a base material layer-a high hardness resin layer-a hard coat layer was bent and molded.
  • a high hardness resin (B2) (methyl methacrylate constituent unit: 21% by mass, styrene constituent unit: 64% by mass, and maleic anhydride constituent unit: 15% by mass) are used in a single shaft extruder having a shaft diameter of 35 mm.
  • a polycarbonate resin (Iupizeta T-1380; manufactured by Mitsubishi Gas Chemical Company) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge speed of 83.0 kg / h.
  • the extruded high-hardness resin and polycarbonate resin were introduced into a feed block equipped with two types of two-layer distribution pins, and the high-hardness resin and polycarbonate resin were laminated at a temperature of 240 ° C. Further, it is introduced into a T-die having a temperature of 240 ° C., extruded into a sheet, and cooled and stretched from the upstream side with three mirror-finishing rolls having temperatures of 120 ° C., 130 ° C., and 190 ° C. while transferring the mirror surface to achieve high hardness.
  • a laminate of a resin layer and a base material layer was obtained. The draw ratio was 1.3 times.
  • the thickness of the obtained laminate was 2 mm, and the thickness of the high hardness resin layer was 60 ⁇ m near the center.
  • a hard coat layer was formed on the high hardness resin layer side of the laminate (base material layer-high hardness resin layer) obtained above.
  • the material of the hard coat layer is as follows.
  • U6HA 6-functional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 60% by mass
  • 4EG-A PEG200 # diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 35% by mass
  • ⁇ RS-90 Fluorine-containing group, hydrophilic group, lipophilic group, UV-reactive group-containing oligomer (manufactured by DIC Co., Ltd.) 5% by mass with respect to 100 parts by mass of the mixture.
  • -Photopolymerization initiator 1 part by mass of I-184 (manufactured by BASF [compound name: 1-hydroxy-cyclohexylphenyl ketone]).
  • the above material was applied to the high hardness resin layer of the laminated body with a bar coater, and a glass plate having a haze of 10% and a thickness of 2 mm was placed over the layer.
  • a metal halide lamp (20 mW / cm 2 ) was applied from the top of the glass plate for 5 seconds to cure the hard coat, and the hard coat layer was adhered. Then, by peeling off the glass plate, a resin sheet having a structure of a base material layer-a high hardness resin layer-a hard coat layer was produced.
  • the film thickness of the hard coat layer was 6 ⁇ m.
  • the produced resin sheet was cut into a rectangle of 80 mm ⁇ 170 mm and installed between the upper and lower molds made of 50 mmR aluminum.
  • the upper and lower molds were closed with a force of 0.6 MPa to perform thermal bending molding of the resin sheet.
  • the temperature of the upper and lower molds made of aluminum was 124 ° C.
  • the mold closing time was 5 minutes. It should be noted that warpage occurred at both ends of the obtained bent molded product.
  • Polycarbonate resin (Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company, Inc.)) is continuously introduced using a single-layer extruder with a single-screw shaft diameter of 65 mm, and the conditions are a cylinder temperature of 280 ° C. and a discharge rate of 83.0 kg / h. Extruded with.
  • the extruded polycarbonate resin is introduced into a T-die having a temperature of 280 ° C., extruded into a sheet, and cooled and stretched while transferring the mirror surface with three mirror-finishing rolls having temperatures of 120 ° C., 130 ° C., and 190 ° C. from the upstream side.
  • a resin sheet made of a base material layer of a polycarbonate resin was produced.
  • the draw ratio was 1.17 times.
  • the thickness of the obtained resin sheet was 2 mm.
  • a resin sheet (base material layer-high hardness resin) in which a 6 mm thick hard coat layer is laminated on the high hardness resin layer side of a 2 mm thick laminate (base material layer-high hardness resin layer) by the same method as in Example 1. Layer-hard coat layer) was prepared.
  • Bending molding was performed in the same manner as in Example 1 except that the produced resin sheet was cut into a rectangle of 60 mm ⁇ 170 mm. It should be noted that warpage occurred at both ends of the obtained bent molded product.
  • Bending molding was performed in the same manner as in Example 1 except that the produced resin sheet was cut into a rectangle of 60 mm ⁇ 170 mm. It should be noted that warpage occurred at both ends of the obtained bent molded product.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
PCT/JP2021/040578 2020-11-09 2021-11-04 樹脂シートの曲げ成形品の製造方法および曲げ成形品 WO2022097677A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004338277A (ja) * 2003-05-16 2004-12-02 Araco Corp 板状成形体の曲げ加工方法
JP2005177790A (ja) * 2003-12-17 2005-07-07 Nisshin Steel Co Ltd 金属板の曲げ加工方法
JP2009241109A (ja) * 2008-03-31 2009-10-22 Kobe Steel Ltd チャンネル部材の曲げ成形方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004338277A (ja) * 2003-05-16 2004-12-02 Araco Corp 板状成形体の曲げ加工方法
JP2005177790A (ja) * 2003-12-17 2005-07-07 Nisshin Steel Co Ltd 金属板の曲げ加工方法
JP2009241109A (ja) * 2008-03-31 2009-10-22 Kobe Steel Ltd チャンネル部材の曲げ成形方法

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